CN101774814B - Ceramic and carbon nano-fiber composite material and preparation method thereof - Google Patents
Ceramic and carbon nano-fiber composite material and preparation method thereof Download PDFInfo
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- CN101774814B CN101774814B CN2010100313493A CN201010031349A CN101774814B CN 101774814 B CN101774814 B CN 101774814B CN 2010100313493 A CN2010100313493 A CN 2010100313493A CN 201010031349 A CN201010031349 A CN 201010031349A CN 101774814 B CN101774814 B CN 101774814B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 111
- 239000000919 ceramic Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 15
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
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- -1 terepthaloyl moietie Chemical compound 0.000 claims description 9
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- 229910052742 iron Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
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- 239000002994 raw material Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- PFTIVKCRALCOLB-UHFFFAOYSA-N [SiH4].[N] Chemical compound [SiH4].[N] PFTIVKCRALCOLB-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
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- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 238000005245 sintering Methods 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 16
- 238000011065 in-situ storage Methods 0.000 abstract description 7
- 229920006253 high performance fiber Polymers 0.000 abstract description 3
- 239000011226 reinforced ceramic Substances 0.000 abstract description 2
- 239000003863 metallic catalyst Substances 0.000 abstract 2
- 230000000630 rising effect Effects 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 description 26
- 239000011159 matrix material Substances 0.000 description 19
- 239000000835 fiber Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- ADKPKEZZYOUGBZ-UHFFFAOYSA-N [C].[O].[Si] Chemical compound [C].[O].[Si] ADKPKEZZYOUGBZ-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- JGWUKKFNKOUBPW-UHFFFAOYSA-N 2-ethenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 JGWUKKFNKOUBPW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical class N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001709 polysilazane Polymers 0.000 description 2
- 239000012686 silicon precursor Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XTUNVEMVWFXFGV-UHFFFAOYSA-N [C].CCO Chemical compound [C].CCO XTUNVEMVWFXFGV-UHFFFAOYSA-N 0.000 description 1
- FAGDCURWIIDQAA-UHFFFAOYSA-N [C].[O].[Si].[B] Chemical compound [C].[O].[Si].[B] FAGDCURWIIDQAA-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
The invention relates to a ceramic and carbon nano-fiber composite material and a preparation method thereof. The preparation method has a principle of directly growing carbon nano-fiber in a ceramic hole which is formed in a ceramic body in the ceramic forming process to prepare the ceramic and composite material. The specific process comprises the following steps: mixing a metallic catalyst and ceramics; inputting carbonous gas to a system in an intermediate stage of preparing the ceramics by sintering or pyrogenation; directly growing the carbon nano-fiber in the hole by utilizing the metallic catalyst formed in the ceramic hole; and further rising the temperature and sintering or pyrolyzing the ceramics which grows the carbon nano-fiber to prepare the carbon nano-fiber and ceramic composite material. Through the in-situ preparation method, the ceramic composite material with the uniformly-distributed carbon nano-fiber can be prepared. As the growing of the carbon nano-fiber is completed by one step in the process of sintering or pyrolyzing the ceramics, the flow process is simple and controllable, and has the characteristics of low preparation temperature; the composite materials with different shapes and sizes can be prepared; and the flow process can be applied to the preparation of the high-performance fiber reinforced ceramic composite material and in an application field thereof.
Description
Technical field
The present invention relates to a kind of pottery and carbon nano-fiber composite material and preparation method, specifically is that the growth in situ single stage method prepares carbon nanofiber and ceramic composite, belongs to technical field of material.
Background technology
Pottery has advantages such as low density, high firmness, excellent high-temperature performance, is the important materials of hi-techs such as aerospace, the energy and building and civil area.The high performance fiber of fiber composite ceramics material use can be toughness reinforcing with intensified ceramic, stop crackle, improve the mechanical property of pottery, can obtain to conduct electricity simultaneously material with functional performance.Traditional fiber and ceramic composite are normally based on the thomel of micron order diameter and pottery preparation; The method of preparation is that fiber production is become precast body; Through mode and Ceramic Composite such as liquid phase or gas-phase permeations, through oversintering or pyrogenically prepared fiber and ceramic composite.The thomel diameter is big, the surface is that inertia and toughness are lower, and problems such as it and ceramic matrix exist that the interface does not match, heat or structural stress have influenced performances such as the mechanics of matrix material, high temperature resistant, anti-oxidant and heat shock resistance.
