CN105693262A - Fiber-reinforced ceramic matrix composite and preparation method for graphene/carbon nano-tube interface - Google Patents
Fiber-reinforced ceramic matrix composite and preparation method for graphene/carbon nano-tube interface Download PDFInfo
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Abstract
The invention relates to a fiber-reinforced ceramic matrix composite and preparation method for a graphene/carbon nano-tube interface.The composite is structurally characterized in that a carbon fiber is wrapped by a carbon nano-tube, the carbon nano-tube is wrapped by graphene, and a Sic base body is arranged on the outermost layer.The deposit rate of the carbon nano-tube, the graphene and the Sic base body is regulated by regulating the solution concentration and deposition time, and the sequence and the number of layers of a 'carbon nano-tube/graphene' interface layer are designed by changing the deposition sequence and the number of deposition times.The introduced carbon nano-tube and graphene are good in dispersibility, the mass fraction is adjustable within a large scope, and the interface can be designed.An interface phase with the strength reasonable can be designed, and the effect of a fiber-reinforced body can be given to full play; secondary toughening can be conducted on the composite through CNT and the layered graphene, the pulling-out and bridging effects as well as the effect of deflecting cracks of the fiber, the CNT and the graphene can be given to full play, and mechanical properties of the composite are effectively improved.By means of the method, interface layer preparation time is short, efficiency is high, and design can be regulated.
Description
Technical field
The present invention relates to the FRCMC preparation method at a kind of graphene/carbon nano-tube interface, carry out, by electroreduction deposited oxide Graphene (GO) and electrophoretic deposition CNT (CNT), the method that design interface prepares FRCMC, particularly relate to the preparation method that under a kind of CVI technique, continuous carbon fibre strengthens carbon/silicon carbide ceramic matrix composite (C/SiC) GO/CNT interface。
Background technology
The carbon/silicon carbide ceramic matrix composite (CMC) of continuous lod has low-density, Gao Biqiang, Gao Bimo, the excellent properties such as high temperature resistant, corrosion-resistant, wear-resistant。Being different from traditional ceramics, it has the fracture behaviour of metalloid, crackle is insensitive and the features such as catastrophic failure do not occur, and is widely used in the fields such as Aero-Space, military affairs, the energy as high-temperature structural material。Interface plays transmission load as the third phase being present between CMC fiber and matrix, alleviates the vital effects such as fiber does not mate with matrix thermal stress。The technique that current chemical vapour deposition technique (CVI) prepares pyrolytic carbon (PyC) interface and boron nitride (BN) interface FRCMC is ripe。CVI technique generally adopts relatively low temperature (< 1000 DEG C) and pressure, this avoid the high-temperature damage of carbon fiber, but to be deposition velocity slow, manufacturing cycle is long for its shortcoming。
CNT (CNT) is due to the mechanical property of its excellence, there is high draw ratio and high chemically and thermally stability, and its energy of rupture having subsided by hollow space, thus the advantages such as energy can be absorbed in the application of composite greatly, the obdurability of material can be improved significantly。Graphene is the two-dimension nano materials that carbon atom hexagonal connects topology formation, has high-specific surface area, high intensity, high-modulus, and the two-dimensional nanostructure of its uniqueness, excellent mechanical property make it have important application potential in development high-performance composite materials。
