CN103724043B - High thermal conductivity C/C composite and preparation method - Google Patents
High thermal conductivity C/C composite and preparation method Download PDFInfo
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- CN103724043B CN103724043B CN201310653557.0A CN201310653557A CN103724043B CN 103724043 B CN103724043 B CN 103724043B CN 201310653557 A CN201310653557 A CN 201310653557A CN 103724043 B CN103724043 B CN 103724043B
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Abstract
A high thermal conductivity C/C composite comprises carbon fiber base bodies, nano carbon pipes, and pyrolytic carbons, wherein the nano carbon pipes are vertically distributed on the surfaces of the carbon fiber base bodies; the pyrolytic carbons are deposited on the surfaces of the carbon fibers and the nano carbon pipes in a 'three-dimensional' manner to form a high-texture CNT/PyC interface transitional layer. The preparation method comprises the following steps: laminating unidirectlonal weftless cloth to form unidirectional long carbon fibers base bodies, soaking in a nickel nitrate solution, drying and calcining; introducing H2 for reduction; after in-situ growth of nano carbon pipes, performing CVD deposition and graphitization processing to obtain the C/C composite. The composite is reasonable in structure, high in thermal conductivity, simple in process, and convenient in operation; the nano carbon pipes are vertically distributed on the surfaces of the carbon fibers; the high-texture CNT/PyC interface transitional layer is formed between the carbon fibers and the base body carbons through the processes of CVD deposition and graphitization processing, so that the heat conduction efficiency of the base bodies and the transitional layer is greatly improved. Therefore, the composite is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of high heat conduction C/C composite and preparation method, specifically relate to a kind of high heat conduction C/C composite in the modification of carbon fiber surface vertical-growth CNT and preparation method.Belong to C/C technical field of composite preparation.
Background technology
Carbon fiber reinforced carbon base is (referred to as charcoal/charcoal, specific to the present invention and C/C) composite is high with its density low and high temperature intensity, modulus is high, high high-temp stability good, linear expansion coefficient is little, thermal conductivity is high, stable friction factor, resistance to ablation, a series of excellent properties such as corrosion-resistant, be considered to the most rising a kind of novel fire resistant structural material, and be widely used in the fields such as space flight and aviation.Along with the develop rapidly of China's aeronautical and space technology, aerospace vehicle performance improves constantly, therefore also more and more higher to the performance requirement of Aero-Space anti-yaw damper, heat insulation material.High power density electronic device, nuclear fusion device can produce and accumulate a large amount of heats with in the face of plasma material in running, for ensureing equipment steady-state operation, the heat of generation need be derived in time, thus very high requirement be proposed to the heat conductivility of material.
C/C(carbon fiber reinforced carbon matrix) lattice vibration of carbon atom is the heat conducting basis of material in composite, be directly proportional to the degree of order of the microstructure of Carbon Materials.Carbon fibe kind, carbon matrix are heat conducting main thoroughfares, and Carbon fibe/carbon matrix interface then serves " bridge " effect of heat trnasfer between Carbon fibe and carbon matrix.For the thermal conduction mechanism of C/C composite, the concrete measure improving its heat conductivility has: (1) uses the high heat conductivity carbon fiber (as high-modulus Carbon fibe, pitch based carbon fiber) of the crystallite degree of order high (highly-textured); (2) carbon matrix (as Mesophase Pitch-based Carbon) that the crystallite degree of order is high is used; (3) interface modification, adjustment improves the microstructure at Carbon fibe/carbon matrix interface, reduces boundary defect, improves the heat conduction efficiency of composite median surface.At present, high heat conductivity carbon fiber, the first body of high heat conduction substrate charcoal is expensive, being difficult to import, therefore material manufacturing cost can being caused to increase considerably by using high heat conductivity carbon fiber or carbon matrix to prepare high heat conduction C/C composite.In prior art, preparing high heat conduction C/C composite is all select mesophase pitch as the precursor of carbon matrix, and as youth Liu, Shi Jingli etc., preparation cost is high.By contrast, interface modification is carried out to material, the interface transition layer that the design forming microstructure degree of order is high, be one on existing raw-material basis, realize the method for material height heat conduction by technique adjustment.In prior art, the modification of C/C composite material interface is substantially for improving the interface cohesion between Carbon fibe and resin carbon, rare for the interface modification between Carbon fibe and pyrolytic carbon matrix; Lu Xuefeng etc. utilize nano carbon fiber to regulate Carbon fibe and pyrolytic carbon interface, but do not form complete interface transition layer, and are mainly used in improving the mechanical property of material, and to the raising of heat conductivility also and not obvious.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art and a kind of rational in infrastructure, high heat conduction C/C composite that thermal conductivity is high is provided; In high heat conduction C/C composite prepared by the present invention, vertical carbon fiber surface is evenly distributed with CNT (CNT), and pyrolytic carbon, at Carbon fibe and CNT surface deposition, forms highly-textured CNT/PyC interface transition layer.
