CN100411866C - Carbon fiber composite single carbon nano tube and its preparing method - Google Patents
Carbon fiber composite single carbon nano tube and its preparing method Download PDFInfo
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- CN100411866C CN100411866C CNB2005100116780A CN200510011678A CN100411866C CN 100411866 C CN100411866 C CN 100411866C CN B2005100116780 A CNB2005100116780 A CN B2005100116780A CN 200510011678 A CN200510011678 A CN 200510011678A CN 100411866 C CN100411866 C CN 100411866C
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Abstract
The present invention provides a carbon fiber composite single carbon nanometer tube which is composed of a carbon nanometer tube, conical carbon fiber and a substrate. The present invention is characterized in that the carbon nanometer tube vertically grows on the substrate, and is coated in the conical carbon fiber, and simultaneously, the top end of the conical carbon fiber extends out to form a needle tip shape. The present invention also provides a method for preparing the carbon fiber composite single carbon nanometer tube, which comprises the steps: (1) the substrate is washed cleanly; (2) a transition metal catalyst is attached to the surface of the substrate; (3) the substrate is arranged in a heating device capable of being vacuumized, and is used as one of electrodes, and the substrate is in contact with the other electrode; (4) after the heating device is vacuumized, mixed gas of reducing gas and carbon source gas is slowly introduced; (5) when the heating device reaches certain pressure intensity, current is applied between the two electrodes, and thus, the substrate temperature reaches a certain value within the range of 1600 to 2400 DEG C for maintaining for 30 to 120 seconds, and then, a powder supply is cut off; (6) the reducing gas continues to being introduced until the substrate is cooled down.
Description
Technical field
The present invention relates to a kind of CNT and preparation method thereof, more specifically, relate to a kind of carbon fiber composite single carbon nano tube that grows in graphite base and preparation method thereof.
Background technology
CNT has perfect structure and outstanding electricity and mechanical characteristic, can be used for many nanometer small size devices, as the needle point of single field emitting electronic source and various PSTMs.
At present, existing is the nano-device of core component with the single-root carbon nano-tube, for example: single feds, can be used for the needle point of PSTM etc., mostly be after CNT is synthetic, single-root carbon nano-tube is assembled into the tip of metal needle point by the little control system in the electron microscope, as shown in Figure 1, be assembly type single-root carbon nano-tube (de Jonge N, Lamy Y, Schoots K, Oosterkamp TH, High brightness electron beam from a multi-walledcarbon nanotube, Nature 2002,420,6914.), wherein CNT 1 is assembled on the metal needle point 4 by the little control system in the electron microscope.The complex process of this assembling mode, and CNT and combining of metal needle point mostly are physical property, the interface binding power of CNT and supporter and metal needle point is less, potential barrier is bigger, therefore is only applicable to study device property, is not suitable for constituting industrial device.
Also having a kind of method is that CNT is directly grown on the undersized supporter, as shown in Figure 2, CNT (Cui H for diauxic growth, Y.ang X, Baylor LR, Lowndes DH.Growth of multiwalled-carbonnanotubes using vertically aligned carbon nanofibers as templates/scaffolds andimproved field-emission properties, Applied Physics Letters 2005,86,053110.).The chemical vapour deposition technique that this method using plasma is strengthened, utilize a PE-CVD to be reflected at earlier and form taper carbon fiber 2 in the substrate 3, and then at the top of taper carbon fiber 2 deposited catalyst particle, vertical-growth goes out CNT 1 to utilize PE-CVD to react thereon at last again.The defective of this structure need to be twice complete growth course to form, and it is in conjunction with still outstanding inadequately.
In addition, the single-root carbon nano-tube that utilizes prior art for preparing generally with silicon as substrate, and form heterogeneous the contact between the CNT easily, also can influence the operating characteristic of CNT.