Carbon nanofiber is that diameter is nano level carbon fibre material; Comprise solid carbon nanofiber and hollow carbon nano-tube material; It has the vertical ratio of high length, high-specific surface area, HS, high-modulus, H.T. and excellent physics, mechanics and functional performance such as high conductivity, high thermal conductivity; Be ideal material (W.A.Curtin and B.W.Sheldon, " CNT-Reinforced Ceramics and Metals, " the Materials Today that strengthens stupalith; 7,44-49 (2004)).At present, adopting carbon nanofiber to strengthen pottery mainly is that the carbon nanofiber of preparing is joined in the pottery, mixes or dispersion through machinery or liquid phase etc., and then carries out sintering or pyrolysis preparation.Another composite pathway is on ceramic powder particle, to grow carbon nanotube earlier, and then the composite powder sintering is prepared carbon nanotube and ceramic composite (E.Flahaut, A.Peigney; Ch.Laurent; Ch.Marliere, F.Chastel F and A.Rousset, " Carbon Nanotube-Metal-OxideNanocomposites:Microstructure; Electrical Conductivity and Mechanical Properties; " ActaMater, 48,3803-12 (2000)).But these methods exist the problem of general character, and promptly carbon nanofiber is reunited in pottery easily, is difficult to reach evenly compound; Simultaneously, carbon nanofiber is stochastic distribution in matrix, and non-orientation because agglomeration traits is difficult to reach the dispersion of higher volumes.These difficulties are subject matter (X.T.Wang that the restriction composite property improves; N.P.Padture and H.Tanaka; " Contact-Damage-Resistant Ceramic/Single-Wall carbonNanotubes and Ceramic/Graphite Composites; " Nat.Mater.3,539-544 (2004)).On the other hand, adopt these methods because carbon nanofiber is distributed in ceramic grain surface, it stops intergranular sintering in the ceramic post sintering process; Make material be difficult to densification, and the high temperature sintering that adopts or fast plasma sintering because high sintering temperature, the structure of the compound intravital carbon nanofiber of easy damaged; Thereby influence performance of composites (C.Balazsi; Z.Konya, F.Weber, L.P.Biro and P.Arato; " Preparation and Characterization of Carbon NanotubeReinforced Silicon Nitride Composites; " Materials Science and Engineering, 23,1133-37 (2003)).
To above problem, the invention provides carbon nanofiber and ceramic composite of growth in situ in ceramic matrix and preparation method thereof.Direct growth goes out carbon nanofiber to principle in the hole that forms in the ceramic body in order in the process of sintering or pyrolysis preparation pottery, to be utilized in.The principle of Growth of Carbon nanofiber is can on metal catalysts such as iron, cobalt, nickel, form (A.C.Dupuis by the catalytic pyrolysis carbon-containing atmosphere at a certain temperature according to carbon nanofiber; " The Catalyst in the CCVD of CarbonNanotubes:a Review; " Progress in Materials Science; 50,929-61 (2005)).
Concrete grammar is for introducing granules of catalyst in ceramic hole, preparing in sintering or pyrolysis provides carbon source in the ceramic process, under suitable temperature, in the hole of pottery, grow carbon nanofiber.Adopt this method in ceramic matrix, direct growth to go out carbon nanofiber; The carbon nanofiber that grows forms homodisperse in pottery; Growth back further elevated temperature makes ceramic densifying, and the contraction of pottery is combined closely the carbon nanofiber and the pottery of growth in it.Can solve carbon nanofiber with this method and in ceramic matrix, disperse uneven problem, prepare that a step composite growth goes out carbon nanofiber in the ceramic process, prepare the ceramic composite of fine and close carbon nanofiber.Adopt this method, can under lower temperature, just prepare the matrix material of carbon nanofiber and pottery.