Another object of the present invention is to provide the CNT (CNT) that a kind of technique is simple, easy to operate, can form Vertical Uniform distribution at carbon fiber surface, make pyrolytic carbon at Carbon fibe and CNT (CNT) surface deposition, form the preparation method of the high heat conduction C/C composite containing highly-textured CNT/PyC interface transition layer.
A kind of high heat conduction C/C composite of the present invention, described C/C composite is made up of Carbon fibe matrix, CNT, pyrolytic carbon, described CNT is distributed in Carbon fibe matrix surface, pyrolytic carbon realizes " three-dimensional " deposition at carbon fiber surface and CNT surface, forms highly-textured CNT/PyC interface transition layer.
A kind of high heat conduction C/C composite of the present invention, described Carbon fibe matrix is formed by same direction lamination by without latitude cloth, and in described Carbon fibe matrix, the volume fraction of fiber is 30 ~ 40%.
A kind of high heat conduction C/C composite of the present invention, the diameter of described CNT is 50 ~ 150nm, length 1um ~ 10um, and the mass percent of CNT and Carbon fibe matrix is 2.5% ~ 7%.
A kind of high heat conduction C/C composite of the present invention, described CNT is uniformly distributed perpendicular to Carbon fibe matrix surface.
The preparation method of a kind of high heat conduction C/C composite of the present invention, comprises the steps:
The first step: the preparation of Carbon fibe matrix
Get without latitude cloth carry out surface remove photoresist process after, form unidirectional long stapled Carbon fibe matrix by same direction lamination;
Second step: Carbon fibe matrix surface growing nano carbon pipe
Dry after the Carbon fibe matrix that the first step obtains is soaked in nickel nitrate solution, then, put into CVD horizontal pipe stove, at N
2nO is removed in 400 ~ 500 DEG C of calcinings in atmosphere
3after root, be warming up to 500 ~ 600 DEG C, pass into H
2reduce, obtain the Carbon fibe matrix of fiber surface even attached catalyst nickel particle; Reduction process control H
2with N
2volume ratio is 3:2 ~ 4, after reduction terminates, stops logical H
2, continue to be warming up to 750 ~ 800 DEG C, stop logical N
2, pass into carbon-source gas, carrier gas, reducing gas, growth in situ CNT simultaneously, after completion of the reaction, close carbon-source gas, carrier gas, reducing gas, more logical N
2cool to room temperature, obtain the precast body that CNT is distributed in Carbon fibe matrix surface, in Growth of Carbon Nanotubes process, the flow-rate ratio of carbon-source gas and reducing gas is 1:4 ~ 4.5, can guarantee that hydrocarbon gas keeps substantially identical precipitation rate by the carbon atom after catalyst n i particle Solid solution precipitation in the different activities face of Ni particle, thus ensure that tube wall vertically grows and do not bend, namely obtain the CNT perpendicular to carbon fiber surface growth;
3rd step: remaining catalyst fines is removed in acidifying:
Be placed in by the precast body of second step gained after red fuming nitric acid (RFNA) soaks and take out, repeatedly cleaning to pH by deionized water is 6.5-7.5, and then, drying, is purified rear precast body;
4th step: CVD density
Precast body after 3rd step gained purification is put into isothermal CVD stove, and carbon-source gas is the one in propylene, methane, natural gas, and diluent gas is nitrogen, hydrogen or its mist, carry out CVD deposition, after deposition terminates, carry out graphitization processing, obtain high heat conduction C/C composite.
