CN103724043A - 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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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 matrix material and preparation method, specifically relate to a kind of high heat conduction C/C matrix material and preparation method in the modification of carbon fiber surface vertical-growth CNT (carbon nano-tube).Belong to C/C matrix material preparing technical field.
Background technology
Carbon fiber reinforced carbon base is (referred to as charcoal/charcoal, specific to the present invention, being C/C) matrix material is high with its density low and high temperature intensity, modulus is high, high high-temp stability good, linear expansivity 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 structured 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, aerospacecraft performance improves constantly, therefore also more and more higher to the performance requriements of anti-ablation for aerospace, heat insulation material.High power density electron device, nuclear fusion device can produce and accumulate a large amount of heats with plasma facing material in operational process, for guaranteeing equipment steady-state operation, the heat of generation need be derived in time, thereby the heat conductivility of material has been proposed to very high requirement.
C/C(carbon fiber reinforced carbon matrix) lattice vibration of carbon atom is the heat conducting basis of material in matrix material, be directly proportional to the degree of order of the microlitic structure of Carbon Materials.Charcoal kinds of fibers, carbon matrix are heat conducting principal passages, and " bridge " effect that between charcoal fiber and carbon matrix, heat is transmitted has been played at charcoal fiber/matrix charcoal interface.For the thermal conduction mechanism of C/C matrix material, the concrete measure that improves its heat conductivility has: (1) is used the high heat-conductive carbon fiber (as high-modulus charcoal fiber, pitch-based carbon fiber) of the crystallite degree of order high (highly-textured); (2) use the high carbon matrix (as Mesophase Pitch-based Carbon) of the crystallite degree of order; (3) interface modification, adjusts the microlitic structure of improving charcoal fiber/matrix charcoal interface, reduces boundary defect, improves the heat conduction efficiency of matrix material median surface.At present, high heat-conductive carbon fiber, the first body of high heat conduction substrate charcoal is expensive, is difficult to import, therefore by preparing high heat conduction C/C matrix material with high heat-conductive carbon fiber or carbon matrix, can cause material manufacturing cost to increase considerably.In prior art scheme, preparing high heat conduction C/C matrix material is all to select the precursor of mesophase pitch as carbon matrix, and as youth Liu, Shi Jingli etc., preparation cost is high.By contrast, material is carried out to interface modification, the interface transition layer that the design forming microtexture degree of order is high, be one on existing raw-material basis, can realize by technique adjustment the method for the high heat conduction of material.In prior art scheme, the modification of C/C composite material interface is combined for the interface of improving between charcoal fiber and resin carbon substantially, rare for the interface modification between charcoal fiber and pyrolytic carbon matrix; Lu Xuefeng etc. utilize nano carbon fiber to regulate charcoal fiber and pyrolytic carbon interface, but do not form complete interface transition layer, and are mainly used in improving the mechanical property of material, and also also not obvious to the raising of heat conductivility.
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 matrix material that thermal conductivity is high is provided; In high heat conduction C/C matrix material prepared by the present invention, vertical carbon fiber surface is evenly distributed with CNT (carbon nano-tube) (CNT), and pyrolytic carbon, at charcoal fiber and CNT (carbon nano-tube) surface deposition, forms highly-textured CNT/PyC interface transition layer.
Another object of the present invention is to provide the CNT (carbon nano-tube) (CNT) that a kind of technique is simple, easy to operate, can form at carbon fiber surface Vertical Uniform distribution, make pyrolytic carbon at charcoal fiber and CNT (carbon nano-tube) (CNT) surface deposition, form the preparation method containing the high heat conduction C/C matrix material of highly-textured CNT/PyC interface transition layer.
A kind of high heat conduction C/C matrix material of the present invention, described C/C matrix material is comprised of charcoal fibrous matrix, CNT (carbon nano-tube), pyrolytic carbon, described CNT (carbon nano-tube) is distributed in charcoal fibrous matrix surface, pyrolytic carbon is realized " three-dimensional " deposition at carbon fiber surface and CNT (carbon nano-tube) surface, forms highly-textured CNT/PyC interface transition layer.
A kind of high heat conduction C/C matrix material of the present invention, described charcoal fibrous matrix is by forming by same direction lamination without latitude cloth, and in described charcoal fibrous matrix, the volume fraction of fiber is 30～40%.