Summary of the invention
The object of the present invention is to provide a kind of pottery and carbon nano-fiber composite material and preparation method; Said material is to prepare one step of carbon nanofiber that original position grows in pottery; The preparation method is for growing carbon nanofiber in the nanoporous that in the process of sintering and pyrolysis pottery, in ceramic body, forms; Thereafter sintering and pyrolysis make ceramic densifying under the elevated temperature, therefore adopt present method a step to obtain closely knit shaped ceramic bodies.This growth in situ method goes out owing to carbon nanofiber direct growth in pottery; Do not need processes such as blending in of fibers, functionalization and dispersion, a preparation fiber and matrix material step in sintering or pyrolysis accomplishes; Therefore; It is simple that the present invention has the preparation process, and the advantage that the material formation temperature is lower is fit to scale preparation.Adopt the carbon nano-fiber composite material of this growth in situ method preparation to have homodisperse characteristics, can be used for preparing high performance carbon nano-fiber composite material.Therefore, the present invention is a kind of ideal method of preparation carbon nanofiber and ceramic composite.
Pottery provided by the invention and carbon nano-fiber composite material are to be matrix with the pottery, grow carbon nanofiber in the nanoporous that in the preparation pottery, forms within it, form matrix material through sintering or pyrolysis.
The principle of the present invention's technology is that foundation prepares in the pottery at sintering or pyrolysis, and the development and the densification process of material experience micron and nanoporous utilize the micron, the nanoporous that produce in the ceramic forming process, direct growth carbon nanofiber in these holes.Being implemented in the approach that grows carbon nanofiber in the ceramic hole is in pottery, to sneak into a certain amount of metal catalyst or metallic precursor in advance; In the process of sintering or pyrolysis pottery; Carbonaceous gas is provided in protective atmosphere, is implemented in the space in the pottery and grows carbon nanofiber.
In preparation pottery or ceramic forerunner, add metallic catalyzer, in pottery forms, in system, import carbonaceous gas or liquid, the granules of catalyst that in ceramic hole, forms, the catalytic pyrolysis carbonaceous gas grows carbon nanofiber in the hole.
Described carbon nanofiber refers to that carbon has the carbon material of 1-dimention nano diameter, comprises solid carbon fiber and hollow tubulose thomel etc., and the diameter of carbon nanofiber is 1-500nm.
Described pottery is siliceous pottery, comprises potteries such as SiOC, SiCN, SiC, SiBCN, or contain Fe simultaneously in the middle of them, metallic element such as Ni, Co, Al, Zr, Cu.
Described pottery is the compound of oxide ceramics such as silit, silicon nitride, carbonitride of silicium, silicon oxide carbide pottery and alumina-ceramic, zirconia ceramics.
In described pottery, can add sintering aid, sintered ceramic is used MgO and Y usually
2O
3Deng and composition thereof.
Described ceramic forerunner is siliceous polymkeric substance, one or more the mixing that includes but not limited to ZGK 5, Polycarbosilane, polysilazane, gathers the silicon borine.
Described catalyzer is metal, MOX, metal-salt or their mixing, comprises Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt and oxide compound thereof, metal-salt or their mixing.
The step that the preparation method of a kind of pottery provided by the invention and carbon nano-fiber composite material comprises:
To contain in the silicon precursor that to add the carbon nanofibers grow catalyst mix even, pour the mould cross moulding into, under atmosphere protection, be heated to certain temperature, and feed carbon source for growth and go out carbon nanofiber, make pottery and carbon nano-fiber composite material.
Described carbon source is one or more mixing of hydrocarbon polymer, hydrocarbon, hydrocarbon oxygen compound.
Described atmosphere is non-oxidizing atmosphere, comprises inert atmospheres such as reducing atmospheres such as hydrogen, ammonia and argon gas, helium, nitrogen.