The preparation method of a kind of high heat conduction C/C composite of the present invention, in the first step, carrying out surface process of removing photoresist without latitude cloth is soak being placed on without latitude cloth in acetone or benzene 24 ~ 28 hours, the organic gel of carbon fiber surface and impurity in removing precast body, makes it actively increase; Then repeatedly clean 5 ~ 8 times by deionized water, removing remains in the organic matter of carbon fiber surface; Without the natural drying of latitude cloth or drying box will be put in 60 ~ 80 DEG C of oven dry 8 ~ 10 hours again; Fold without the latitude cloth number of plies by controlling institute, in control Carbon fibe matrix, the volume fraction of fiber is 30 ~ 40%.
The preparation method of a kind of high heat conduction C/C composite of the present invention, in second step, the mass percentage concentration of nickel nitrate solution is 0.1 ~ 0.3%, soak time 4 ~ 6 hours; After immersion, be placed in dry 8 ~ 10 hours of the insulating box of 90-110 DEG C, removing moisture, carbon fiber surface evenly adheres to nickel nitrate particle; Then, at N
21-~ 2 hour are calcined in atmosphere.
The preparation method of a kind of high heat conduction C/C composite of the present invention, in second step, passes into H
2the time of carrying out reducing is 1.0 ~ 2.0h, obtains the Carbon fibe matrix of fiber surface even attached catalyst nickel particle, and nickel particle size is 0.05um ~ 0.2um.
The preparation method of a kind of high heat conduction C/C composite of the present invention, in second step, in growth in situ CNT process, carbon-source gas is the one in CO, methane, acetylene, and carrier gas and reducing gas are H
2, carbon-source gas and carrier gas and reducing gas flow-rate ratio are 1:4 ~ 4.5, and growth time is 40 ~ 60min.
The preparation method of a kind of high heat conduction C/C composite of the present invention, in second step, the diameter growing the CNT obtained is 50 ~ 150nm, length 1um ~ 10um, and the mass percent of CNT and Carbon fibe matrix is 2.5% ~ 7%.
The preparation method of a kind of high heat conduction C/C composite of the present invention, in the 3rd step, the mass percentage concentration of red fuming nitric acid (RFNA) is 69%, and temperature is 100 ~ 120 DEG C, and soak time is 8 ~ 14min.
The preparation method of a kind of high heat conduction C/C composite of the present invention, in the 4th step, CVD thickening technology parameter is, depositing temperature 900 ~ 1000 DEG C, propylene flow: 10 ~ 15L/min, nitrogen flow: 20 ~ 30L/min, gun pressure: 1 ~ 2Kpa, sedimentation time 150 ~ 250 hours; Graphitization processing treatment temperature is 2000 ~ 2500 DEG C, and the graphitization processing time is: 2 ~ 4 hours; Obtain the high heat conduction C/C composite containing CNT/PyC boundary layer.