A kind of high heat conduction C/C matrix material of the present invention, the diameter of described CNT (carbon nano-tube) is 50～150nm, length 1um～10um, the mass percent of CNT (carbon nano-tube) and charcoal fibrous matrix is 2.5%～7%.
A kind of high heat conduction C/C matrix material of the present invention, described CNT (carbon nano-tube) distributes perpendicular to charcoal fibrous matrix surface uniform.
The preparation method of a kind of high heat conduction C/C matrix material of the present invention, comprises the steps:
The first step: the preparation of charcoal fibrous matrix
Get without latitude cloth carry out surface remove photoresist process after, by same direction lamination, form unidirectional long stapled charcoal fibrous matrix;
Second step: charcoal fibrous matrix surface growth CNT (carbon nano-tube)
Dry after the charcoal fibrous matrix that the first step is obtained soaks in nickel nitrate solution, then, put into CVD horizontal pipe stove, at N
2in atmosphere, in 400～500 ℃ of calcinings, remove NO
3after root, be warming up to 500～600 ℃, pass into H
2reduce, obtain the charcoal fibrous matrix of the even attached catalyst nickel of fiber surface particle; Reduction process control H
2with N
2volume ratio is 3:2～4, after reduction finishes, stops logical H
2, continue to be warming up to 750～800 ℃, stop logical N
2, passing into carbon-source gas, carrier gas, reducing gas simultaneously, growth in situ CNT (carbon nano-tube), after completion of the reaction, closes carbon-source gas, carrier gas, reducing gas, more logical N
2cool to room temperature, obtain the precast body that CNT (carbon nano-tube) is distributed in charcoal fibrous matrix surface, in Growth of Carbon Nanotubes process, the throughput ratio of carbon-source gas and reducing gas is 1:4～4.5, can guarantee that the carbon atom that hydrocarbon gas passes through after catalyst n i particle Solid solution precipitation keeps essentially identical precipitation rate at the different activities face of Ni particle, thereby assurance tube wall is vertically grown and is not bent, and obtains the CNT (carbon nano-tube) perpendicular to carbon fiber surface growth;
The 3rd step: remainder catalyst particle is removed in acidifying:
The precast body of second step gained is placed in after concentrated nitric acid soaks and is taken out, with deionized water repeatedly clean to pH be 6.5-7.5, then, dry, be purified rear precast body;
The 4th step: CVD density
After the 3rd step gained is purified, precast body is put into isothermal CVD stove, and carbon-source gas is the one in propylene, methane, Sweet natural gas, and diluent gas is nitrogen, hydrogen or its mixed gas, carry out CVD deposition, after deposition finishes, carry out graphitization processing, obtain high heat conduction C/C matrix material.
The preparation method of a kind of high heat conduction C/C matrix material of the present invention, in the first step, carries out surface without latitude cloth and removes photoresist that to process be to be placed in acetone or benzene and to soak 24～28 hours without latitude cloth, removes organic gel and the impurity of carbon fiber surface in precast body, makes its active increase; Then with deionized water, repeatedly clean 5～8 times, remove the organism that remains in carbon fiber surface; To or put into loft drier without the seasoning of latitude cloth again dries 8～10 hours in 60～80 ℃; By controlling fold without the latitude cloth number of plies, the volume fraction of controlling fiber in charcoal fibrous matrix is 30～40%.
The preparation method of a kind of high heat conduction C/C matrix material 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, the thermostat container that is placed in 90-110 ℃ is dried 8～10 hours, removes moisture, and carbon fiber surface evenly adheres to nickelous nitrate particle; Then, at N
2in atmosphere, calcine 1-～2 hour.
The preparation method of a kind of high heat conduction C/C matrix material of the present invention, in second step, passes into H
2the time of reducing is 1.0～2.0h, obtains the charcoal fibrous matrix of the even attached catalyst nickel of fiber surface particle, and nickel particle size is 0.05um～0.2um.
The preparation method of a kind of high heat conduction C/C matrix material of the present invention, in second step, in growth in situ CNT (carbon nano-tube) process, carbon-source gas is the one in CO, methane, acetylene, carrier gas and reducing gas are H
2, carbon-source gas and carrier gas and reducing gas throughput ratio are 1:4～4.5, growth time is 40～60min.
The preparation method of a kind of high heat conduction C/C matrix material of the present invention, in second step, the diameter of the CNT (carbon nano-tube) that growth obtains is 50～150nm, length 1um～10um, the mass percent of CNT (carbon nano-tube) and charcoal fibrous matrix is 2.5%～7%.
