CN1267341C - Carbon/carbon composite material based on oriented nano carbon tube and its preparation process - Google Patents
Carbon/carbon composite material based on oriented nano carbon tube and its preparation process Download PDFInfo
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- CN1267341C CN1267341C CN 200410009951 CN200410009951A CN1267341C CN 1267341 C CN1267341 C CN 1267341C CN 200410009951 CN200410009951 CN 200410009951 CN 200410009951 A CN200410009951 A CN 200410009951A CN 1267341 C CN1267341 C CN 1267341C
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Abstract
The present invention belongs to the processing and the application range of carbon nanophase materials, which relates to a carbon/carbon composite material based on an oriented nano carbon tube and a preparation process. The composite material uses a chemical gas phase permeation method. Firstly, the composite material is put in a chemical gas phase deposition furnace through a directional nano carbon tube array which is purified and treated in a prior period; then, shield gas is introduced into the chemical gas phase deposition furnace which is evacuated. The chemical gas phase deposition furnace is heated to a setting temperature. Carrier gas flow rate is adjusted, a carbon source is introduced in the furnace, and pressure in the furnace is adjusted. An obtained composite material is deposited for one period or a plurality of periods and is graphitized after the obtained composite material is cooled. A composite material structure is mainly in a roughness layer structure and has good interface combination. Nano carbon tubes are uniformly dispersed. Shown by the test for heat conducting performance, an original state heat conducting coefficient is approximately from 13 to 42 W/m. k under the density of 0.8 to 1.5 g/cm<3>. After the graphitizing processing at 3000 DEG C, the heat conducting coefficient is improved to 70 to 190 W/m. k. The carbon/carbon composite material of the present invention, based on an oriented nano carbon tube, can be applied to high temperature dispersion devices and some electronic devices.
Description
Technical field
The invention belongs to carbon nanomaterial processing and range of application, relate to carbon/carbon composite, especially relate to a kind of carbon/carbon composite and preparation method based on aligned carbon nanotube.
Background technology
Carbon nanotube because it has particular structure and excellent performance, has made it become the focus of material area research since 1991 are found.Carbon nanotube is embodied in macrostructure or functional materials at the excellent properties that microcosm embodied become carbon nanotube in the important topic that is faced aspect the application and development.Researchers have been studied carbon nanotube and other material, as polymkeric substance, the matrix material that pottery and metal etc. are made, as: carbon nano-tube/poly benzene composite material (Appl.Phys.Lett.76 (2000) 2868-70), carbon nano tube/epoxy resin (Chemistry of Materials 12 (2000) 1049-52), carbon nanotube/silicon carbide (Journal of Materials Science 33 (1998) 5243-6), carbon nanotube/aluminium (Carbon 37 (1999) 855-8) etc., find that the result is far below desired value, the excellent properties of carbon nanotube is difficult to embody, trace it to its cause: at first, the dispersion of carbon nanotube in matrix is bad, is difficult to reach homogeneous; Next, carbon nanotube forms strong interface than difficulty with matrix and combines.This becomes two difficult problems of puzzlement carbon nano tube compound material development.
Carbon/carbon composite is that carbon fiber strengthens based composite material of carbon.Carbon/carbon composite at the interface, there is excellent performance structure, heat conduction and aspect such as anti-oxidant, and in association area the application of success is arranged, as Aeronautics and Astronautics, medical treatment, sports goods etc.The at present domestic aircraft brake sheet that the research and the application of carbon/carbon composite mainly also are confined to military domain and civil area.On research direction, domestic mainly concentrating on optimized the technology shortening cycle and traditional carbon/carbon composite carried out improvement in performance research, wherein add refractory metal improving ablation resistance, complex gradient coating all has breakthrough with the research that improves antioxidant property etc.