Mechanism of the present invention sketch under:
Because CNT is a kind of novel high performance carbon material, have like the structural pipe wall of graphite synusia and the caliber size of nanometer scale, have excellent mechanics, electricity and thermal property, its theoretical thermal conductivity factor is up to 6400W/m-
1k
-1.In addition, surperficial pi-electron cloud energy induced pyrolysis charcoal orderly deposition on its surface in chemical vapor deposition processes that CNT is special, forms highly-textured interfaces transition Rotating fields.Therefore, the present invention, under the prerequisite considering Proper Match between material manufacturing cost, manufacturability, heat conductivility, introduces CNT (CNT), i.e. carbon fiber surface growth in situ CNT in the material.The growth mechanism of CNT is: hydrocarbon gas divides and parses carbon atom, and carbon atom is spread by solid solution in catalyst n i particle, separates out form CNT in catalyst activity face.Growth temperature 750 ~ 800 DEG C is controlled in Growth of Carbon Nanotubes process, the flow-rate ratio of strict control carbon-source gas and reducing gas is between 1:4 ~ 4.5 simultaneously, can guarantee that hydrocarbon gas keeps substantially identical precipitation rate by the carbon atom after catalyst n i particle Solid solution precipitation in the different activities face of Ni particle, thus ensure that CNT tube wall vertically grows and do not bend, ensure that CNT distributes at carbon fiber surface Vertical Uniform, in CVD process subsequently, make pyrolytic carbon be converted to pyrolytic carbon in " two dimension " deposition of carbon fiber surface to deposit in order in " three-dimensional " on Carbon fibe and CNT surface, form highly-textured PyC/CNT interface transition layer, both make use of the high thermal conductivity of CNT, achieve again the modification of the interfacial microstructure of material, improve the thermal conductivity at interface, kill two birds with one stone, greatly improve the heat conduction efficiency of composite material interface.The present invention is owing to adopting technique scheme, first surface preparation is carried out to the Carbon fibe in Carbon fibe matrix, take nickel as catalyst, catalytic growth CNT, then the Carbon fibe matrix of nano carbon tube there is is to carry out density in CVD cvd furnace growth on Carbon fibe, obtained CNT modification C/C composite.Have the following advantages and good effect:
1, with nickel be catalyst at carbon fiber surface growth in situ CNT, preparation method is simple, easy to operate, and be uniformly distributed at the CNT of carbon fiber surface growth, quality is high.Relative to the method for directly adding CNT, overcome CNT and be difficult to equally distributed problem.
2, quantity and form by regulating Growth of Carbon Nanotubes technique can control CNT, obtain heap(ed) capacity 2.5% ~ 7%, diameter 50 ~ 150nm, length 1um ~ 10um, perpendicular to the CNT of carbon fiber surface homoepitaxial.
3, the CNT of vertical carbon fiber surface growth, in CVD process, induced pyrolysis charcoal is converted to pyrolytic carbon deposits in order in " three-dimensional " on Carbon fibe and CNT surface in " two dimension " deposition of carbon fiber surface, form highly-textured CNT/PyC interface transition layer, substantially increase the heat conduction efficiency of matrix and transition zone.
4, the CNT/PyC interface modification C/C composite prepared of the present invention, compared with common C/C composite, material thermal conductivity improves 2 ~ 3 times being parallel to Carbon fibe direction, improves 5 times perpendicular to Carbon fibe direction.It is the high heat conduction C/C composite with broad prospect of application.
In sum, the present invention is rational in infrastructure, thermal conductivity is high, technique is simple, easy to operate, can carbon fiber surface be formed Vertical Uniform distribution CNT (CNT), make pyrolytic carbon at Carbon fibe and CNT (CNT) surface deposition, between Carbon fibe and pyrolytic carbon, form highly-textured CNT/PyC interface transition layer, substantially increase the heat conduction efficiency of matrix and transition zone.Be suitable for suitability for industrialized production.
Accompanying drawing explanation
Accompanying drawing 1 is the pattern of the carbon fiber surface growth in situ CNT that the embodiment of the present invention 1 prepares.
Accompanying drawing 2 is the sample pyrolytic carbon polarisation metallograph that the embodiment of the present invention 1 prepares.
Accompanying drawing 3 is the example interface transition zone TEM photo that the embodiment of the present invention 1 prepares.
Be uniformly distributed as can be seen from accompanying drawing 1: CNT perpendicular to carbon fiber surface.
Can find out from accompanying drawing 2: nearly fiber pyrolytic carbon is obvious highly-textured pyrolytic carbon structure.