The patent of invention CN104150939A that Chinese patent literature discloses discloses " preparation method that a kind of electrophoretic deposition CNTs strengthens ceramic matric composite ", described preparation method is that the method utilizing electrophoresis has deposition CNTs on the carbon cloth of PyC heavy, then silicon carbide substrate is prepared by the method for CVI, the method still needs to preparation pyrolytic carbon interface, and interface manufacturing cycle is long。Li et al. (F.Li.Polymer, 2015,59:155-165) increase graphene oxide layer on chopped carbon fiber surface and strengthen polyether sulfone, it stretches and bending property is all improved, but the method that the method employing fiber mixes with Graphene is to prepare graphene oxide interface, and is used on enhancing macromolecule。Zang et al. (C.G.Zang.JournalofAppliedPolymerScience, 2015,132 (19)) by introducing functional group at fiber and graphenic surface, make its reaction forming be prepared for carbon fiber/graphite alkene associating reinforcement together, the nylon 6 composite material mechanics electric property of its enhancing is improved, this method utilizes functional group's bonding to prepare Graphene interface, and is also for strengthening macromolecule。
At present, based on the ceramic matric composite of continuous lod, the method of electroreduction graphene oxide and electrophoresis CNT of directly utilizing will introduce interface between fiber and matrix both it, and the method replacing the interface phase that pyrolytic carbon or boron carbide etc. are prepared with chemical vapour deposition technique yet there are no open report。
Summary of the invention
Solve the technical problem that
In order to avoid the deficiencies in the prior art part, the present invention proposes FRCMC and the preparation method at a kind of graphene/carbon nano-tube interface, give full play to CNT and Graphene improve the advantage of ceramic matric composite mechanical property, it is to avoid traditional handicraft CNT and Graphene ceramic matrix mutually in bad dispersibility and the shortcoming of preparing interface phase cycle length with chemical vapour deposition technique。
Technical scheme
The FRCMC structure at a kind of graphene/carbon nano-tube interface, it is characterised in that include carbon fiber, CNT, Graphene and SiC matrix；The outside enveloped carbon nanometer tube of carbon fiber, the outside coated graphite alkene of CNT, outermost layer is SiC matrix。
The locations of structures of described CNT and Graphene is exchanged mutually。
The outside being coated on carbon fiber that described CNT and Graphene adulterate mutually。
Described CNT and Graphene are spaced multiple structure。
A kind of method of the FRCMC preparing described graphene/carbon nano-tube interface, it is characterised in that: the outside enveloped carbon nanometer tube of carbon fiber, the outside coated graphite alkene of CNT, outermost layer is SiC matrix；Or multiple structure preparation process that CNT and Graphene are spaced is as follows:
Step 1: the CNT of 1 mass fraction is distributed in the deionized water solution of 1000～4000 mass fractions, add the TritonX of 0.2 mass fraction, configuration concentration is the CNT suspension of 0.25mg/ml～1mg/ml, by this CNT suspension ultrasound wave material emulsion dispersion device ultrasonic disperse 20～30min, obtain homodisperse CNT aqueous solution；
Step 2: be distributed in the deionized water solution of 1000～2000 mass fractions by the graphene oxide of 1 mass fraction, disperse 5h with ultrasonic cleaner, is configured to the graphene oxide water solution of 0.5～1mg/ml；
Step 3: utilizing the method for electrophoretic deposition that carbon fiber electrophoretic deposition in prepared CNT aqueous solution must be arrived surface and have the carbon fiber of CNT, sedimentation time is 15～30min；
Step 4: utilize the surface that step 3 is obtained by the method for electroreduction to have the carbon fiber of CNT deposited graphite alkene in prepared graphene oxide water solution, obtaining surface deposition has the carbon fiber of CNT and Graphene, and sedimentation time is 10～30 minutes；
Or repeat step 3～step 4, obtain spaced CNT and graphene-structured；
Step 5: adopt deposition SiC matrix on CVI technique carbon fiber after step 4 processes, process conditions are as follows: trichloromethyl silane is presoma, argon is diluent gas, flow 300～400ml/min, hydrogen is carrier gas, flow 200～350ml/min, and the mol ratio of hydrogen and trichloromethyl silane is 10:1, depositing temperature is 1000～1100 DEG C, and sedimentation time 120～960h obtains the silicon carbide fiber reinforced ceramic matric composite at carbon nano tube/graphene interface。
A kind of method of the FRCMC preparing described graphene/carbon nano-tube interface, it is characterised in that: the outside coated graphite alkene of carbon fiber, the outside enveloped carbon nanometer tube of Graphene, outermost layer is SiC matrix；Or CNT and Graphene are spaced multiple structure；Preparation process is as follows:
