CN102330328A - Three-dimensional fiber/carbon nano tube multistage reinforcement and preparation method thereof - Google Patents
Three-dimensional fiber/carbon nano tube multistage reinforcement and preparation method thereof Download PDFInfo
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- CN102330328A CN102330328A CN201110158123A CN201110158123A CN102330328A CN 102330328 A CN102330328 A CN 102330328A CN 201110158123 A CN201110158123 A CN 201110158123A CN 201110158123 A CN201110158123 A CN 201110158123A CN 102330328 A CN102330328 A CN 102330328A
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Abstract
The invention provides a three-dimensional fiber/carbon nano tube multistage reinforcement. Carbon nano tubes (CNTs) as a nano wild phase grow in a three-dimensional fiber prefabricated member by using a chemical vapor infiltration (CVI) process to obtain the multistage reinforcement. The invention also provides a preparation method of the multistage reinforcement.
Description
Technical field
The present invention relates to a kind of composite and preparation method thereof, relate to a kind of multistage enhancing system is equipped with and CNT is evenly grown technology and method particularly in the three-dimensional preformed body.
Background technology
As strengthening body, the performance that enhancing and the toughening effect through fiber makes material is enhanced traditional composite based on the fiber of micro-meter scale.Like the introducing of FRCMC through fibre reinforcement, destructive process shows as non-brittle characteristic, thereby makes reliability of material obtain significantly improving.
CNT (CNTs) was found by Japanese scholar Iijima that its excellent mechanics, calorifics and electric property caused global research boom in 1991.CNT is curled by the latticed SP2 hydridization of hexagon carbon atom and forms, can see to make the hollow cylinder that graphite flake curls into, and the about 1nm of diameter, length can reach Centimeter Level even longer.Geometry that it is peculiar and electronic structure make it integrate numerous advantages: Young's modulus reaches as high as 1TPa and tensile strength＞100GPa, and thermal conductivity reaches as high as 6000W/mK etc.Above-mentioned superior performance has determined that CNTs is the ultimate enhancing body of composite, comes reinforced composite to become present international research focus CNTs.Present main research mainly is the performance that improves material through the mode of in material, directly introducing CNTs.Yet because CNTs has very large specific area, its surface energy is very high, thereby so CNTs be easy to take place to reunite cause in material, obtaining evenly dispersion, can't give full play to the excellent properties of nanometer wild phase.Be difficult to evenly disperseed owing to it simultaneously, thereby make the amount of introducing the nanometer wild phase in the material very little.For the scattering problem that solves CNTs be difficult to be added in a large number in the composite, effective ways are that CNTs is coated on the carbon fiber or is filled in the space between fibre bundle.2002, (E.T.Thostenson, J.Appl.Phys. such as Thostenson; Vol.91; No.9,1 May 2002) at first the method for successful use chemical vapor deposition (CVD) has deposited CNTs on carbon fiber surface, and a large amount of subsequently detailed researchs are carried out gradually.The chemical vapor deposition growth CNT mainly concentrates on carbon fiber one dimension (Hui Qian on carbon fiber substrates at present; J.Mater.Chem.; 2010,20,4751-4762) or two-dimentional cloth (Qiao-Juan Gong; Composites Science and Technology 67 (2007) 2986-2989) on, evenly carbon nano-tube does not still have relevant report in the three-dimensional fiber knitted body.
Different with one dimension and two-dimensional fiber enhancing body, the three-dimensional fiber precast body therefore at the depth growth mechanism of growth course important consideration CNTs wild phase, is implemented in the inner growth of three-dimensional fiber precast body owing to have certain thickness.Utilize the technology of present chemical vapour deposition (CVD) in the three-dimensional fiber precast body, to grow in the process of CNTs, CNTs can only be grown in the precast body surface usually, and precast body inner generate be mainly cracking carbon rather than CNTs.Therefore studying the technology and the method that are suitable for even growth CNTs nanometer wild phase in the three-dimensional fiber precast body is a difficult problem of CNTs growth.The breakthrough of this difficult problem is to realizing that multistage fortifying fibre strengthens the practical applications of body in multistage reinforced composite and has very important significance.
In sum, this area lacks multistage enhancing body of a kind of three-dimensional fiber CNT and preparation method thereof.
Summary of the invention
The objective of the invention is to obtain the multistage enhancing body of a kind of three-dimensional fiber CNT.
Second purpose of the present invention is to obtain the preparation method of the multistage enhancing body of a kind of three-dimensional fiber CNT.
First aspect of the present invention provides a kind of three-dimensional fiber/CNT multistage enhancing body, in the three-dimensional fiber precast body, grows as the CNT (CNTs) of nanometer wild phase through chemical vapor infiltration (CVI) technology, obtains said multistage enhancing body.