As can be seen from accompanying drawing 3: the boundary layer microstructure degree of order is high, no significant defect, it is heat conducting efficient passage.
Detailed description of the invention
In the embodiment of the present invention, following equipment or method is adopted to measure or observe to the performance of high heat conduction C/C composite of preparation, pattern, structure:
1, the density of Archimedes's drainage test material is adopted;
2, Jeol JSM-5600LV type scanning electron microscopic observation CNT pattern and structure is utilized;
3, POLYVAR-MET Big Gold phase microscope is utilized to observe the interface microstructure of composite;
4, transmission electron microscope observation CNT/PyC boundary layer is utilized;
5, utilize JR-3 type laser heat conducting instrument to measure the thermal conductivity factor of material, be divided into: vertical fibers direction thermal conductivity factor (⊥), parallel fibers direction thermal conductivity factor (//).
Embodiment 1:
(1) PAN base T300(12K toray company (Toray) produced) after Carbon fibe to be distributed in acetone soln ultrasonic vibration half an hour without latitude, to soak 24 hours, dry stand-by after then repeatedly cleaning 6 times by deionized water in drying box;
(2) in the same direction by step (1) process after carry out lamination without latitude cloth, obtain the unidirectional long fibre Carbon fibe matrix that fiber volume fraction is 36%;
(3) Carbon fibe matrix step (2) obtained is soak 4h in the nickel nitrate solution of 0.2% in mass concentration, and volatilize in air after taking out moisture.Then precast body is put into tube furnace, at N
2be heated to 450 DEG C of calcinings in atmosphere, insulation 1.5h, to remove NO
3root; Be warmed up to 550 DEG C again, pass into H
2reduce, to obtain catalyst nickel particle, H
2with N
2volume ratio is 3:2, stops logical H after reduction 1.0h
2; Obtain catalyst nickel uniform particles and be attached to fiber surface, granular size is 0.05um ~ 0.2um;
(4) continue to be warming up to 750 DEG C and stop logical N
2, pass into volume ratio is CO/H simultaneously
2the mist of=1:4.3, insulation 40min growing nano carbon pipe.After completion of the reaction, CO and H is closed
2, more logical N
2cool to room temperature.The mass percent obtaining CNT CNT and Carbon fibe matrix is the CNT-C/C precast body of 2.5%.
(5) red fuming nitric acid (RFNA) is heated to 100 ~ 110 DEG C, then the CNT-C/C precast body that step (4) obtains is put into red fuming nitric acid (RFNA) and soak 8 ~ 10min, take out, repeatedly clean in deionized water to PH and be about 7, then be put in drying box and dry;
(6) precast body after step (5) being processed is placed in CVD stove, and be main charcoal source gas with propylene, nitrogen is carrier gas, carries out pyrolytic carbon deposition.Depositing temperature 980 DEG C, propylene flow: 13L/min, nitrogen flow 26L/min, gun pressure: 1.5Kpa, sedimentation time 200 hours.Obtaining density is 1.66g/cm
3cNT-C/C composite
(7) composite that step (6) density obtains is placed in graphitizing furnace and is heated to 2300 DEG C, be incubated 3 hours, carry out graphitization processing and obtain high heat conduction C/C composite.
The heat conductivility of high heat conduction C/C composite prepared by the present embodiment is: vertical Carbon fibe direction thermal conductivity is 36.18Wm
-1k
-1, parallel Carbon fibe direction is 170.38Wm
-1k
-1.