Step 1: the CNT of 1 mass fraction is distributed in the deionized water solution of 1000～4000 mass fractions, add the TritonX of 0.2 mass fraction, configuration concentration is the CNT suspension of 0.25mg/ml～1mg/ml, by this CNT suspension ultrasound wave material emulsion dispersion device ultrasonic disperse 20～30min, obtain homodisperse CNT aqueous solution；
Step 2: be distributed in the deionized water solution of 1000～2000 mass fractions by the graphene oxide of 1 mass fraction, disperse 5h with ultrasonic cleaner, is configured to the graphene oxide water solution of 0.5～1mg/ml；
Step 3: utilizing the method for electroreduction by carbon fiber deposited graphite alkene in graphene oxide water solution, obtaining surface deposition has the carbon fiber of Graphene, and sedimentation time is 10～30 minutes；
Step 4: utilizing the surface deposition that step 3 is obtained by the method for electrophoretic deposition to have carbon fiber electrophoretic deposition in CNT aqueous solution of Graphene must arrive surface and have the carbon fiber of Graphene and CNT, sedimentation time is 15～30min；
Or repeat step 3～step 4, obtain spaced Graphene and CNT structure；
Step 5: adopt deposition SiC matrix on CVI technique carbon fiber after step 4 processes, process conditions are as follows: trichloromethyl silane is presoma, argon is diluent gas, flow 300～400ml/min, hydrogen is carrier gas, flow 200～350ml/min, and the mol ratio of hydrogen and trichloromethyl silane is 10:1, depositing temperature is 1000～1100 DEG C, and sedimentation time 120～960h obtains the silicon carbide fiber reinforced ceramic matric composite at carbon nano tube/graphene interface。
A kind of method of the FRCMC preparing described graphene/carbon nano-tube interface, it is characterised in that: the outside being coated on carbon fiber that CNT and Graphene adulterate mutually, preparation process is as follows:
Step 1: the CNT of 1 mass fraction is distributed in the deionized water solution of 1000～4000 mass fractions, add the TritonX of 0.2 mass fraction, configuration concentration is the CNT suspension of 0.25mg/ml～1mg/ml, by this CNT suspension ultrasound wave material emulsion dispersion device ultrasonic disperse 20～30min, obtain homodisperse CNT aqueous solution；
Step 2: be distributed in the deionized water solution of 1000～2000 mass fractions by the graphene oxide of 1 mass fraction, disperse 5h with ultrasonic cleaner, is configured to the graphene oxide water solution of 0.5～1mg/ml；
Step 3: CNT aqueous solution and graphene oxide water solution are mixed to form mixed solution, carbon fiber is placed in mixed solution, the method utilizing electrophoretic deposition deposits CNT at carbon fiber surface, the method simultaneously utilizing electroreduction obtains graphene oxide at carbon fiber surface, and obtaining surface deposition has CNT and the carbon fiber of the mutual doped structure of Graphene；Sedimentation time is 10～30min；
Step 5: adopt deposition SiC matrix on CVI technique carbon fiber after step 4 processes, process conditions are as follows: trichloromethyl silane is presoma, argon is diluent gas, flow 300～400ml/min, hydrogen is carrier gas, flow 200～350ml/min, and the mol ratio of hydrogen and trichloromethyl silane is 10:1, depositing temperature is 1000～1100 DEG C, and sedimentation time 120～960h obtains the silicon carbide fiber reinforced ceramic matric composite at carbon nano tube/graphene interface。
In described step 5, add nitrogenous source NH3, flow is the 0.1～10 of carrier gas hydrogen, depositing temperature 800～1100 DEG C, and deposition 150～300h obtains micro nanometer fiber/Si3N4Ceramic matric composite。
CNT in described step 1 is many walls or single wall。
Carbon fiber in described step 4 is single bundle carbon fiber or carbon cloth。
Beneficial effect
The FRCMC at a kind of graphene/carbon nano-tube interface that the present invention proposes and preparation method, its structure is the outside enveloped carbon nanometer tube of carbon fiber, and the outside coated graphite alkene of CNT, outermost layer is SiC matrix。CNT, Graphene and SiC matrix regulate and control deposition by regulating and controlling solution concentration and sedimentation time, are designed order and the number of plies of " carbon nano tube/graphene " boundary layer by change sedimentary sequence and frequency of depositing。The CNT and the graphene dispersion that introduce are good, and mass fraction is adjustable on a large scale, and interface can be designed。Strong and weak reasonably interface phase can be designed, give full play to the effect of fibre reinforcement；And CNT and lamellar graphite alkene can be toughness reinforcing to composite secondary。The effect that fiber, CNT and Graphene are extracted and bridged and the effect making crack deflection can be given full play to, be effectively improved the mechanical property of composite。