In a specific embodiment of the present invention, said three-dimensional fiber precast body is selected from three-dimensional four-way precast body, three-dimensional five and sews up precast body, the three-dimensional precast body of 2.5D, three-dimensional acupuncture precast body, three-dimensional puncture precast body, three-dimensional orthogonal precast body or its combination to precast body, two dimension
In a specific embodiment of the present invention, in the said three-dimensional fiber precast body, the fiber that is adopted is selected from carbon fiber, silicon carbide fibre, BN fiber, ceramic fibre or its combination.
In a specific embodiment of the present invention, in the said three-dimensional fiber precast body, fiber surface deposits boundary layer, and said boundary layer comprises PyC interface, SiC interface, BN interface, Si
3N
4Interface, ZrC interface, ZrB
2Interface, HfC interface, HfB
2Interface, TaC interface, TiC interface and the compound interface of forming by above-mentioned interface.
In a specific embodiment of the present invention, the concrete steps of said growing method are following:
The three-dimensional fiber knitted body soaks in the complex catalyst precursor liquid solution and is dry; Dried knitted body is carried out high-temperature heat treatment and under reducing atmosphere, reduces, make the catalyst of load be converted into metal nanoparticle, obtain said three-dimensional fiber precast body;
Adopt chemical vapor infiltration technology carbon nano-tube (CNTs) in said three-dimensional fiber precast body, obtain said multistage enhancing body.
In a preference, said three-dimensional fiber knitted body carries out preliminary treatment, and said preliminary treatment comprises one or more combinations in drying, cleaning, pickling, unsticking, the deposition interface layer.
In a preference, the immersion way that is adopted comprises common immersion, vacuum impregnation, pressure impregnation.
In a preference, heat treated environment can be vacuum, protective atmosphere or air atmosphere.
In a preference, reducing atmosphere comprises H
2The mixed atmosphere of atmosphere, CO atmosphere or above-mentioned gas and other inert gases.
In a specific embodiment of the present invention, the catalyst precursor that is adopted comprises the salt and the multiple combination thereof of iron content, cobalt, nickel.
In a specific embodiment of the present invention, the concentration of the complex catalyst precursor liquid solution that is adopted is the saturated solution of 0.01mol/L to catalyst precursor.
In a specific embodiment of the present invention, heat treated temperature is 200-1400 ℃, preferred 650-1000 ℃.
In a specific embodiment of the present invention, reduction reaction temperature is 500-1400 ℃, preferred 500-1000 ℃.
In a specific embodiment of the present invention, the depositing temperature of said chemical vapor infiltration technology is 500-1400 ℃, preferred 600-1000 ℃.
In a specific embodiment of the present invention, the sedimentation time of said chemical vapor infiltration technology is 5min-10h, preferred 0.5h-3h.
In a specific embodiment of the present invention, the carbon source that is adopted during carbon nano-tube is a hydrocarbon, optimization methane, ethene, acetylene or its combination.
In a specific embodiment of the present invention, the deposition region gas hold-up time of said chemical vapor infiltration technology is 0.001s/cm-1s/cm, preferred 0.01s/cm-0.3s/cm.
In a specific embodiment of the present invention, the deposition pressure of said chemical vapor infiltration technology is 0.1KPa-50KPa, preferred 0.5-20KPa.
In a specific embodiment of the present invention, introduce other metals or the inert component that stops catalyst at high temperature to be reunited in the catalyst of employing simultaneously.
In a specific embodiment of the present invention, feed portion C O or H simultaneously in the said chemical vapor infiltration technical process
2As reducing gas, to avoid catalyst oxidation or poisoning; Or feed other inert gases simultaneously as diluent gas in the said chemical vapor infiltration technical process.
Second aspect of the present invention provides the preparation method of described multistage enhancing body, and said method is in the three-dimensional fiber precast body, to grow as the CNT (CNTs) of nanometer wild phase through chemical vapor infiltration (CVI) technology, obtains said multistage enhancing body.
In a specific embodiment of the present invention, said three-dimensional fiber precast body is selected from three-dimensional four-way precast body, three-dimensional five and sews up precast body, the three-dimensional precast body of 2.5D, three-dimensional acupuncture precast body, three-dimensional puncture precast body, three-dimensional orthogonal precast body or its combination to precast body, two dimension
In a specific embodiment of the present invention, in the said three-dimensional fiber precast body, the fiber that is adopted is selected from carbon fiber, silicon carbide fibre, BN fiber, ceramic fibre or its combination.
In a specific embodiment of the present invention, in the said three-dimensional fiber precast body, the boundary layer of fiber surface deposition comprises PyC interface, SiC interface, BN interface, Si
3N
4Interface, ZrC interface, ZrB
2Interface, HfC interface, HfB
2Interface, TaC interface, TiC interface and the compound interface of forming by above-mentioned interface.
In a specific embodiment of the present invention, make by following method:
The three-dimensional fiber knitted body soaks in the complex catalyst precursor liquid solution and is dry; Dried knitted body is carried out high-temperature heat treatment and under reducing atmosphere, reduces, make the catalyst of load be converted into metal nanoparticle, obtain said three-dimensional fiber precast body;
Adopt chemical vapor infiltration technology carbon nano-tube (CNTs) in said three-dimensional fiber precast body, obtain said multistage enhancing body.