Embodiment 2:
(1) PAN base T300(12K toray company (Toray) produced) after Carbon fibe to be distributed in acetone soln ultrasonic vibration half an hour without latitude, to soak 24 hours, dry stand-by after then repeatedly cleaning 6 times by deionized water in drying box;
(2) in the same direction by step (1) process after carry out lamination without latitude cloth, obtain the unidirectional long fibre Carbon fibe matrix that fiber volume fraction is 30%;
(3) Carbon fibe matrix step (2) obtained is soak 4h in the nickel nitrate solution of 0.1% in mass concentration, and volatilize in air after taking out moisture.After soaking pernitric acid nickel solution, precast body is put into tube furnace, at N
2be heated to 450 DEG C of calcinings in atmosphere, insulation 1.5h, to remove NO
3root; Be warmed up to 550 DEG C again, pass into H
2reduce, to obtain catalyst nickel particle, H
2with N
2volume ratio is 3:2, stops logical H after reduction 1.0h
2; Obtain catalyst nickel uniform particles and be attached to fiber surface, granular size is 0.05um ~ 0.2um;
(4) continue to be warming up to 750 DEG C and stop logical N
2, pass into volume ratio methane/H simultaneously
2=1:4 mist, insulation 50min growing nano carbon pipe.After completion of the reaction, CO and H is closed
2, more logical N
2cool to room temperature.Obtain the CNT-C/C precast body that CNT heap(ed) capacity is 3.2%.
(5) red fuming nitric acid (RFNA) is heated to 100 ~ 110 DEG C, then the CNT-C/C precast body that step (4) obtains is put into red fuming nitric acid (RFNA) and soak 8 ~ 10min, take out, repeatedly clean in deionized water to PH and be about 7, then be put in drying box and dry;
(6) precast body after step (5) being processed is placed in CVD stove, and be main charcoal source gas with natural gas, nitrogen is carrier gas, carries out pyrolytic carbon deposition.Depositing temperature 980 DEG C, propylene flow: 13L/min, nitrogen flow 39L/min, gun pressure: 1.5Kpa, sedimentation time 200 hours.Obtaining density is 1.64g/cm
3cNT-C/C composite
(7) composite that step (6) density obtains is placed in graphitizing furnace and is heated to 2300 DEG C, be incubated 3 hours, carry out graphitization processing and obtain high heat conduction C/C composite
The heat conductivility of high heat conduction C/C composite prepared by the present embodiment is: vertical Carbon fibe direction thermal conductivity is 38.74Wm
-1k
-1, parallel Carbon fibe direction is 172.38Wm
-1k
-1
Embodiment 3
(1) PAN base T300(12K toray company (Toray) produced) after Carbon fibe to be distributed in acetone soln ultrasonic vibration half an hour without latitude, to soak 24 hours, dry stand-by after then repeatedly cleaning 6 times by deionized water in drying box;
(2) in the same direction by step (1) process after carry out lamination without latitude cloth, obtain the unidirectional long fibre Carbon fibe matrix that fiber volume fraction is 34%
(3) the Carbon fibe matrix that step (2) obtains is soaked 4h in the nickel nitrate solution of 0.1%, volatilize in air after taking out moisture.After soaking pernitric acid nickel solution, precast body is put into tube furnace, at N
2be heated to 450 DEG C of calcinings in atmosphere, insulation 1.5h, to remove NO
3root; Be warmed up to 550 DEG C again, pass into H
2reduce, to obtain catalyst nickel particle, H
2with N
2volume ratio is 3:2, stops logical H after reduction 1.0h
2; Obtain catalyst nickel uniform particles and be attached to fiber surface, granular size is 0.05um ~ 0.2um;
(4) continue to be warming up to 750 DEG C and stop logical N
2, pass into volume ratio is acetylene/H simultaneously
2=1:4.5 mist, insulation 60min growing nano carbon pipe.After completion of the reaction, CO and H is closed
2, more logical N
2cool to room temperature.Obtain the CNT-C/C precast body that CNT heap(ed) capacity is 7%.