The preparation method of a kind of high heat conduction C/C matrix material of the present invention, in the 3rd step, the mass percentage concentration of concentrated nitric acid is 69%, and temperature is 100～120 ℃, and soak time is 8～14min.
The preparation method of a kind of high heat conduction C/C matrix material of the present invention, in the 4th step, CVD thickening technology parameter is, 900～1000 ℃ of depositing temperatures, propylene flow: 10～15L/min, nitrogen flow: 20～30L/min, gun pressure: 1～2Kpa, depositing time 150～250 hours; Graphitization processing treatment temp is 2000～2500 ℃, and the graphitization processing time is: 2～4 hours; Obtain the high heat conduction C/C matrix material containing CNT/PyC interfacial 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, there is excellent mechanics, electricity and thermal property, its theoretical thermal conductivity is up to 6400W/m-
1k
-1.In addition, surperficial π-electron cloud energy induced pyrolysis charcoal in chemical vapor deposition processes that CNT is special, in the orderly deposition on its surface, forms highly-textured interface transition layer structure.Therefore, the present invention is considering under the prerequisite of rational Match between material manufacturing cost, manufacturability, heat conductivility, introduces CNT (carbon nano-tube) (CNT), i.e. carbon fiber surface growth in situ CNT (carbon nano-tube) in material.The growth mechanism of CNT (carbon nano-tube) is: hydrocarbon gas divides and parses carbon atom, and carbon atom spreads by solid solution in catalyst n i particle, in catalyst activity face, separates out and forms CNT (carbon nano-tube).In Growth of Carbon Nanotubes process, control 750～800 ℃ of growth temperatures, the strict throughput ratio of controlling carbon-source gas and reducing gas is between 1:4～4.5 simultaneously, can guarantee that the carbon atom that hydrocarbon gas passes through after catalyst n i particle Solid solution precipitation keeps essentially identical precipitation rate at the different activities face of Ni particle, thereby assurance CNT (carbon nano-tube) tube wall is vertically grown and is not bent, guarantee that CNT (carbon nano-tube) distributes at carbon fiber surface Vertical Uniform, in CVD process subsequently, making pyrolytic carbon be converted to pyrolytic carbon in " two dimension " deposition of carbon fiber surface deposits in order in " three-dimensional " on charcoal fiber and CNT (carbon nano-tube) surface, form highly-textured PyC/CNT interface transition layer, both utilized the high thermal conductivity of CNT (carbon nano-tube), realized again the modification of the interfacial microstructure of material, improved 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 the charcoal fiber in charcoal fibrous matrix is carried out to surface preparation, take nickel as catalyzer, catalytic growth CNT (carbon nano-tube), then there is the charcoal fibrous matrix of carbon nanotube in CVD cvd furnace, to carry out density growth on charcoal fiber, make CNT modification C/C matrix material.Have the following advantages and positively effect:
1, take nickel as catalyzer in carbon fiber surface growth in situ CNT (carbon nano-tube), preparation method is simple, easy to operate, in the CNT (carbon nano-tube) of carbon fiber surface growth, is uniformly distributed, quality is high.With respect to the method for direct interpolation CNT (carbon nano-tube), overcome CNT (carbon nano-tube) and be difficult to equally distributed problem.
2, by regulating Growth of Carbon Nanotubes technique can control quantity and the form of CNT (carbon nano-tube), obtain heap(ed) capacity 2.5%～7%, diameter 50～150nm, length 1um～10um, perpendicular to the evenly CNT (carbon nano-tube) of growth of carbon fiber surface.
3, the CNT (carbon nano-tube) of vertical carbon fiber surface growth, in CVD process, induced pyrolysis charcoal is converted to pyrolytic carbon and deposits in order in " three-dimensional " on charcoal fiber and CNT (carbon nano-tube) surface in " two dimension " deposition of carbon fiber surface, form highly-textured CNT/PyC interface transition layer, greatly improved the heat conduction efficiency of matrix and transition layer.