In a preference, said three-dimensional fiber knitted body carries out preliminary treatment, and said preliminary treatment comprises one or more combinations in drying, cleaning, pickling, unsticking, the deposition interface layer.
In a preference, the immersion way that is adopted comprises common immersion, vacuum impregnation, pressure impregnation.
In a preference, heat treated environment can be vacuum, protective atmosphere or air atmosphere.
In a preference, reducing atmosphere comprises H
2The mixed atmosphere of atmosphere, CO atmosphere or above-mentioned gas and other inert gases.
In a specific embodiment of the present invention, the catalyst precursor that is adopted comprises the salt and the multiple combination thereof of iron content, cobalt, nickel.
In a specific embodiment of the present invention, the concentration of the complex catalyst precursor liquid solution that is adopted is the saturated solution of 0.01mol/L to catalyst precursor.
In a specific embodiment of the present invention, heat treated temperature is 200-1400 ℃, preferred 650-1000 ℃.
In a specific embodiment of the present invention, reduction reaction temperature is 500-1400 ℃, preferred 500-1000 ℃.
In a specific embodiment of the present invention, the depositing temperature of said chemical vapor infiltration technology is 500-1400 ℃, preferred 600-1000 ℃.
In a specific embodiment of the present invention, the sedimentation time of said chemical vapor infiltration technology is 5min-10h, preferred 0.5h-3h.
In a specific embodiment of the present invention, the carbon source that is adopted during carbon nano-tube is a hydrocarbon, optimization methane, ethene, acetylene or its combination.
In a specific embodiment of the present invention, the deposition region gas hold-up time of said chemical vapor infiltration technology is 0.001s/cm-1s/cm, preferred 0.01s/cm-0.3s/cm.
In a specific embodiment of the present invention, the deposition pressure of said chemical vapor infiltration technology is 0.1KPa-50KPa, preferred 0.5-20KPa.
In a specific embodiment of the present invention, introduce other metals or the inert component that stops catalyst at high temperature to be reunited in the catalyst of employing simultaneously.
In a specific embodiment of the present invention, feed portion C O or H simultaneously in the said chemical vapor infiltration technical process
2As reducing gas, to avoid catalyst oxidation or poisoning; Or feed other inert gases simultaneously as diluent gas in the said chemical vapor infiltration technical process.
Description of drawings
Fig. 1: the preparation technology of the heterogeneous enhancing body of three-dimensional fiber/CNT
Fig. 2: the SEM photo of three-dimensional fiber knitted body inner carbon nanotube.
The specific embodiment
The invention discloses multistage enhancing body of a kind of three-dimensional fiber/CNT and preparation method thereof.Realize the preparation of three-dimensional multistage enhancing body through chemical vapor infiltration (CVI) technology carbon nano-tube (CNTs) in the three-dimensional fiber precast body as the nanometer wild phase.Accomplished the present invention on this basis.
Below detail to various aspects of the present invention:
Multistage enhancing body of three-dimensional fiber/CNT and preparation method thereof
Multistage enhancing body of the present invention is after three-dimensional fiber enhancing body is carried out preliminary treatment; In CVI equipment, feed carbon source as process gas; The carbon source pyrolysis product is under catalyst action, and the fiber surface original position evenly generates CNTs in the three-dimensional preformed body, prepares multistage fortifying fibre and strengthens body.
In a specific embodiment of the present invention, the concrete steps of said growing method are following:
The three-dimensional fiber knitted body soaks in the complex catalyst precursor liquid solution and is dry; Dried knitted body is carried out high-temperature heat treatment and under reducing atmosphere, reduces, make the catalyst of load be converted into metal nanoparticle, obtain said three-dimensional fiber precast body;
Adopt chemical vapor infiltration technology carbon nano-tube (CNTs) in said three-dimensional fiber precast body, obtain said multistage enhancing body.
Said three-dimensional fiber knitted body can commercially available acquisition or those skilled in the art through the routine techniques preparation.
In a specific embodiment of the present invention, said three-dimensional fiber precast body is selected from three-dimensional four-way precast body, three-dimensional five and sews up precast body, the three-dimensional precast body of 2.5D, three-dimensional acupuncture precast body, three-dimensional puncture precast body, three-dimensional orthogonal precast body or its combination to precast body, two dimension
In a specific embodiment of the present invention, in the said three-dimensional fiber precast body, the fiber that is adopted is selected from carbon fiber, silicon carbide fibre, BN fiber, ceramic fibre or its combination.
In a specific embodiment of the present invention, in the said three-dimensional fiber precast body, fiber surface deposits boundary layer, and said boundary layer comprises PyC interface, SiC interface, BN interface, Si
3N
4Interface, ZrC interface, ZrB
2Interface, HfC interface, HfB
2Interface, TaC interface, TiC interface and the compound interface of forming by above-mentioned interface.