Summary of the invention
At the problems referred to above, the carbon fiber composite single carbon nano tube that provides a kind of sound construction, electricity and mechanical characteristic good is provided one object of the present invention, form by CNT, taper carbon fiber and substrate, it is characterized in that, described CNT vertical-growth is in substrate, and be wrapped in the taper carbon fiber, form " core " structure and expose automatically at the tip of taper carbon fiber.Wherein, described substrate is a graphite, contacts with forming homogeneity (all being carbon simple substance) between the CNT, makes carbon nano tube device provided by the invention have excellent electric property.
Wherein, described CNT is the multi-walled carbon nano-tubes of diameter in 5 to 50 nanometers, or diameter is at the SWCN of 1 to 5 nanometer; Described taper fiber comprises spiral blade dress coating, and its root diameter (RD) is at 1 to 50 micron, and tip diameter is 10 to 100 nanometers, and length is 1 to 50 micron.
Another object of the present invention is to provide a kind of preparation method of carbon fiber composite single carbon nano tube, comprises the steps:
(1) substrate is cleaned up;
(2) with transition-metal catalyst attached to substrate surface;
(3) firing equipment that will place vacuum-pumping with the substrate of catalyst is as one of electrode, and contacts with another electrode;
(4) firing equipment is vacuumized after, slowly feed the gaseous mixture of reducing gas and carbon-source gas;
(5) when the pressure in the firing equipment reaches 0.01MPa to 0.1MPa, adjust carbon source and reducing gas flow and be stabilized in two interior values of 0-100 ml/min separately, between two electrodes, add electric current, make base reservoir temperature reach a certain value in 1600 ℃ to the 2400 ℃ scopes, go out carbon atom by the carbon-source gas cracking and be deposited in the substrate this moment near substrate (being heating source), form the composite construction of carbon fiber parcel CNT, kept reaction temperature 30 to 120 seconds, cut off the electricity supply then;
(6) continue to feed reducing gas, cool off up to substrate.
Wherein, the reducing gas in the step (2) can be a hydrogen, also can be ammonia, and described carbon-source gas is selected from: methane, acetylene or ethene; The branch air pressure ratio of described reducing gas and carbon-source gas is 1: 5 to 5: 1.
Wherein, another electrode described in the step (3) can also be a graphite rod except that the electrode that this area is used always; And the purpose of two electrodes contacts is to occur electric discharge phenomena when preventing between two electrodes making alive.
Carbon fiber composite carbon nanometer tube provided by the invention, wherein the single-root carbon nano-tube vertical-growth of the carbon fiber of micro-nano magnitude and parcel thereof is on graphite base, following advantage is arranged when it is used for ballistic electronic emitting source: the first, have the fineness ratio bigger than general CNT feds (aspect ratio), this point is the characteristics of outstanding needle point field emmision material indispensability; The second, whole cone and CNT " core " vertical-growth be on graphite base, more existing assembly device, and in conjunction with more firm, structure is more stable; Three, substrate is similarly carbon simple substance material (graphite), excellent contact can provide relatively little interface potential barrier between homogeneous material, the electronics emission is just arranged under low voltage, and more help to form ballistic electronic emitting source (electronics transmits no scattering in device, that the electron waves that send have is superpower, high brightness and strong relevant characteristic).
Carbon fiber composite carbon nanometer tube provided by the invention is used for the needle point of scanning probe microscopy, and following advantage is arranged: the structure of the first, bottom taper support, nose-circle column needle point is the optimum structure of scanning probe microscopy needle point just; The second, whole cone vertical-growth is on substrate, and is highly stable; Three, fiber size is about tens of micron, even can use very convenient in the assembling of light microscope lower-pilot.
Description of drawings
Fig. 1 represents the assembly type single-root carbon nano-tube;
Fig. 2 represents the CNT of diauxic growth;
Fig. 3 represents the structural representation of carbon fiber composite single carbon nano tube;
Fig. 4 represents the pictorial diagram of carbon fiber composite single carbon nano tube;
Fig. 5 represents the view in transverse section of carbon fiber composite single carbon nano tube;
Wherein:
1-CNT 2-taper carbon fiber 3-substrate 4-metal needle point
The specific embodiment
As shown in Figure 3, be the structural representation of carbon fiber composite single carbon nano tube provided by the invention, wherein, CNT 1 vertical-growth is in substrate 3, be wrapped in simultaneously in the taper carbon fiber 2, form " core " (filament) structure, and lean out the formation tip-like at the tip of carbon fiber.