Described catalyzer is metal, MOX, metal-salt or their mixing, comprises Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt and oxide compound thereof, metal-salt or their mixing.The content of described catalyzer in raw material can be 0.1-10wt.%.
Described feeding carbon source temperature is 500-1400 ℃.
A kind of pottery provided by the invention and carbon nano-fiber composite material are to be raw material with siliceous ceramic forerunner and carbon source; Contain and add the carbon nanofibers grow catalyzer in the silicon precursor; Cross moulding in mould is heated to 600-1200 ℃ then under argon gas, hydrogen, nitrogen or the protection of their mixed atmosphere, feed carbon source; Grow carbon nanofiber, make pottery and carbon nano-fiber composite material.Siliceous ceramic forerunner: ZGK 5, Polycarbosilane, gather nitrogen silane, gather Si-B-C-N, gather silicon boron oxygen carbon one or more mixing (for example: the mixing of hydrogen-containing siloxane, vinyl cyclotetrasiloxane and YSR 3286).Carbon source: the mixing of one or more of hydrocarbon polymer, hydrocarbon, hydrocarbon oxygen compound can be selected from one or more mixing of ethanol, terepthaloyl moietie, acetone, YLENE, normal hexane, methane, acetylene or ethene.The Growth of Carbon nano-fiber catalyst: the mixing of metal, MOX, metal-salt or several kinds comprises the mixing of for example Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt and oxide compound thereof, metal-salt or several kinds.Preferred iron(ic)chloride or ferrocene.
The present invention grows carbon nanofiber in a step in the process of preparation pottery in pottery, to the pottery of the carbon nanofiber of growth further under the elevated temperature sintering make its densification with pyrolysis, therefore obtain the shaped ceramic bodies of densification.This growth in situ method does not need processes such as fiber dispersion, functionalization and mixing owing to direct growth in pottery goes out fiber; Because preparation is step completion in sintering or pyrolysis; Can under lower temperature, prepare carbon nanofiber and ceramic composite, therefore, it is simple that technology of the present invention has a preparation process; Advantages such as preparation cost is low are fit to scale preparation.Simultaneously; Adopt the carbon nano-fiber composite material of this growth in situ method preparation to have homodisperse characteristics; And can prepare three-dimensional block matrix material; Can develop into and have high performance carbon nano-fiber composite material, can be applicable to prepare high-performance fiber and strengthen ceramic composite and Application Areas thereof.
Description of drawings
SiOC pottery and carbon nano-fiber composite material profile scanning Electronic Speculum figure that Fig. 1 makes for the embodiment of the invention 1.
SiOC pottery and carbon nano-fiber composite material sem photograph that Fig. 2 makes for the embodiment of the invention 1.
SiOC pottery and carbon nano-fiber composite material transmission electron microscope picture that Fig. 3 makes for the embodiment of the invention 1.
SiOC pottery and carbon nano-fiber composite material transmission electron microscope picture that Fig. 4 makes for the embodiment of the invention 1.
SiOC pottery and carbon nano-fiber composite material profile scanning Electronic Speculum figure that Fig. 5 makes for the embodiment of the invention 4.
SiOC pottery and carbon nano-fiber composite material profile scanning Electronic Speculum figure that Fig. 6 makes for the embodiment of the invention 7.
SiOC pottery and carbon nano-fiber composite material profile scanning Electronic Speculum figure that Fig. 7 makes for the embodiment of the invention 8.
SiCN pottery and carbon nano-fiber composite material profile scanning Electronic Speculum figure that Fig. 8 makes for the embodiment of the invention 14.