Said boundary layer can deposit according to the interface deposition technique of routine.
In a preference, said three-dimensional fiber knitted body carries out preliminary treatment, and said preliminary treatment comprises one or more combinations in drying, cleaning, pickling, unsticking, the deposition interface layer.
In a preference, the immersion way that is adopted comprises common immersion, vacuum impregnation, pressure impregnation.
In a preference, heat treated environment can be vacuum, protective atmosphere or air atmosphere.
In a preference, reducing atmosphere comprises H
2The mixed atmosphere of atmosphere, CO atmosphere or above-mentioned gas and other inert gases.
In a specific embodiment of the present invention, the catalyst precursor that is adopted comprises the salt and the multiple combination thereof of iron content, cobalt, nickel.
Said salt comprises the various water solubles of said metal or the salt of organic solvent.
In a specific embodiment of the present invention, the concentration of the complex catalyst precursor liquid solution that is adopted is the saturated solution of 0.01mol/L to catalyst precursor.
In a specific embodiment of the present invention, heat treated temperature is 200-1400 ℃, preferred 650-1000 ℃.
In a specific embodiment of the present invention, reduction reaction temperature is 500-1400 ℃, preferred 500-1000 ℃.
In a specific embodiment of the present invention, the depositing temperature of said chemical vapor infiltration technology is 500-1400 ℃, preferred 600-1000 ℃.
In a specific embodiment of the present invention, the sedimentation time of said chemical vapor infiltration technology is 5min-10h, preferred 0.5h-3h.
In a specific embodiment of the present invention, the carbon source that is adopted during carbon nano-tube is a hydrocarbon, optimization methane, ethene, acetylene or its combination.
In a specific embodiment of the present invention, the deposition region gas hold-up time of said chemical vapor infiltration technology is 0.001s/cm-1s/cm, preferred 0.01s/cm-0.3s/cm.
In a specific embodiment of the present invention, the deposition pressure of said chemical vapor infiltration technology is 0.1KPa-50KPa, preferred 0.5-20KPa.
In a specific embodiment of the present invention, introduce other metals or the inert component that stops catalyst at high temperature to be reunited in the catalyst of employing simultaneously.
Said other metals or inert component are known to those skilled in the art.
In a specific embodiment of the present invention, feed portion C O or H simultaneously in the said chemical vapor infiltration technical process
2As reducing gas, to avoid catalyst oxidation or poisoning; Or feed other inert gases simultaneously as diluent gas in the said chemical vapor infiltration technical process.
The feeding amount of said gas is not specifically limited, as long as reach required purpose.
For realizing the even growth of CNTs nanometer wild phase in the three-dimensional fiber precast body, the specific embodiment of the inventive method comprises: (1) will carry out pretreated three-dimensional fiber knitted body and in certain density complex catalyst precursor liquid solution, soak also dry.(2) dried precast body is carried out high-temperature heat treatment and under reducing atmosphere, reduce, make the catalyst of load be converted into metal nanoparticle.(3) adopt CVI technology to have carbon nano-tube (CNTs) in the three-dimensional preformed body of catalyst to realize the preparation of multistage enhancing three-dimensional preformed body in load.Utilize this technology, pure, high coverage rate, the CNT that does not contain cracking carbon can evenly grow in inside and outside the three-dimensional fiber knitted body, have prepared the three-dimensional multistage enhancing body that fibre reinforcement and even carbon nanotube distribute.
The present invention adopts following technical scheme best:
(1) will carry out pretreated three-dimensional fiber knitted body soaks also dry in certain density complex catalyst precursor liquid solution.
(2) dried precast body is carried out high-temperature heat treatment and under reducing atmosphere, reduce, make the catalyst of load be converted into metal nanoparticle.
(3) adopt CVI technology to have carbon nano-tube (CNTs) in the three-dimensional preformed body of catalyst to realize the preparation of multistage enhancing three-dimensional preformed body in load.
Utilize this technology, the CNT that pure high coverage rate does not contain cracking carbon can evenly grow in inside and outside the three-dimensional fiber knitted body, prepares the three-dimensional multistage enhancing body that fibre reinforcement and even carbon nanotube distribute.