4, the CNT/PyC interface modification C/C matrix material that prepared by the present invention, compared with common C/C matrix material, material thermal conductivity has improved 2～3 times being parallel to charcoal fiber direction, perpendicular to charcoal fiber direction, has improved 5 times.It is the high heat conduction C/C matrix material 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 form Vertical Uniform distribute CNT (carbon nano-tube) (CNT), make pyrolytic carbon at charcoal fiber and CNT (carbon nano-tube) (CNT) surface deposition, between charcoal fiber and pyrolytic carbon, form highly-textured CNT/PyC interface transition layer, greatly improved the heat conduction efficiency of matrix and transition layer.Be suitable for suitability for industrialized production.
Accompanying drawing explanation
The pattern of the carbon fiber surface growth in situ CNT (carbon nano-tube) that accompanying drawing 1 prepares for the embodiment of the present invention 1.
The sample pyrolytic carbon polarisation metallograph that accompanying drawing 2 prepares for the embodiment of the present invention 1.
The example interface transition layer TEM photo that accompanying drawing 3 prepares for the embodiment of the present invention 1.
From accompanying drawing 1, can find out: CNT is uniformly distributed perpendicular to carbon fiber surface.
From accompanying drawing 2, can find out: nearly fiber pyrolytic carbon is obvious highly-textured pyrolytic carbon structure.
From accompanying drawing 3, can find out: the interfacial layer microlitic structure degree of order is high that no significant defect is heat conducting efficient passage.
Embodiment
In the embodiment of the present invention, performance, pattern, the structure of the high heat conduction C/C matrix material to preparation adopt following equipment or method to measure or observe:
1, adopt the density of Archimedes's drainage test material;
2, utilize Jeol JSM-5600LV type scanning electron microscopic observation CNT pattern and structure;
3, utilize POLYVAR-MET Big Gold phase microscope to observe the interface microstructure of matrix material;
4, utilize transmission electron microscope observation CNT/PyC interfacial layer;
5, utilize JR-3 type laser heat conducting instrument to measure the thermal conductivity of material, be divided into: vertical fibers direction thermal conductivity (⊥), parallel fibers direction thermal conductivity (//).
Embodiment 1:
(1) PAN base T300(12K toray company (Toray) being produced) charcoal fiber laid is distributed in acetone soln after ultrasonic vibration half an hour, soaks 24 hours, dries after then repeatedly cleaning 6 times with deionized water stand-by in loft drier;
(2) by after treatment step (1), without latitude cloth, carry out lamination in the same direction, obtain fiber volume fraction and be 36% unidirectional macrofiber charcoal fibrous matrix;
(3) in the nickel nitrate solution that charcoal fibrous matrix step (2) being obtained is 0.2% in mass concentration, soak 4h, moisture volatilizees in air after taking out.Then precast body is put into tube furnace, at N
2in atmosphere, be heated to 450 ℃ of calcinings, insulation 1.5h, to remove NO
3root; Be warmed up to again 550 ℃, pass into H
2reduce, to obtain catalyzer nickel particle, H
2with N
2volume ratio is 3:2, stops logical H after reduction 1.0h
2; Obtain catalyzer nickel uniform particles and be attached to fiber surface, granular size is 0.05um～0.2um;
(4) continue to be warming up to 750 ℃ and stop logical N
2, pass into volume ratio is CO/H simultaneously
2the mixed gas of=1:4.3, insulation 40min growing nano carbon pipe.After completion of the reaction, close CO and H
2, more logical N
2cool to room temperature.The CNT-C/C precast body that the mass percent that obtains CNT (carbon nano-tube) CNT (carbon nano-tube) and charcoal fibrous matrix is 2.5%.
(5) concentrated nitric acid is heated to 100～110 ℃, the CNT-C/C precast body then step (4) being obtained is put into concentrated nitric acid and is soaked 8～10min, takes out, and repeatedly cleans to PH and is about 7, then be put in loft drier and dry in deionized water;
(6) step (5) precast body after treatment is placed in to CVD stove, take propylene as main charcoal source gas, nitrogen is carrier gas, carries out pyrolytic carbon deposition.980 ℃ of depositing temperatures, propylene flow: 13L/min, nitrogen flow 26L/min, gun pressure: 1.5Kpa, depositing time 200 hours.Obtaining density is 1.66g/cm
3cNT-C/C matrix material
(7) matrix material step (6) density being obtained is placed in graphitizing furnace and is heated to 2300 ℃, is incubated 3 hours, carries out graphitization processing and obtains high heat conduction C/C matrix material.
The heat conductivility of high heat conduction C/C matrix material prepared by the present embodiment is: vertical charcoal fiber direction thermal conductivity is 36.18Wm
-1k
-1, parallel charcoal fiber direction is 170.38Wm
-1k
-1.