With reference to figure 4, be the preferred embodiment of carbon fiber composite single carbon nano tube provided by the invention.Among the figure, the bottom diameter of taper carbon fiber 2 is 5 microns, and the length of CNT 1 is 30 microns, and CNT 1 leans out the head portion of taper carbon fiber 2 and grows 10 microns.
Below describe the preparation method of carbon fiber composite single carbon nano tube provided by the invention in detail by preferred embodiment:
Embodiment one:
Step is as follows:
(1) graphite rod is placed analyzes absolute alcohol solution and deionized water ultrasonic cleaning repeatedly, each 5 minutes, remove the deionized water drop of remained on surface at last with alcoholic solution;
(2) method of utilizing vacuum evaporation in graphite base surface evaporation layer of metal nickel particles as catalyst;
(3) will place the reaction chamber of vacuum-pumping with the substrate of Raney nickel, and as one of electrode, and form with another electrode and contact, the tightness degree of contact will can be avoided producing when adding electric current and discharge; Two electrodes all link to each other with chamber power supply outward;
(4) reaction chamber is vacuumized, then by 1: 5 branch air pressure than slowly charging into hydrogen and methane;
(5) when the pressure in the reaction chamber reaches 0.01MPa, hydrogen flowing quantity is maintained 60 ml/min, methane flow is in 30 ml/min, between two electrodes, add electric current, the temperature at contact electrode place is raise, when base reservoir temperature reaches 1600 ℃, keep this temperature powered-down after 120 seconds;
(6) continue to charge into hydrogen, until chamber and substrate cooling.
Take out product, can see under SEM: vertical-growth a large amount of carbon fibers and the composite construction of single-root carbon nano-tube, carbon fiber composite single carbon nano tube promptly provided by the invention on the graphite base surface.
Embodiment two:
Step is as follows:
(1) ultrasonic cleaning is clean repeatedly graphite rod to be placed alcoholic solution and deionized water, removes the deionized water drop of remained on surface at last with alcoholic solution;
(2) method of utilizing vacuum evaporation at graphite base surface evaporation layer of metal iron particle as catalyst:
(3) will place the reaction chamber of vacuum-pumping with the substrate of iron catalyst, and as one of electrode, and form with another electrode and contact, the tightness degree of contact will can be avoided producing when adding electric current and discharge; Two electrodes all link to each other with chamber power supply outward;
(4) reaction chamber is vacuumized, then by 1: 1 branch air pressure than slowly charging into ammonia and acetylene;
(5) when the pressure in the reaction chamber reaches 0.05MPa, ammonia flow is maintained 80 ml/min, the acetylene flow is in 40 ml/min, between two electrodes, add electric current, the temperature at contact electrode place is raise, when base reservoir temperature reaches 2000 ℃, keep this temperature, powered-down after 60 seconds;
(6) continue to charge into ammonia, until chamber and substrate cooling.
Embodiment three:
Step is as follows:
(1) graphite rod is placed the ultrasonic cleaning repeatedly of alcoholic solution and deionized water, remove impurity, remove the deionized water drop of remained on surface at last with alcoholic solution;
(2) method of utilizing vacuum evaporation at graphite base surface evaporation layer of metal cobalt particle as catalyst;
(3) will place the reaction chamber of vacuum-pumping with the substrate of Co catalysts, and as one of electrode, and form with another electrode and contact, the tightness degree of contact will can be avoided producing when adding electric current and discharge; Two electrodes all link to each other with chamber power supply outward;
(4) reaction chamber is vacuumized, then by 5: 1 branch air pressure than slowly charging into hydrogen and ethene;
(5) when the pressure in the reaction chamber reaches 0.1MPa, hydrogen flowing quantity is maintained 80 ml/min, the ethene flow is in 40 ml/min, between two electrodes, add electric current, the temperature at contact electrode place is raise, when base reservoir temperature reaches 2400 ℃, keep this temperature powered-down after 30 seconds;
(6) continue to charge into hydrogen, until chamber and substrate cooling.