(5) red fuming nitric acid (RFNA) is heated to 100 ~ 110 DEG C, then the CNT-C/C precast body that step (4) obtains is put into red fuming nitric acid (RFNA) and soak 8 ~ 10min, take out, repeatedly clean in deionized water to PH and be about 7, then be put in drying box and dry;
(6) precast body after step (5) being processed is placed in CVD stove, and be main charcoal source gas with propylene, nitrogen is carrier gas, carries out pyrolytic carbon deposition.Depositing temperature 980 DEG C, propylene flow: 13L/min, nitrogen flow 26L/min, gun pressure: 1.5Kpa, sedimentation time 200 hours.Obtaining density is 1.65g/cm
3cNT-C/C composite
(7) composite that step (6) density obtains is placed in graphitizing furnace and is heated to 2300 DEG C, be incubated 3 hours, carry out graphitization processing and obtain high heat conduction C/C composite
The heat conductivility of high heat conduction C/C composite prepared by the present embodiment is: vertical Carbon fibe direction thermal conductivity is 40.16Wm
-1k
-1, parallel Carbon fibe direction is 162.47Wm
-1k
-1
The thermo-physical performance parameters of material prepared by the embodiment of the present invention 1,2,3 and C/C composite prepared by conventional method is in table 1.
Table 1
Data in comparison sheet 1 are known: the high heat conduction C/C composite prepared by the present invention is 2.5 times of unmodified contrast sample along the thermal conductivity factor of machine direction, and the thermal conductivity factor in vertical fibers direction is 5 times of unmodified contrast sample.
Claims (6)
1. the preparation method of one kind high heat conduction C/C composite, described C/C composite is made up of Carbon fibe matrix, CNT, pyrolytic carbon, described CNT is distributed in Carbon fibe matrix surface, pyrolytic carbon, in carbon fiber surface and CNT surface " three-dimensional " deposition, forms highly-textured CNT/PyC interface transition layer between Carbon fibe and pyrolytic carbon;
Described Carbon fibe matrix is formed by same direction lamination by without latitude cloth, and in described Carbon fibe matrix, the volume fraction of fiber is 30 ~ 40%;
The diameter of described CNT is 50 ~ 150nm, length 1 μm ~ 10 μm, and the mass percent of CNT and Carbon fibe matrix is 2.5% ~ 7%;
Described CNT is uniformly distributed perpendicular to Carbon fibe matrix surface;
Its preparation method, comprises the steps:
The first step: the preparation of Carbon fibe matrix
Get without latitude cloth carry out surface remove photoresist process after, form unidirectional long stapled Carbon fibe matrix by same direction lamination;
Second step: Carbon fibe matrix surface growing nano carbon pipe
Dry after the Carbon fibe matrix that the first step obtains is soaked in nickel nitrate solution, then, at N
2in atmosphere after 400 ~ 500 DEG C of calcinings, be warming up to 500 ~ 600 DEG C, pass into H
2reduction, obtains the Carbon fibe matrix of fiber surface even attached catalyst nickel particle; Reduction process control H
2with N
2volume ratio is 3:2 ~ 4, after reduction terminates, stops logical H
2, continue to be warming up to 750 ~ 800 DEG C, stop logical N
2, pass into carbon-source gas, carrier gas, reducing gas, growth in situ CNT simultaneously, after completion of the reaction, close carbon-source gas, carrier gas, reducing gas, more logical N
2cool to room temperature, obtains the precast body that CNT is distributed in Carbon fibe matrix surface, and in Growth of Carbon Nanotubes process, the flow-rate ratio of carbon-source gas and reducing gas is 1:4 ~ 4.5;
3rd step: remaining catalyst fines is removed in acidifying:
Be placed in by the precast body of second step gained after red fuming nitric acid (RFNA) soaks and take out, repeatedly cleaning to pH by deionized water is 6.5-7.5, and then, drying, is purified rear precast body;
4th step: CVD density
Precast body after 3rd step gained purification is put into isothermal CVD stove, and carbon-source gas is the one in propylene, methane, natural gas, and diluent gas is nitrogen, hydrogen or its mist, carry out CVD deposition, after deposition terminates, carry out graphitization processing, obtain high heat conduction C/C composite.