Embodiment 2:
(1) PAN base T300(12K toray company (Toray) being produced) charcoal fiber laid is distributed in acetone soln after ultrasonic vibration half an hour, soaks 24 hours, dries after then repeatedly cleaning 6 times with deionized water stand-by in loft drier;
(2) by after treatment step (1), without latitude cloth, carry out lamination in the same direction, obtain fiber volume fraction and be 30% unidirectional macrofiber charcoal fibrous matrix;
(3) in the nickel nitrate solution that charcoal fibrous matrix step (2) being obtained is 0.1% in mass concentration, soak 4h, moisture volatilizees in air after taking out.Soak after peroxy-nitric acid nickel solution, precast body is put into tube furnace, at N
2in atmosphere, be heated to 450 ℃ of calcinings, insulation 1.5h, to remove NO
3root; Be warmed up to again 550 ℃, pass into H
2reduce, to obtain catalyzer nickel particle, H
2with N
2volume ratio is 3:2, stops logical H after reduction 1.0h
2; Obtain catalyzer nickel uniform particles and be attached to fiber surface, granular size is 0.05um～0.2um;
(4) continue to be warming up to 750 ℃ and stop logical N
2, pass into volume ratio methane/H simultaneously
2=1:4 mixed gas, insulation 50min growing nano carbon pipe.After completion of the reaction, close CO and H
2, more logical N
2cool to room temperature.Obtain CNT (carbon nano-tube) heap(ed) capacity and be 3.2% CNT-C/C precast body.
(5) concentrated nitric acid is heated to 100～110 ℃, the CNT-C/C precast body then step (4) being obtained is put into concentrated nitric acid and is soaked 8～10min, takes out, and repeatedly cleans to PH and is about 7, then be put in loft drier and dry in deionized water;
(6) step (5) precast body after treatment is placed in to CVD stove, take Sweet natural gas as main charcoal source gas, nitrogen is carrier gas, carries out pyrolytic carbon deposition.980 ℃ of depositing temperatures, propylene flow: 13L/min, nitrogen flow 39L/min, gun pressure: 1.5Kpa, depositing time 200 hours.Obtaining density is 1.64g/cm
3cNT-C/C matrix material
(7) matrix material step (6) density being obtained is placed in graphitizing furnace and is heated to 2300 ℃, is incubated 3 hours, carries out graphitization processing and obtains high heat conduction C/C matrix material
The heat conductivility of high heat conduction C/C matrix material prepared by the present embodiment is: vertical charcoal fiber direction thermal conductivity is 38.74Wm
-1k
-1, parallel charcoal fiber direction is 172.38Wm
-1k
-1
Embodiment 3
(1) PAN base T300(12K toray company (Toray) being produced) charcoal fiber laid is distributed in acetone soln after ultrasonic vibration half an hour, soaks 24 hours, dries after then repeatedly cleaning 6 times with deionized water stand-by in loft drier;
(2) by after treatment step (1), without latitude cloth, carry out lamination in the same direction, obtain fiber volume fraction and be 34% unidirectional macrofiber charcoal fibrous matrix
(3) charcoal fibrous matrix step (2) being obtained soaks 4h in 0.1% nickel nitrate solution, and moisture volatilizees in air after taking out.Soak after peroxy-nitric acid nickel solution, precast body is put into tube furnace, at N
2in atmosphere, be heated to 450 ℃ of calcinings, insulation 1.5h, to remove NO
3root; Be warmed up to again 550 ℃, pass into H
2reduce, to obtain catalyzer nickel particle, H
2with N
2volume ratio is 3:2, stops logical H after reduction 1.0h
2; Obtain catalyzer nickel uniform particles and be attached to fiber surface, granular size is 0.05um～0.2um;
(4) continue to be warming up to 750 ℃ and stop logical N
2, pass into volume ratio is acetylene/H simultaneously
2=1:4.5 mixed gas, insulation 60min growing nano carbon pipe.After completion of the reaction, close CO and H
2, more logical N
2cool to room temperature.Obtain CNT (carbon nano-tube) heap(ed) capacity and be 7% CNT-C/C precast body.