It is short that the inventive method prepares the boundary layer time, and efficiency is high, and controllable design。
Accompanying drawing explanation
Fig. 1: the outside of carbon fiber is the structure chart of carbon nanotube layer and graphene layer
Fig. 2: the outside of carbon fiber is the structure chart of graphene layer and carbon nanotube layer
Fig. 3: the outside of carbon fiber is the structure chart of Graphene and CNT mixed layer
Fig. 4: scanning electron microscope (SEM) figure of carbon fiber surface carbon nano tube/graphene
The SEM figure of fracture after Fig. 5: C/ (CNT/GO)/SiCmini composite tension failure
The SEM figure of fiber surface is extracted after Fig. 6: C/ (CNT/GO)/SiCmini composite tension failure
Detailed description of the invention
In conjunction with embodiment, accompanying drawing, the invention will be further described:
Embodiment 1:
(1) 0.5g CNT is scattered in 1000ml deionized water, adds 0.1g carbon nano-tube aqueous solutions dispersant, then with ultrasound wave material emulsion dispersion device ultrasonic disperse 30min, obtain the CNT aqueous solution of 0.5mg/ml。
(2) 0.5g graphene oxide is distributed in 500ml deionized water, disperses 5h with ultrasonic cleaner, be configured to 1mg/ml graphene solution。
(3) being immersed by carbon cloth in the CNT solution of step (1), electrophoretic deposition CNT15min, taking-up is dried；Then being immersed by carbon fiber in the graphite weak solution of step (2), electroreduction deposited graphite alkene 15 minutes, taking-up is dried again；Obtain the heavy carbon cloth having CNT/GO interface
(4) by the carbon cloth lamination of preparation in 20 steps (3), with the clamping sizing of the graphite cake of two pieces of porous, adopt relay-type needle-punching method by template and the stitching of middle lamination carbon cloth, prepare into surface and sink the precast body having CNT/GO/CNT。
(5) on the precast body that step (4) obtains, adopt CVI process deposits SiC matrix, process conditions are as follows: trichloromethyl silane is precursor gas, argon is diluent gas (flow 300ml/min), hydrogen is carrier gas (flow 200ml/min), the mol ratio of hydrogen and trichloromethyl silane is 10:1, depositing temperature is 1000 DEG C, sedimentation time 720h, obtain the Ceramic Matrix Composites Reinforced by Carbon Fibers at CNT/GO/CNT interface, compared with the carbon/silicon carbide ceramic matrix of the continuous lod at pyrolytic carbon interface (C/PyC/SiC) composite, the prepared the highest raising 25% of Two-dimensional Composites bending strength。
Or before step 4, carbon cloth being immersed in the CNT solution of step (1), electrophoretic deposition CNT15min, taking-up is dried, and obtains the heavy carbon cloth having CNT/GO/CNT interface。
Or before step 4, repeat step 3 many times, obtain the carbon cloth at multi-layer C NT/GO interface。
Embodiment 2:
(1) 0.5g CNT is scattered in 1000ml deionized water, adds 0.1g carbon nano-tube aqueous solutions dispersant, then with ultrasound wave material emulsion dispersion device ultrasonic disperse 30min, obtain the CNT aqueous solution of 0.5mg/ml。
(2) 0.5g graphene oxide is distributed in 500ml deionized water, disperses 5h with ultrasonic cleaner, be configured to 1mg/ml graphene solution。
(3) being immersed by carbon fiber in the graphite weak solution of step (2), electroreduction deposited graphite alkene 15 minutes, taking-up is dried；Being immersed by carbon cloth in the CNT solution of step (1), electrophoretic deposition CNT15min, taking-up is dried again；Obtain the heavy carbon cloth having GO/CNT interface。
(4) by the carbon cloth lamination of preparation in 20 steps (3), with the clamping sizing of the graphite cake of two pieces of porous, adopt relay-type needle-punching method by template and the stitching of middle lamination carbon cloth, prepare into surface and sink the precast body having CNT/GO/CNT。