Wherein, the fiber that is adopted comprises carbon fiber, silicon carbide fibre, BN fiber and boron fibre and other ceramic fibres; Three-dimensional fiber strengthens body and comprises that three-dimensional four-way precast body, three-dimensional five is to precast body, two dimension stitching precast body, the three-dimensional precast body of 2.5D, three-dimensional acupuncture precast body, three-dimensional puncture precast body, three-dimensional orthogonal precast body; The fibre reinforcement preliminary treatment comprises one or more combinations in drying, cleaning, pickling, unsticking, the deposition interface layer; The catalyst precursor that is adopted comprises the salt and the multiple combination thereof of iron content, cobalt, nickel; The concentration of complex catalyst precursor liquid solution is the saturated solution of 0.01mol/L to catalyst precursor; The immersion way that is adopted comprises common immersion, vacuum impregnation, pressure impregnation; Heat treatment environment can be vacuum, protective atmosphere or air atmosphere; Heat treated temperature is 200-1400 ℃, preferred 650-1000 ℃; Reducing atmosphere comprises the mixed atmosphere of H2 atmosphere, CO atmosphere or above-mentioned gas and other inert gases; The temperature of reduction reaction is 500-1400 ℃, preferred 500-1000 ℃; The CVI depositing temperature is 500-1400 ℃, preferred 600-1000 ℃; The CVI sedimentation time is 5min-10h, preferred 0.5h-3h; The carbon source that is adopted is a hydrocarbon, optimization methane, ethene, acetylene; Gas is 0.001s/cm-1s/cm in the holdup time of deposition region, preferred 0.01s/cm-0.3s/cm; The CVI deposition pressure is 0.1KPa-50KPa, preferred 0.5-20KPa; The boundary layer of fiber surface deposition comprises PyC interface, SiC interface, BN interface, Si
3N
4Interface, ZrC interface, ZrB
2Interface, HfC interface, HfB
2Interface, TaC interface, TiC interface and the compound interface of forming by above-mentioned interface; Can introduce other metals of part or inert component in the catalyst that adopts simultaneously stops catalyst at high temperature to be reunited; Can feed portion C O or H simultaneously in the CVI process
2As reducing gas, avoid catalyst oxidation or poisoning or feed other inert gases of part as diluent gas.
Specify like nothing, various raw materials of the present invention all can obtain through commercially available; Or prepare according to the conventional method of this area.Only if definition or explanation are arranged in addition, all specialties used herein are identical with the meaning that scientific words and those skilled in the art are familiar with.Any in addition with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.
Other aspects of the present invention are because the disclosure of this paper is conspicuous to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all ratio is flow-rate ratio (volume ratio).
Only if definition or explanation are arranged in addition, all specialties used herein are identical with the meaning that scientific words and those skilled in the art are familiar with.Any in addition with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.
The specific embodiment
Below in conjunction with the specific embodiment, only the present invention is done further description, rather than to the restriction of protection domain of the present invention.
The even distribution situation of said CNT and carbon fiber is confirmed through the SEM photo.Fig. 2 shows and reaches " the pure no cracking carbon of CNT or few, high coverage rate (CNT is wrapped in fiber surface) " required standard picture.
Embodiment 1:
Three-dimensional acupuncture carbon fiber knit body is come unstuck, put into dense HNO behind the cleaning-drying
3Middle activation 0.5～2h cleans to neutral and drying, is the Fe (NO of 0.02mol/L in concentration with its vacuum impregnation then
3)
3Acetone soln in 2h.The three-dimensional carbon fiber knit body of the supported catalyst of drying is put in chemical vapour deposition (CVD)/penetration equipment, rise to 600 ℃ under argon gas/nitrogen atmosphere after, stop gas and feed hydrogen and argon gas Fe (NO
3)
3Be reduced into the nanometer Fe particle, close gas and feed ethene then, response parameter is C
2H
4Holdup time 0.1s/cm, furnace pressure are 40Kpa, and the reaction time is 5h.After reaction finishes; Close gas, be cooled to room temperature under the argon gas atmosphere, obtain the three-dimensional multistage enhancing body that carbon fiber and even carbon nanotube distribute; The pure cracking carbon of the CNT of knitted body growth inside impurity is few, high coverage rate (evenly wrapping up fiber surface), like Fig. 2.
Embodiment 2:
The three-dimensional fiber knitted body that adopts be three-dimensional five to knitted body, other are identical with embodiment 1.The pure cracking carbon of the CNT of knitted body growth inside impurity is few, high coverage rate (evenly wrapping up fiber surface).
Embodiment 3:
The three-dimensional fiber knitted body that adopts is that two dimension is sewed up knitted body, and other are identical with embodiment 1.The pure cracking carbon of the CNT of knitted body growth inside impurity is few, high coverage rate (evenly wrapping up fiber surface).。
Embodiment 4:
The interface of adopting is Si
3N
4, other are identical with embodiment 1.The pure cracking carbon of the CNT of knitted body growth inside impurity is few, high coverage rate (evenly wrapping up fiber surface).
Embodiment 5:
With the three-dimensional puncture silicon carbide fibre knitted body at deposition PyC interface, put into dense H behind the cleaning-drying
2SO
4Middle activation 4h cleans to neutral and drying, is the Ni (NO of 0.5mol/L in concentration with its impregnating by pressure then
3)
2/ Al (NO
3)
3Ethanolic solution in 4h.The three-dimensional fiber knitted body of the supported catalyst of drying is put in chemical vapour deposition (CVD)/penetration equipment, rise to 700 ℃ under the vacuum atmosphere after, feed hydrogen and argon gas with Ni (NO
3)
2/ Al (NO
3)
3Be reduced into nanometer Ni/Al
2O
3Particle feeds acetylene then, and response parameter is C
2H
2: H2=1: 100, C
2H
2Holdup time is 0.01s/cm, and furnace pressure is 50Kpa, and the reaction time is 10min.After reaction finishes; Close gas, be cooled to room temperature under the argon gas atmosphere, obtain the three-dimensional multistage enhancing body that silicon carbide fibre and even carbon nanotube distribute; The pure cracking carbon of the CNT of knitted body growth inside impurity is few, high coverage rate (evenly wrapping up fiber surface), type Fig. 2.