The back just is difficult to be greatly improved again but the performance of the intensity of carbon/carbon composite, heat conduction, aspect such as anti-oxidant acquires a certain degree, and this is also relevant with the limitation of the intensity of charcoal fiber own, heat conduction, resistance of oxidation except outside the Pass having with preparation technology.Carbon nanotube is compared with carbon fiber, has certain advantage at aspects such as structure, intensity, heat conduction, resistance of oxidation, therefore, in conjunction with the chemical vapor infiltration technology of traditional carbon/carbon composite, it is feasible utilizing directional carbon nanotube array to prepare novel carbon/carbon composite.On the one hand, the novel carbon/carbon composite of this in-situ deposition charcoal preparation has been avoided carbon nanotube dispersive obstacle; On the other hand, pyrolytic carbon combines well with the carbon nanotube interface, and thisly adjusts controllable interface by technology and fully played in conjunction with the intensity that can make carbon nanotube, heat conduction, performance such as anti-oxidant.Utilizing directional carbon nanotube array to prepare carbon/carbon composite does not appear in the newspapers both at home and abroad as yet.
The present invention uses for reference the preparation technology of traditional carbon/carbon composite, makes full use of the characteristics of directional carbon nanotube array and chemical vapor infiltration method, prepares the interface in conjunction with good, the finely dispersed matrix material of carbon nanotube.This novel aligned carbon nanotube/carbon composite has that proportion is little, heat conduction, conduction, friction, characteristics that antioxidant property is good, is better than traditional carbon/carbon composite in some aspects.This type material can partly replace traditional carbon/carbon composite in some field, and owing to its high directed heat conduction, high temperature resistant, oxidation resistant characteristics, may will have a wide range of applications aspect electron device.
Summary of the invention
One of purpose of the present invention provides that a kind of proportion is little, good heat conductivity, aligned carbon nanotube/carbon composite that frictional behaviour is good.
Two of purpose of the present invention provides the preparation method that a kind of technology is simple, be applicable to the carbon nano tube compound material of suitability for industrialized production.
A kind of carbon/carbon composite that the present invention proposes based on aligned carbon nanotube, it is characterized in that: described matrix material is skeleton with the directional carbon nanotube array, utilize the chemical vapor infiltration method to deposit pyrolytic carbon on carbon nanotube, reaching density of material is 0.7～1.7g/cm
3After, carry out graphitization processing, obtain the good carbon/carbon composite of graphite-structure.
The preparation method of the present invention proposes a kind of carbon/carbon composite based on aligned carbon nanotube, adopt the chemical vapor infiltration method, it is characterized in that: described method at first will through the early stage purification process directional carbon nanotube array put into chemical vapor deposition stove, vacuumize, feed high pure nitrogen or argon shield then, flow is 1～2L/min; Heat temperature raising is to 900～1100 ℃ of design temperatures; After stablizing 1h, adjusting carrier gas flux, feed carbon source then, is carbon source with methane or propane or propylene, is carrier gas with high pure nitrogen or argon gas, and the flow proportional of carbon source and carrier gas is 1: 1～1: 4; Adjust furnace pressure simultaneously to operating pressure 1000～5000Pa; Depositing time is an one-period with 80～120h in the described chemical vapor infiltration method, and deposition one-period or a plurality of cycle, sample is taken out in the cooling back, carries out graphitization processing then.
The carbon/carbon composite that the present invention proposes based on aligned carbon nanotube, described matrix material carbon structure is mainly rough laminar microstructure, the interface is in conjunction with good, carbon nanotube is uniformly dispersed, material proportion is little, heat conduction, conduction, anti-oxidant, frictional behaviour good.
Utilize the carbon/carbon composite of preparation method's preparation of the present invention based on aligned carbon nanotube, when depositing time is 100h, the SEM pictorial display of sample has deposited continuous and uniform pyrolytic carbon layer on aligned carbon nanotube, inner pyrolysis carbon layer is about 100～150nm.HRTEM pictorial display, pyrolytic carbon layer are that core distributes in the form of a ring with the carbon nanotube.The polarisation metallurgical microscopic image shows that this novel aligned carbon nanotube/carbon composite is mainly rough laminar microstructure.Before and after 3000 ℃ of graphitization processing, density only is 0.8g/cm
3Aligned carbon nanotube/carbon composite resistivity be respectively 32 * 10
-6With 62 * 10
-6Ω m, the starting temperature of thermal ablation weightlessness is respectively 750 and 850 ℃ in air.The heat conductivility test shows that this material is at 0.8～1.5g/cm
3Density under, former primary state thermal conductivity is about 13～42W/mK, after 3000 ℃ of graphitization processing, thermal conductivity is brought up to 70～190W/mK.This carbon/carbon composite based on aligned carbon nanotube can be applicable to high-temperature heat radiation device and portions of electronics device.