(5) concentrated nitric acid is heated to 100～110 ℃, the CNT-C/C precast body then step (4) being obtained is put into concentrated nitric acid and is soaked 8～10min, takes out, and repeatedly cleans to PH and is about 7, then be put in loft drier and dry in deionized water;
(6) step (5) precast body after treatment is placed in to CVD stove, take propylene as main charcoal source gas, nitrogen is carrier gas, carries out pyrolytic carbon deposition.980 ℃ of depositing temperatures, propylene flow: 13L/min, nitrogen flow 26L/min, gun pressure: 1.5Kpa, depositing time 200 hours.Obtaining density is 1.65g/cm
3cNT-C/C matrix material
(7) matrix material step (6) density being obtained is placed in graphitizing furnace and is heated to 2300 ℃, is incubated 3 hours, carries out graphitization processing and obtains high heat conduction C/C matrix material
The heat conductivility of high heat conduction C/C matrix material prepared by the present embodiment is: vertical charcoal fiber direction thermal conductivity is 40.16Wm
-1k
-1, parallel charcoal fiber direction is 162.47Wm
-1k
-1
The heat physical properties parameter of C/C matrix material prepared by the material of the embodiment of the present invention 1,2,3 preparations and ordinary method is in Table 1.
Table 1
Data in comparison sheet 1 are known: the prepared high heat conduction C/C matrix material of the present invention is 2.5 times of unmodified contrast sample along the thermal conductivity of fiber direction, and the thermal conductivity of vertical fibers direction is 5 times of unmodified contrast sample.
Claims (10)
1. one kind high heat conduction C/C matrix material, described C/C matrix material is comprised of charcoal fibrous matrix, CNT (carbon nano-tube), pyrolytic carbon, described CNT (carbon nano-tube) is distributed in charcoal fibrous matrix surface, pyrolytic carbon, in carbon fiber surface and CNT (carbon nano-tube) surface " three-dimensional " deposition, forms highly-textured CNT/PyC interface transition layer between charcoal fiber and pyrolytic carbon.
2. the high heat conduction C/C of one according to claim 1 matrix material, is characterized in that: described charcoal fibrous matrix is by forming by same direction lamination without latitude cloth, and in described charcoal fibrous matrix, the volume fraction of fiber is 30～40%.
3. the high heat conduction C/C of one according to claim 1 matrix material, is characterized in that: the diameter of described CNT (carbon nano-tube) is 50～150nm, length 1um～10um, and the mass percent of CNT (carbon nano-tube) and charcoal fibrous matrix is 2.5%～7%.
4. the high heat conduction C/C of one according to claim 1 matrix material, is characterized in that: described CNT (carbon nano-tube) distributes perpendicular to charcoal fibrous matrix surface uniform.
5. according to the preparation method of a kind of high heat conduction C/C matrix material described in claim 1-4 any one, comprise the steps:
The first step: the preparation of charcoal fibrous matrix
Get without latitude cloth carry out surface remove photoresist process after, by same direction lamination, form unidirectional long stapled charcoal fibrous matrix;
Second step: charcoal fibrous matrix surface growth CNT (carbon nano-tube)
Dry after the charcoal fibrous matrix that the first step is obtained soaks in nickel nitrate solution, then, at N
2in atmosphere, after 400～500 ℃ of calcinings, be warming up to 500～600 ℃, pass into H
2reduce, obtain the charcoal fibrous matrix of the even attached catalyst nickel of fiber surface particle; Reduction process control H
2with N
2volume ratio is 3:2～4, after reduction finishes, stops logical H
2, continue to be warming up to 750～800 ℃, stop logical N
2, passing into carbon-source gas, carrier gas, reducing gas simultaneously, growth in situ CNT (carbon nano-tube), after completion of the reaction, closes carbon-source gas, carrier gas, reducing gas, more logical N
2cool to room temperature, obtains CNT (carbon nano-tube) and is distributed in the precast body on charcoal fibrous matrix surface, and in Growth of Carbon Nanotubes process, the throughput ratio of carbon-source gas and reducing gas is 1:4～4.5;
The 3rd step: remainder catalyst particle is removed in acidifying:
The precast body of second step gained is placed in after concentrated nitric acid soaks and is taken out, with deionized water repeatedly clean to pH be 6.5-7.5, then, dry, be purified rear precast body;
The 4th step: CVD density
After the 3rd step gained is purified, precast body is put into isothermal CVD stove, and carbon-source gas is the one in propylene, methane, Sweet natural gas, and diluent gas is nitrogen, hydrogen or its mixed gas, carry out CVD deposition, after deposition finishes, carry out graphitization processing, obtain high heat conduction C/C matrix material.