Embodiment 6:
The 3 D weaving body that adopts in the present embodiment is the three-dimensional carborundum knitted body of 2.5D, and other technologies are identical with embodiment 5.The pure no cracking carbon impurity of the CNT of knitted body growth inside, high coverage rate (evenly wrapping up fiber surface).
Embodiment 7:
With the three-dimensional aluminum oxide fibrage body of deposition PyC/SiC, putting into volume ratio behind the cleaning-drying is 3: 1HNO
3/ H
2SO
4=middle activation 6h cleans to neutral and dry, is immersed in the Co (NO that concentration is 1.0mol/L after then it being vacuumized
3)
2Ethylene glycol solution in 12h.The three-dimensional aluminum oxide fibrage body of the supported catalyst of drying is put in chemical vapour deposition (CVD)/penetration equipment, rise to 800 ℃ under the nitrogen atmosphere after, stop nitrogen and feed hydrogen Co (NO
3)
2Be reduced into the nano Co particle, feed methane then, response parameter is CH
4: H
2=1: 20, CH
4Holdup time be 1s/cm, furnace pressure is 5Kpa, the reaction time is 10hr.After reaction finishes; Close gas; Be cooled to room temperature under the argon gas atmosphere, obtain the three-dimensional multistage enhancing body that alumina fibre and even carbon nanotube distribute, the pure cracking carbon of the CNT of knitted body growth inside impurity is few, high coverage rate (evenly wrapping up fiber surface).
Embodiment 8:
With the three-dimensional orthogonal boron fibre knitted body of deposition BN, put into dense HNO behind the cleaning-drying
3Middle activation 6h cleans and drying, is immersed in the Fe (NO that concentration is 2.0mol/L after then it being vacuumized
3)
3/ Ni (NO
3)
3/ Al (NO
3)
3Xylene solution in 24h.The three-dimensional orthogonal boron fibre knitted body of the supported catalyst of drying is put in chemical vapour deposition (CVD)/penetration equipment, rise to 850 ℃ under the vacuum atmosphere after, feed hydrogen with Fe (NO
3)
3/ Ni (NO
3)
3/ Al (NO
3)
3Be reduced into nanometer Fe/Ni/Al
2O
3Particle feeds propane then, and response parameter is propane: H
2=1: 80, the propane holdup time is 0.001s/cm, and furnace pressure is 20Kpa, and the reaction time is 5hr.After reaction finishes; Close gas, be cooled to room temperature under the argon gas atmosphere, obtain the three-dimensional multistage enhancing body that boron fibre and even carbon nanotube distribute; The pure no cracking carbon impurity of the CNT of knitted body growth inside, high coverage rate (evenly wrapping up fiber surface), similar Fig. 2.
Embodiment 9:
With the three-dimensional four-way BN fibrage body of deposition PyC/SiC, put into dense HNO behind the cleaning-drying
3Middle activation 1h cleans and drying, then its impregnating by pressure is amounted to the Fe (NO of 1mol/L in concentration
3)
3/ Ni (NO
3)
2Ethanolic solution in 24h.The three-dimensional carbon fiber knit body of the supported catalyst of drying is put in chemical vapour deposition (CVD)/penetration equipment, rise to 1000 ℃ under argon gas/nitrogen atmosphere after, stop gas and feed hydrogen/argon gas mist (the Ar volume fraction is 10%) Fe (NO
3)
3/ Ni (NO
3)
2Be reduced into nanometer Fe/Ni particle, feed methane then, response parameter is CH
4: H
2=1: 5, CH
4Holdup time is 0.01s/cm, and furnace pressure is 0.2Kpa, and the reaction time is 2hr.Reaction is closed gas after finishing, and is cooled to room temperature under the argon gas atmosphere, obtains the three-dimensional multistage enhancing body that BN fiber and even carbon nanotube distribute, and the pure cracking carbon of the CNT of knitted body growth inside impurity is few, high coverage rate (evenly wrapping up fiber surface)
Embodiment 10:
With the three-dimensional orthogonal carbon fiber knit body of deposition PyC, put into dense H after putting into the distilled water cleaning-drying
2SO
4Middle activation 4h, washed with de-ionized water is immersed in the Fe (NO that concentration is 0.3mol/L to neutral and dry after then it being vacuumized
3)
3/ Co (NO
3)
3Ethanolic solution in 2h.The three-dimensional carbon fiber knit body of the supported catalyst of drying is put in chemical vapour deposition (CVD)/penetration equipment, rise to 900 ℃ under the vacuum atmosphere after, feed hydrogen/argon gas (the argon gas volume fraction is 50%) with Fe (NO
3)
3/ Co (NO
3)
3Be reduced into nanometer Fe/Co particle, feed ethene and CO then, response parameter is C
2H
4: CO=1: 80, C
2H
4Holdup time is 0.2s/cm, and furnace pressure is 10Kpa, and the reaction time is 60min.Reaction is closed gas after finishing, and is cooled to room temperature under the argon gas atmosphere, obtains the three-dimensional multistage enhancing body that carbon fiber and even carbon nanotube distribute, and the pure cracking carbon of the CNT of knitted body growth inside impurity is few, high coverage rate (evenly wrapping up fiber surface).。
Embodiment 11:
The interface of adopting is HfC
2/ ZrC boundary layer, other are identical with embodiment 10.The pure cracking carbon of the CNT of knitted body growth inside impurity is few, high coverage rate (evenly wrapping up fiber surface).。
The above is merely preferred embodiment of the present invention; Be not in order to limit essence technology contents scope of the present invention; Essence technology contents of the present invention is broadly to be defined in the claim scope of application, and if any technological entity or method that other people accomplish are defined identical with the claim scope of application; Also or a kind of change of equivalence, all will be regarded as and be covered by among this claim scope.