Embodiment
Embodiment 1: 2g hydrogen-containing siloxane, 1g vinyl cyclotetrasiloxane and 1.5g YSR 3286 are mixed, add 45mg FeCl
3, add the 45mg platinum catalyst, pour mould into; 80 ℃ of heating 4h obtain formed body, and formed body is put into stove; Be warming up to 850 ℃ in the argon gas, feed 15ml/h ethanol Growth of Carbon pipe 30min, temperature is risen to 1000 ℃ of pyrolysis 1h prepare silicon-oxygen-carbon ceramic and carbon nano-fiber composite material body.Pound disconnected matrix material with blunt, vertical many carbon nanofibers (accompanying drawing 1) that from ceramic matrix, detaches are arranged with the fresh section of scanning electron microscopic observation.The carbon nanofiber (accompanying drawing 2) of vertical many bridgings is arranged in the new crack that forms, another zone of scanning electron microscopic observation composite bodies, further specify and in ceramic body, grow carbon nanofiber.Observed carbon nanofiber diameter 5-100nm.With the broken sample of transmission electron microscope observing, to observe carbon nanofiber and have hollow structure, two sidewalls are the graphite linings that number equates, prove that the carbon nanofiber that forms is carbon nanotube structure (accompanying drawing 3).Observe carbon nanofiber (accompanying drawing 4) simultaneously, diameter 100-500nm with solid construction.
Embodiment 2: adopt the identical method of instance 1, with the FeCl that adds in the ceramic forerunner
3The amount of catalyzer is reduced to 4.5mg, and pyrolysis obtains SiOC pottery and carbon nano-fiber composite material.
Embodiment 3: adopt the identical method of instance 1, with the FeCl that adds in the ceramic forerunner
3The amount of catalyzer is reduced to 450mg, and pyrolysis obtains SiOC pottery and carbon nano-fiber composite material.
Embodiment 4: adopt the identical method of instance 1, will feed the carbon source temperature and be upgraded to 1000 ℃, obtain SiOC pottery and carbon nano-fiber composite material after Growth of Carbon nanofiber and the pyrolysis.Scanning electron microscopic observation matrix material section has the carbon nanofiber of extracting from matrix, and like accompanying drawing 5, Fibre diameter is 20-50nm.
Embodiment 5: adopts the identical method of instance 1, changes the amount of silicon-oxygen-carbon ceramic presoma, and 1.5g hydrogen-containing siloxane/1.5g vinyl cyclotetrasiloxane/1.5g YSR 3286, pyrolysis obtains SiOC pottery and carbon nano-fiber composite material.
Embodiment 6: adopts the identical method of instance 1, changes the amount of silicon-oxygen-carbon ceramic presoma, and 2g hydrogen-containing siloxane/1g vinyl cyclotetrasiloxane, pyrolysis obtains SiOC pottery and carbon nano-fiber composite material.
Embodiment 7: adopt the identical method of instance 1, protective atmosphere is a nitrogen, and pyrolysis obtains SiOC silicon-oxygen-carbon ceramic and carbon nano-fiber composite material.Scanning electron microscopic observation matrix material section has carbon nanofiber, like accompanying drawing 6.
Embodiment 8: adopt the identical method of instance 6, carbon source kind is an ethene, and pyrolysis obtains SiOC silicon-oxygen-carbon ceramic and carbon nano-fiber composite material.Scanning electron microscopic observation matrix material section has carbon nanofiber, like accompanying drawing 7.
Embodiment 9: adopt the identical method of instance 7, change the feeding amount and the feeding time of carbon source, ethene feeds with the speed of 30ml/h, and 15min stops, and pyrolysis obtains SiOC pottery and carbon nano-fiber composite material.
Embodiment 10: adopt the identical method of instance 1, protective atmosphere is a hydrogen, and pyrolysis obtains SiOC pottery and carbon nano-fiber composite material.
Embodiment 11: adopt the identical method of instance 1, protective atmosphere is argon gas and hydrogen, and pyrolysis obtains SiOC pottery and carbon nano-fiber composite material.
Embodiment 12: adopt the identical method of instance 1, it is 600 ℃ that carbon source feeds temperature, and pyrolysis obtains SiOC pottery and carbon nano-fiber composite material.