2. the preparation method of a kind of high heat conduction C/C composite according to claim 1, it is characterized in that: in the first step, without latitude cloth carry out surface remove photoresist process be by be placed on without latitude cloth in acetone or benzene soak 24 ~ 28 hours, remove organic gel and the impurity of carbon fiber surface in precast body, make its active increase; Then repeatedly clean 5 ~ 8 times by deionized water, removing remains in the organic matter of carbon fiber surface; Without the natural drying of latitude cloth or drying box will be put in 60 ~ 80 DEG C of oven dry 8 ~ 10 hours again; Fold without the latitude cloth number of plies by controlling institute, in control Carbon fibe matrix, the volume fraction of fiber is 30 ~ 40%.
3. the preparation method of a kind of high heat conduction C/C composite according to claim 2, it is characterized in that: in second step, the mass percentage concentration of nickel nitrate solution is 0.1 ~ 0.3%, soak time 4 ~ 6 hours; After immersion, be placed in dry 8 ~ 10 hours of the insulating box of 90-110 DEG C, removing moisture, carbon fiber surface evenly adheres to nickel nitrate particle; Then, at N
2calcine after 1 ~ 2 hour in atmosphere, pass into H
2, carry out reduction 1.0 ~ 2.0h, obtain the Carbon fibe matrix of fiber surface even attached catalyst nickel particle, nickel particle size is 0.05 μm ~ 0.2 μm.
4. the preparation method of a kind of high heat conduction C/C composite according to claim 3, it is characterized in that: in second step, in growth in situ CNT process, carbon-source gas is the one in CO, methane, acetylene, and carrier gas and reducing gas are H
2, carbon-source gas and carrier gas and reducing gas flow-rate ratio are 1:4 ~ 4.5, and growth time is 40 ~ 60min.
5. the preparation method of a kind of high heat conduction C/C composite according to claim 4, it is characterized in that: in the 3rd step, the mass percentage concentration of red fuming nitric acid (RFNA) is 69%, and temperature is 100 ~ 120 DEG C, and soak time is 8 ~ 14min.
6. the preparation method of a kind of high heat conduction C/C composite according to claim 5, it is characterized in that: in the 4th step, CVD thickening technology parameter is, depositing temperature 900 ~ 1000 DEG C, propylene flow: 10 ~ 15L/min, nitrogen flow: 20 ~ 30L/min, gun pressure: 1 ~ 2KPa, sedimentation time 150 ~ 250 hours; Graphitization processing treatment temperature is 2000 ~ 2500 DEG C, and the graphitization processing time is: 2 ~ 4 hours; Obtain the high heat conduction C/C composite containing CNT/PyC boundary layer.
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| CN104961464B (en) * | 2015-06-17 | 2017-06-06 | 天津大学 | Through-thickness has high resilience and high thermal conductivity coefficient C-base composte material and preparation method |
| CN109112826B (en) * | 2018-08-08 | 2020-10-23 | 湖南东映碳材料科技有限公司 | Preparation method of carbon nanofiber-loaded mesophase pitch-based carbon fiber braided fabric |
| CN109560270B (en) * | 2018-11-19 | 2022-04-05 | 肇庆市华师大光电产业研究院 | Se @ CNT/CP self-supporting flexible electrode material, preparation method and application |
| CN109811327B (en) * | 2019-01-22 | 2021-03-16 | 陕西科技大学 | Nano interface layer/carbon nano tube-C/C composite material and preparation method thereof |
| CN110041685A (en) * | 2019-05-08 | 2019-07-23 | 上海水沐乐歌恒温科技有限公司 | A kind of efficiently temperature inductive combined material, preparation method and the application for preparing temperature-sensing element |
| CN113831139B (en) * | 2021-09-29 | 2022-09-30 | 湖北瑞宇空天高新技术有限公司 | C/SiC composite material for gas rudder of aerospace engine and preparation method thereof |
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| CN102276282A (en) * | 2011-05-19 | 2011-12-14 | 中南大学 | Preparation method of nanometer carbon fiber reinforced carbon/carbon composite material |
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| 炭纤维表面原位生长CNT/CNF及其生长机理;徐先锋 等;《粉末冶金材料科学与工程》;20131031;第18卷(第5期);第769页摘要部分 * |
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