All documents in that the present invention mentions are all quoted as a reference in this application, are just quoted such as a reference separately as each piece document.Should be understood that in addition that after having read foregoing of the present invention those skilled in the art can do various changes or modification to the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (32)
1. the multistage enhancing body of three-dimensional fiber/CNT is characterized in that, in the three-dimensional fiber precast body, grows as the CNT (CNTs) of nanometer wild phase through chemical vapor infiltration (CVI) technology, obtains said multistage enhancing body.
2. multistage enhancing body as claimed in claim 1; It is characterized in that said three-dimensional fiber precast body is selected from three-dimensional four-way precast body, three-dimensional five and sews up precast body, the three-dimensional precast body of 2.5D, three-dimensional acupuncture precast body, three-dimensional puncture precast body, three-dimensional orthogonal precast body or its combination to precast body, two dimension
3. multistage enhancing body as claimed in claim 1 is characterized in that in the said three-dimensional fiber precast body, the fiber that is adopted is selected from carbon fiber, silicon carbide fibre, BN fiber, ceramic fibre or its combination.
4. multistage enhancing body as claimed in claim 1 is characterized in that in the said three-dimensional fiber precast body, fiber surface deposits boundary layer, and said boundary layer comprises PyC interface, SiC interface, BN interface, Si
3N
4Interface, ZrC interface, ZrB
2Interface, HfC interface, HfB
2Interface, TaC interface, TiC interface and the compound interface of forming by above-mentioned interface.
5. multistage enhancing body as claimed in claim 1 is characterized in that the concrete steps of said growing method are following:
The three-dimensional fiber knitted body soaks in the complex catalyst precursor liquid solution and is dry; Dried knitted body is carried out high-temperature heat treatment and under reducing atmosphere, reduces, make the catalyst of load be converted into metal nanoparticle, obtain said three-dimensional fiber precast body;
Adopt chemical vapor infiltration technology carbon nano-tube (CNTs) in said three-dimensional fiber precast body, obtain said multistage enhancing body.
6. multistage enhancing body as claimed in claim 5 is characterized in that the catalyst precursor that is adopted comprises the salt and the multiple combination thereof of iron content, cobalt, nickel.
7. multistage enhancing body as claimed in claim 5 is characterized in that the concentration of the complex catalyst precursor liquid solution that is adopted is the saturated solution of 0.01mol/L to catalyst precursor.
8. multistage enhancing body as claimed in claim 5 is characterized in that heat treated temperature is 200-1400 ℃, preferred 650-1000 ℃.
9. multistage enhancing body as claimed in claim 5 is characterized in that reduction reaction temperature is 500-1400 ℃, preferred 500-1000 ℃.
10. multistage enhancing body as claimed in claim 1 is characterized in that the depositing temperature of said chemical vapor infiltration technology is 500-1400 ℃, preferred 600-1000 ℃.
11. multistage enhancing body as claimed in claim 1 is characterized in that the sedimentation time of said chemical vapor infiltration technology is 5min-10h, preferred 0.5h-3h.
12. multistage enhancing body as claimed in claim 1 is characterized in that the carbon source that is adopted during carbon nano-tube is a hydrocarbon, optimization methane, ethene, acetylene or its combination.
13. multistage enhancing body as claimed in claim 1 is characterized in that the deposition region gas hold-up time of said chemical vapor infiltration technology is 0.001s/cm-1s/cm, preferred 0.01s/cm-0.3s/cm.
14. multistage enhancing body as claimed in claim 1 is characterized in that the deposition pressure of said chemical vapor infiltration technology is 0.1KPa-50KPa, preferred 0.5-20KPa.