Embodiment 13: adopt the identical method of instance 1, change the ceramic forerunner kind, the 10g Polycarbosilane is replaced the ZGK 5 presoma, pyrolysis obtains SiC pottery and carbon nano-fiber composite material.
Embodiment 14: adopt the identical method of instance 1, change the ceramic forerunner kind, the 5g polysilazane is replaced the ZGK 5 presoma, pyrolysis obtains SiCN pottery and carbon nano-fiber composite material.Scanning electron microscopic observation matrix material section has carbon nanofiber, and fiber is evenly distributed in matrix, like accompanying drawing 8.
Embodiment 15: adopt the identical method of instance 1, change catalyzer into the 0.045g ferrocene, pyrolysis obtains pottery and carbon nano-fiber composite material.
Embodiment 16: ferrocene sneaked into in silit, silicon nitride and the alumina powder, and dry-pressing formed, put into stove and heat, to 850 ℃, feed the ethanol carbon source, prepare carbon nanofiber and ceramic composite.
Claims (3)
1. the preparation method of pottery and carbon nano-fiber composite material is characterized in that the step that comprises:
1) adding carbon nanofibers grow catalyst mix in the siliceous ceramic forerunner is even, pour the mould cross moulding into, heating under atmosphere protection feeds carbon source for growth and goes out carbon nanofiber, makes pottery and carbon nano-fiber composite material;
Described siliceous ceramic forerunner is: ZGK 5, Polycarbosilane, gather one or more the mixing in the nitrogen silane;
Described carbon source is selected from: the mixing of one or more of ethanol, terepthaloyl moietie, acetone, YLENE, normal hexane, methane, acetylene or ethene;
Described atmosphere is hydrogen, ammonia, argon gas, helium, nitrogen;
Described carbon nanofibers grow catalyzer is: iron(ic)chloride or ferrocene; The content of described catalyzer in raw material is 0.1-10wt.%;
Described feeding carbon source temperature is 500-1400 ℃.
2. the preparation method of pottery and carbon nano-fiber composite material; It is characterized in that the step that comprises: with siliceous ceramic forerunner and carbon source is raw material, adds carbon nanofibers grow catalyzer, cross moulding in mould in the siliceous ceramic forerunner; Under argon gas, hydrogen, nitrogen or the protection of their mixed atmosphere, be heated to 600-1200 ℃ then; Feed carbon source, grow carbon nanofiber, make pottery and carbon nano-fiber composite material;
Described siliceous ceramic forerunner is: ZGK 5, Polycarbosilane, gather one or more the mixing in the nitrogen silane; Carbon source is selected from: the mixing of one or more of ethanol, terepthaloyl moietie, acetone, YLENE, normal hexane, methane, acetylene or ethene; Described carbon nanofibers grow catalyzer is iron(ic)chloride or ferrocene.
3. according to claim 1 or 2 described methods, it is characterized in that described carbon nanofiber is meant the carbon nanofiber material with nanometer grade diameter with one-dimentional structure of carbon: solid carbon nanofiber and hollow tubulose carbon nanofiber; The diameter of carbon nanofiber is 1-500nm.
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| CN102557637A (en) * | 2011-12-14 | 2012-07-11 | 天津大学 | Silicon boron carbon nitrogen-based composite material and preparation method thereof |
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| CN106565263B (en) * | 2016-11-05 | 2019-07-30 | 天津大学 | A kind of preparation method of carbon nanotube/silicon carbide heat-conductive composite material |
| CN108863434A (en) * | 2017-05-09 | 2018-11-23 | 天津大学 | A kind of high-content carbon nanotube enhancing PRECURSOR-DERIVED CERAMICS composite material and preparation method |
| CN109133958B (en) * | 2018-08-27 | 2021-01-01 | 河南海格尔高温材料有限公司 | In-situ oriented non-oxide reinforced silicon carbide brick and preparation method thereof |
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| CN110483101B (en) * | 2019-08-14 | 2021-10-22 | 中国科学院合肥物质科学研究院 | Preparation method of carbon nanofiber film without metal catalyst |
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