(5) on the precast body that step (4) obtains, adopt CVI process deposits SiC matrix, process conditions are as follows: trichloromethyl silane is precursor gas, argon is diluent gas (flow 300ml/min), hydrogen is carrier gas (flow 200ml/min), the mol ratio of hydrogen and trichloromethyl silane is 10:1, depositing temperature is 1000 DEG C, sedimentation time 720h, obtain the Ceramic Matrix Composites Reinforced by Carbon Fibers at CNT/GO/CNT interface, compared with the carbon/silicon carbide ceramic matrix of the continuous lod at pyrolytic carbon interface (C/PyC/SiC) composite, the prepared the highest raising 25% of Two-dimensional Composites bending strength。
Or before step 4, again carbon cloth being immersed in the graphite weak solution of step (2), electroreduction deposited graphite alkene 15 minutes, taking-up is dried；Obtain the heavy carbon cloth having GO/CNT/GO interface。
Or before step 4, repeat step 3 many times, obtain the carbon cloth at multilamellar GO/CNT interface。
Embodiment 3:
(1) 0.5g CNT is scattered in 1000ml deionized water, adds 0.1g carbon nano-tube aqueous solutions dispersant, then with ultrasound wave material emulsion dispersion device ultrasonic disperse 30min, obtain the CNT aqueous solution of 0.5mg/ml。
(2) 0.5g graphene oxide is distributed in 500ml deionized water, disperses 5h with ultrasonic cleaner, be configured to 1mg/ml graphene solution。
(3) step (1) is mixed with the solution of configuration in step (2), obtain CNT/GO mixed solution。
(4) being immersed by 1K carbon fiber bundle in the CNT/GO mixed solution of step (3), electricity 30 minutes, taking-up is dried, and obtains the heavy carbon fiber bundle having CNT/GO interface。
(5) on the 1K carbon fiber bundle that step (4) obtains, CVI process deposits SiC matrix is adopted, process conditions are as follows: trichloromethyl silane is precursor gas, argon is diluent gas (flow 300ml/min), hydrogen is carrier gas (flow 200ml/min), the mol ratio of hydrogen and trichloromethyl silane is 10:1, depositing temperature is 1000 DEG C, sedimentation time 120h, obtain the silicon carbide fiber reinforced ceramic matric composite of mini at CNT/GO interface, compared with the carbon/silicon carbide ceramic matrix of the continuous lod at pyrolytic carbon interface (C/PyC/SiC) composite, the prepared mini the highest raising 20% of composite hot strength。
Claims (10)
1. the FRCMC structure at a graphene/carbon nano-tube interface, it is characterised in that include carbon fiber, CNT, Graphene and SiC matrix；The outside enveloped carbon nanometer tube of carbon fiber, the outside coated graphite alkene of CNT, outermost layer is SiC matrix。
2. the FRCMC structure at graphene/carbon nano-tube interface according to claim 1, it is characterised in that: the locations of structures of described CNT and Graphene is exchanged mutually。
3. the FRCMC structure at graphene/carbon nano-tube interface according to claim 1, it is characterised in that: the outside being coated on carbon fiber that described CNT and Graphene adulterate mutually。
4. the FRCMC structure at graphene/carbon nano-tube interface according to claim 1 and 2, it is characterised in that: described CNT and Graphene are spaced multiple structure。
5. prepare the method for the FRCMC at graphene/carbon nano-tube interface described in claim 1 or 4 for one kind, it is characterised in that step is as follows:
Step 1: the CNT of 1 mass fraction is distributed in the deionized water solution of 1000～4000 mass fractions, add the TritonX of 0.2 mass fraction, configuration concentration is the CNT suspension of 0.25mg/ml～1mg/ml, by this CNT suspension ultrasound wave material emulsion dispersion device ultrasonic disperse 20～30min, obtain homodisperse CNT aqueous solution；
Step 2: be distributed in the deionized water solution of 1000～2000 mass fractions by the graphene oxide of 1 mass fraction, disperse 5h with ultrasonic cleaner, is configured to the graphene oxide water solution of 0.5～1mg/ml；
Step 3: utilizing the method for electrophoretic deposition that carbon fiber electrophoretic deposition in prepared CNT aqueous solution must be arrived surface and have the carbon fiber of CNT, sedimentation time is 15～30min；
Step 4: utilize the surface that step 3 is obtained by the method for electroreduction to have the carbon fiber of CNT deposited graphite alkene in prepared graphene oxide water solution, obtaining surface deposition has the carbon fiber of CNT and Graphene, and sedimentation time is 10～30 minutes；
Or repeat step 3～step 4, obtain spaced CNT and graphene-structured；
Step 5: adopt deposition SiC matrix on CVI technique carbon fiber after step 4 processes, process conditions are as follows: trichloromethyl silane is presoma, argon is diluent gas, flow 300～400ml/min, hydrogen is carrier gas, flow 200～350ml/min, and the mol ratio of hydrogen and trichloromethyl silane is 10:1, depositing temperature is 1000～1100 DEG C, and sedimentation time 120～960h obtains the silicon carbide fiber reinforced ceramic matric composite at carbon nano tube/graphene interface。