15. multistage enhancing body as claimed in claim 1 is characterized in that, introduces other metals or the inert component that stops catalyst at high temperature to be reunited in the catalyst of employing simultaneously.
16. multistage enhancing body as claimed in claim 1 is characterized in that, feeds portion C O or H simultaneously in the said chemical vapor infiltration technical process
2As reducing gas, to avoid catalyst oxidation or poisoning; Or feed other inert gases simultaneously as diluent gas in the said chemical vapor infiltration technical process.
17. the preparation method of a multistage enhancing body as claimed in claim 1; It is characterized in that; Said method is in the three-dimensional fiber precast body, to grow as the CNT (CNTs) of nanometer wild phase through chemical vapor infiltration (CVI) technology, obtains said multistage enhancing body.
18. method as claimed in claim 17; It is characterized in that said three-dimensional fiber precast body is selected from three-dimensional four-way precast body, three-dimensional five and sews up precast body, the three-dimensional precast body of 2.5D, three-dimensional acupuncture precast body, three-dimensional puncture precast body, three-dimensional orthogonal precast body or its combination to precast body, two dimension
19. method as claimed in claim 17 is characterized in that, in the said three-dimensional fiber precast body, the fiber that is adopted is selected from carbon fiber, silicon carbide fibre, BN fiber, ceramic fibre or its combination.
20. method as claimed in claim 17 is characterized in that, in the said three-dimensional fiber precast body, the boundary layer of fiber surface deposition comprises PyC interface, SiC interface, BN interface, Si
3N
4Interface, ZrC interface, ZrB
2Interface, HfC interface, HfB
2Interface, TaC interface, TiC interface and the compound interface of forming by above-mentioned interface.
21. method as claimed in claim 17 is characterized in that, is made by following method:
The three-dimensional fiber knitted body soaks in the complex catalyst precursor liquid solution and is dry; Dried knitted body is carried out high-temperature heat treatment and under reducing atmosphere, reduces, make the catalyst of load be converted into metal nanoparticle, obtain said three-dimensional fiber precast body;
Adopt chemical vapor infiltration technology carbon nano-tube (CNTs) in said three-dimensional fiber precast body, obtain said multistage enhancing body.
22. method as claimed in claim 21 is characterized in that, the catalyst precursor that is adopted comprises the salt and the multiple combination thereof of iron content, cobalt, nickel.
23. method as claimed in claim 21 is characterized in that, the concentration of the complex catalyst precursor liquid solution that is adopted is the saturated solution of 0.01mol/L to catalyst precursor.
24. method as claimed in claim 21 is characterized in that, heat treated temperature is 200-1400 ℃, preferred 650-1000 ℃.
25. method as claimed in claim 21 is characterized in that, reduction reaction temperature is 500-1400 ℃, preferred 500-1000 ℃.
26. method as claimed in claim 17 is characterized in that, the depositing temperature of said chemical vapor infiltration technology is 500-1400 ℃, preferred 600-1000 ℃.
27. method as claimed in claim 17 is characterized in that, the sedimentation time of said chemical vapor infiltration technology is 5min-10h, preferred 0.5h-3h.
28. method as claimed in claim 17 is characterized in that, the carbon source that is adopted during carbon nano-tube is a hydrocarbon, optimization methane, ethene, acetylene or its combination.
29. method as claimed in claim 17 is characterized in that, the deposition region gas hold-up time of said chemical vapor infiltration technology is 0.001s/cm-1s/cm, preferred 0.01s/cm-0.3s/cm.
30. method as claimed in claim 17 is characterized in that, the deposition pressure of said chemical vapor infiltration technology is 0.1KPa-50KPa, preferred 0.5-20KPa.
31. method as claimed in claim 17 is characterized in that, introduces other metals or the inert component that stops catalyst at high temperature to be reunited in the catalyst of employing simultaneously.
32. method as claimed in claim 17 is characterized in that, feeds portion C O or H simultaneously in the said chemical vapor infiltration technical process
2As reducing gas, to avoid catalyst oxidation or poisoning; Or feed other inert gases simultaneously as diluent gas in the said chemical vapor infiltration technical process.
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| CN103061004A (en) * | 2012-12-29 | 2013-04-24 | 中材科技股份有限公司 | Novel structure three-dimensional fabric and weaving method thereof |
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| CN103951455A (en) * | 2014-04-09 | 2014-07-30 | 天津大学 | Method for preparing dense carbon nanotube-fiber-precursor ceramic composite material with the assistance of freeze drying |
| CN103951455B (en) * | 2014-04-09 | 2015-07-15 | 天津大学 | Method for preparing dense carbon nanotube-fiber-precursor ceramic composite material with the assistance of freeze drying |
| CN104909790A (en) * | 2015-05-26 | 2015-09-16 | 中国科学院上海硅酸盐研究所 | Two-dimensional fiber/boron nitride nanotube multistage reinforcement and preparation method thereof |
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