Description of drawings
Fig. 1 a and Fig. 1 b are the SEM microstructure photograph of directional carbon nanotube array;
Fig. 2 a and Fig. 2 b are respectively the SEM and the HRTEM microstructure photograph of the aligned carbon nanotube/carbon composite behind the chemical vapor infiltration;
Fig. 3 is the polarisation metallography microscope structure photo of aligned carbon nanotube/carbon composite;
Fig. 4 a and Fig. 4 b are respectively the thermal diffusivity α of aligned carbon nanotube/carbon composite and thermal conductivity λ, and (density is 0.8g/cm with the graphitization processing variation of temperature
3);
(density is 0.8g/cm to Fig. 5 with variation of temperature for the resistivity through aligned carbon nanotube/carbon composite after 3000 ℃ of graphitization processing
3);
(density was 0.8g/cm to aligned carbon nanotube/carbon composite after Fig. 6 a and Fig. 6 b were respectively initial state and 3000 ℃ of graphitization processing
3) with the same process condition under common carbon/carbon composite (density is 1.5g/cm
3) aerial oxidation weight loss correlation curve.
Embodiment
The preparation method that the present invention proposes based on the carbon/carbon composite of aligned carbon nanotube; will through early stage purification process directional carbon nanotube array put into chemical vapor deposition stove as skeleton, vacuumize, heat up; feed high pure nitrogen or argon shield simultaneously, flow is 1～2L/min.After temperature reaches design temperature, stablizes 1h, adjust carrier gas flux, feed carbon-source gas then, adjust furnace pressure simultaneously to operating pressure.The deposition one-period, sample is taken out in the cooling back.Sample can carry out the multicycle deposition, to improve density, also can carry out subsequent disposal, as graphitization processing, obtains the good carbon/carbon composite of graphite-structure.This method is substrate with the silica glass, and dimethylbenzene is carbon source, and ferrocene is a catalyzer, and high pure nitrogen or argon gas are carrier gas.Described directional carbon nanotube array can carry out the activation treatment in early stage, and obtaining better deposition effect, activating treatment process comprises hydrogen peroxide activation, air-activated, carbonic acid gas activation, laser treatment.
The present invention will be further described below in conjunction with embodiment:
Embodiment 1
(1) directional carbon nanotube array is put into chemical vapor deposition stove, vacuumize earlier, treat that the pressure-stabilisation post-heating heats up, feed the high pure nitrogen protection then, flow is 1L/min;
(2) be warming up to 950 ℃, stablize 1h;
(3) adjusting the high pure nitrogen flow is 6L/min, feeds propane then, and flow is 3L/min, adjusts furnace pressure simultaneously it is stabilized in about 2000Pa;
(4) behind the deposition 80h, blowing out is cooled to below 300 ℃, takes out bulk sample;
(5) bulk sample is carried out 2500 ℃ of graphitization processing under protection of inert gas.
Embodiment 2
(1) directional carbon nanotube array is put into chemical vapor deposition stove, vacuumize earlier, treat that the pressure-stabilisation post-heating heats up, feed the high pure nitrogen protection then, flow is 1.5L/min;
(2) be warming up to 1000 ℃, stablize 1h;
(3) adjusting the high pure nitrogen flow is 12L/min, feeds third rarely then, and flow is 4L/min, adjusts furnace pressure simultaneously it is stabilized in about 3000Pa;
(4) behind the deposition 100h, blowing out is cooled to below 300 ℃, takes out bulk sample;
(5) surface treatment is carried out in the bulk sample machining, carried out second then under the same conditions and take turns chemical vapour deposition to improve density;
(6) bulk sample is carried out 2300 ℃ of graphitization processing under protection of inert gas.