6. prepare the method for the FRCMC at graphene/carbon nano-tube interface described in claim 2 or 4 for one kind, it is characterised in that step is as follows:
Step 1: the CNT of 1 mass fraction is distributed in the deionized water solution of 1000～4000 mass fractions, add the TritonX of 0.2 mass fraction, configuration concentration is the CNT suspension of 0.25mg/ml～1mg/ml, by this CNT suspension ultrasound wave material emulsion dispersion device ultrasonic disperse 20～30min, obtain homodisperse CNT aqueous solution；
Step 2: be distributed in the deionized water solution of 1000～2000 mass fractions by the graphene oxide of 1 mass fraction, disperse 5h with ultrasonic cleaner, is configured to the graphene oxide water solution of 0.5～1mg/ml；
Step 3: utilizing the method for electroreduction by carbon fiber deposited graphite alkene in graphene oxide water solution, obtaining surface deposition has the carbon fiber of Graphene, and sedimentation time is 10～30 minutes；
Step 4: utilizing the surface deposition that step 3 is obtained by the method for electrophoretic deposition to have carbon fiber electrophoretic deposition in CNT aqueous solution of Graphene must arrive surface and have the carbon fiber of Graphene and CNT, sedimentation time is 15～30min；
Or repeat step 3～step 4, obtain spaced Graphene and CNT structure；
Step 5: adopt deposition SiC matrix on CVI technique carbon fiber after step 4 processes, process conditions are as follows: trichloromethyl silane is presoma, argon is diluent gas, flow 300～400ml/min, hydrogen is carrier gas, flow 200～350ml/min, and the mol ratio of hydrogen and trichloromethyl silane is 10:1, depositing temperature is 1000～1100 DEG C, and sedimentation time 120～960h obtains the silicon carbide fiber reinforced ceramic matric composite at carbon nano tube/graphene interface。
7. prepare the method for the FRCMC at graphene/carbon nano-tube interface described in claim 3 for one kind, it is characterised in that step is as follows:
Step 1: the CNT of 1 mass fraction is distributed in the deionized water solution of 1000～4000 mass fractions, add the TritonX of 0.2 mass fraction, configuration concentration is the CNT suspension of 0.25mg/ml～1mg/ml, by this CNT suspension ultrasound wave material emulsion dispersion device ultrasonic disperse 20～30min, obtain homodisperse CNT aqueous solution；
Step 2: be distributed in the deionized water solution of 1000～2000 mass fractions by the graphene oxide of 1 mass fraction, disperse 5h with ultrasonic cleaner, is configured to the graphene oxide water solution of 0.5～1mg/ml；
Step 3: CNT aqueous solution and graphene oxide water solution are mixed to form mixed solution, carbon fiber is placed in mixed solution, the method utilizing electrophoretic deposition deposits CNT at carbon fiber surface, the method simultaneously utilizing electroreduction obtains graphene oxide at carbon fiber surface, and obtaining surface deposition has CNT and the carbon fiber of the mutual doped structure of Graphene；Sedimentation time is 10～30min；
Step 5: adopt deposition SiC matrix on CVI technique carbon fiber after step 4 processes, process conditions are as follows: trichloromethyl silane is presoma, argon is diluent gas, flow 300～400ml/min, hydrogen is carrier gas, flow 200～350ml/min, and the mol ratio of hydrogen and trichloromethyl silane is 10:1, depositing temperature is 1000～1100 DEG C, and sedimentation time 120～960h obtains the silicon carbide fiber reinforced ceramic matric composite at carbon nano tube/graphene interface。
8. the method preparing the FRCMC at graphene/carbon nano-tube interface according to claim 5 or 6 or 7, it is characterised in that: in described step 5, add nitrogenous source NH3, flow is the 0.1～10 of carrier gas hydrogen, depositing temperature 800～1100 DEG C, and deposition 150～300h obtains micro nanometer fiber/Si3N4Ceramic matric composite。
9. the method preparing the FRCMC at graphene/carbon nano-tube interface according to claim 5 or 6 or 7, it is characterised in that: the CNT in described step 1 is many walls or single wall。
10. the method preparing the FRCMC at graphene/carbon nano-tube interface according to claim 5 or 6 or 7, it is characterised in that: the carbon fiber in described step 4 is single bundle carbon fiber or carbon cloth。
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