6. a kind of preparation method of high heat conduction C/C matrix material according to claim 5, it is characterized in that: in the first step, without latitude cloth carry out surface remove photoresist process be to be placed in acetone or benzene and to soak 24～28 hours without latitude cloth, remove organic gel and the impurity of carbon fiber surface in precast body, make its active increase; Then with deionized water, repeatedly clean 5～8 times, remove the organism that remains in carbon fiber surface; To or put into loft drier without the seasoning of latitude cloth again dries 8～10 hours in 60～80 ℃; By controlling fold without the latitude cloth number of plies, the volume fraction of controlling fiber in charcoal fibrous matrix is 30～40%.
7. a kind of preparation method of high heat conduction C/C matrix material according to claim 6, 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, the thermostat container that is placed in 90-110 ℃ is dried 8～10 hours, removes moisture, and carbon fiber surface evenly adheres to nickelous nitrate particle; Then, at N
2in atmosphere, calcine behind 1-～2 hour, pass into H
2, reduce 1.0～2.0h, obtain the charcoal fibrous matrix of the even attached catalyst nickel of fiber surface particle, nickel particle size is 0.05um～0.2um.
8. a kind of preparation method of high heat conduction C/C matrix material according to claim 7, is characterized in that: in second step, in growth in situ CNT (carbon nano-tube) 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 throughput ratio are 1:4～4.5, growth time is 40～60min.
9. a kind of preparation method of high heat conduction C/C matrix material according to claim 8, is characterized in that: in the 3rd step, the mass percentage concentration of concentrated nitric acid is 69%, and temperature is 100～120 ℃, and soak time is 8～14min.
10. a kind of preparation method of high heat conduction C/C matrix material according to claim 9, it is characterized in that: in the 4th step, CVD thickening technology parameter is, 900～1000 ℃ of depositing temperatures, propylene flow: 10～15L/min, nitrogen flow: 20～30L/min, gun pressure: 1～2Kpa, depositing time 150～250 hours; Graphitization processing treatment temp is 2000～2500 ℃, and the graphitization processing time is: 2～4 hours; Obtain the high heat conduction C/C matrix material containing CNT/PyC interfacial layer.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961464A (en) * | 2015-06-17 | 2015-10-07 | 天津大学 | Carbon-based composite with high rebound resilience and high heat conductivity coefficient along thickness direction and preparation method of carbon-based composite |
| CN109112826A (en) * | 2018-08-08 | 2019-01-01 | 湖南东映碳材料科技有限公司 | A kind of preparation method for the mesophase pitch-based carbon fibers braided fabric loading carbon nano-fiber |
| CN109560270A (en) * | 2018-11-19 | 2019-04-02 | 肇庆市华师大光电产业研究院 | A kind of Se@CNT/CP self-supporting flexible electrode material, preparation method and application |
| CN109811327A (en) * | 2019-01-22 | 2019-05-28 | 陕西科技大学 | A kind of nano-interface layer/carbon nanotube-C/C composite material and preparation method |
| 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 |
| CN113831139A (en) * | 2021-09-29 | 2021-12-24 | 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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| 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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| 徐先锋 等: "炭纤维表面原位生长CNT/CNF及其生长机理", 《粉末冶金材料科学与工程》, vol. 18, no. 5, 31 October 2013 (2013-10-31), pages 769 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961464A (en) * | 2015-06-17 | 2015-10-07 | 天津大学 | Carbon-based composite with high rebound resilience and high heat conductivity coefficient along thickness direction and preparation method of carbon-based composite |
| CN109112826A (en) * | 2018-08-08 | 2019-01-01 | 湖南东映碳材料科技有限公司 | A kind of preparation method for the mesophase pitch-based carbon fibers braided fabric loading carbon nano-fiber |
| CN109560270A (en) * | 2018-11-19 | 2019-04-02 | 肇庆市华师大光电产业研究院 | A kind of Se@CNT/CP self-supporting flexible electrode material, preparation method and application |
| 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 |
| CN109811327A (en) * | 2019-01-22 | 2019-05-28 | 陕西科技大学 | A kind of nano-interface layer/carbon nanotube-C/C composite material and preparation method |
| 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 |
| CN113831139A (en) * | 2021-09-29 | 2021-12-24 | 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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