Embodiment 3
(1) with directional carbon nanotube array under 400 ℃ of argon shields, feed 30% aqueous hydrogen peroxide solution, flow is 0.5ml/min, feeds 10min and carries out purification process;
(2) directional carbon nanotube array after the purification process is put into chemical vapor deposition stove, vacuumize earlier, treat that the pressure-stabilisation post-heating heats up, feed the high pure nitrogen protection then, flow is 2L/min;
(3) be warming up to 1050 ℃, stablize 1h;
(4) adjusting the high pure nitrogen flow is 8L/min, feeds methane then, and flow is 8L/min, adjusts furnace pressure simultaneously it is stabilized in about 4000Pa;
(5) behind the deposition 120h, blowing out is cooled to below 300 ℃, takes out bulk sample;
(6) bulk sample is carried out 2800 ℃ of graphitization processing under protection of inert gas.
Claims (2)
1, a kind of carbon/carbon composite based on aligned carbon nanotube, it is characterized in that: described matrix material is skeleton with the directional carbon nanotube array, utilizes the chemical vapor infiltration method to deposit pyrolytic carbon on carbon nanotube, reaching density of material is 0.7～1.7g/cm
3After, carry out graphitization processing, obtain the good carbon/carbon composite of graphite-structure.
2, the method for a kind of a kind of carbon/carbon composite based on aligned carbon nanotube as claimed in claim 1 of preparation, adopt the chemical vapor infiltration method, it is characterized in that: described method at first will through the early stage purification process directional carbon nanotube array put into chemical vapor deposition stove, vacuumize, feed high pure nitrogen or argon shield then, flow is 1～2L/min; Heat temperature raising is to 900～1100 ℃ of design temperatures; After stablizing 1h, adjusting carrier gas flux, feed carbon source then, is carbon source with methane or propane or propylene, is carrier gas with high pure nitrogen or argon gas, and the flow proportional of carbon source and carrier gas is 1: 1～1: 4; Adjust furnace pressure simultaneously to operating pressure 1000～5000Pa; Depositing time is an one-period with 80～120h in the described chemical vapor infiltration method, and deposition one-period or a plurality of cycle, sample is taken out in the cooling back, carries out graphitization processing then.
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| JP4701431B2 (en) * | 2006-01-06 | 2011-06-15 | 独立行政法人産業技術総合研究所 | Aligned carbon nanotube bulk structure having different density portions, and production method and use thereof |
| CN101186130B (en) * | 2007-12-07 | 2013-01-02 | 中国科学院上海硅酸盐研究所 | Ceramic matrix layered material with high wave absorbing efficiency and preparation method |
| CN101898758B (en) * | 2010-06-29 | 2012-08-29 | 清华大学 | Composite structure of carbon nano tube |
| CN103058167B (en) * | 2012-12-05 | 2015-05-20 | 天津大学 | Composite material of carbon nanotube and carbon, and preparation method thereof |
| CN105271165B (en) | 2014-07-25 | 2017-10-24 | 清华大学 | Carbon-fiber film |
| CN105439114B (en) | 2014-07-25 | 2018-02-27 | 清华大学 | Carbon-fiber film and preparation method thereof |
| CN105406025B (en) | 2014-07-25 | 2017-11-17 | 清华大学 | Negative electrode of lithium ion battery |
| CN105280931B (en) | 2014-07-25 | 2017-10-24 | 清华大学 | Fuel cell membrane electrode |
| CN104692357B (en) * | 2015-02-15 | 2017-10-17 | 清华大学 | A kind of CNT/spherical composite of charcoal multi-stage porous and preparation method thereof |
| CN104892016A (en) * | 2015-05-26 | 2015-09-09 | 南昌大学 | Preparation method of carbon-carbon composite material |
| CN105693263B (en) * | 2016-01-14 | 2018-04-06 | 西北工业大学 | A kind of preparation method of CNT multidimensional braiding precast body ceramic matric composite |
| CN108383536B (en) * | 2018-02-26 | 2021-06-29 | 陕西科技大学 | Preparation method of carbon-based composite material |
| CN115772038A (en) * | 2022-11-29 | 2023-03-10 | 湖北冠毓新材料科技有限公司 | Preparation method of oriented carbon nanotube modified ceramic material |
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