More than by embodiment the present invention is described in detail, the technology of this area is to be understood that with personnel, in the scope that does not exceed spirit of the present invention and essence, the present invention is made certain modification and distortion, clean graphite base such as replace the disclosed method of content embodiment of the present invention with additive method, perhaps the firing equipment with other vacuum-pumpings replaces the disclosed reaction chamber of the present invention, still can realize purpose of the present invention.
Claims (5)
1. the preparation method of a carbon fiber composite single carbon nano tube comprises the steps:
(1) substrate is cleaned up;
(2) with transition-metal catalyst attached to substrate surface;
(3) firing equipment that will place vacuum-pumping with the substrate of catalyst is as one of electrode, and contacts with another electrode;
(4) firing equipment is vacuumized after, slowly feed the gaseous mixture of reducing gas and carbon-source gas, wherein,
Described reducing gas is hydrogen or ammonia, and described carbon-source gas is selected from methane, acetylene or ethene, and the branch air pressure ratio of described reducing gas and carbon-source gas is 1: 5 to 5: 1;
(5) when the pressure in the firing equipment reaches 0.01MPa to 0.1MPa, the flow of keeping carbon-source gas and reducing gas is below 100 ml/min, between two electrodes, add electric current, make base reservoir temperature reach in 1600 ℃ to the 2400 ℃ scopes a certain value and kept 30 to 120 seconds, cut off the electricity supply then;
(6) continue to feed reducing gas, cool off up to substrate, go out the composite construction of a large amount of taper carbon fibers and single-root carbon nano-tube at the substrate surface vertical-growth, wherein CNT is wrapped in the taper carbon fiber, and leans out the formation tip-like from the top of taper carbon fiber.
2. the preparation method of carbon fiber composite single carbon nano tube as claimed in claim 1 is characterized in that, described substrate is a graphite.
3. the preparation method of a kind of carbon fiber composite single carbon nano tube as claimed in claim 1 or 2 is characterized in that, in described step (2), adopt vacuum vapour deposition with the transition metal particle attached on the substrate surface.
4. the preparation method of carbon fiber composite single carbon nano tube as claimed in claim 1 or 2 is characterized in that, described transition metal is iron, cobalt or nickel.
5. the preparation method of carbon fiber composite single carbon nano tube as claimed in claim 3 is characterized in that, described transition metal is iron, cobalt or nickel.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101271969B (en) * | 2007-03-23 | 2010-08-25 | 清华大学 | Carbon nano-tube combination electrode material, its production method and electrode |
| CN101821089B (en) * | 2007-09-10 | 2014-12-10 | 新加坡国立大学 | Polymeric membranes incorporating nanotubes |
| JP5497109B2 (en) * | 2012-07-03 | 2014-05-21 | 昭和電工株式会社 | Composite carbon fiber |
| CN104241061B (en) * | 2014-09-28 | 2017-05-03 | 苏州大学 | Device for suppressing secondary electron emission |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1225603A (en) * | 1996-05-15 | 1999-08-11 | 海珀里昂催化国际有限公司 | Rigid porous carbon structure, method of making, method of using and products contg. same |
| CN1344674A (en) * | 2000-09-26 | 2002-04-17 | 天津南开戈德集团有限公司 | Prepn of nano-carbon tube |
| CN1417829A (en) * | 2002-12-30 | 2003-05-14 | 中国电子科技集团公司第十二研究所 | Grid controlled carbon nanotube/carbon fiber field emitting array cathode and its making process |
| EP1413551A1 (en) * | 2002-10-22 | 2004-04-28 | Toyota Jidosha Kabushiki Kaisha | Methods for Manufacturing Multi-Wall Carbon Nanotubes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225603A (en) * | 1996-05-15 | 1999-08-11 | 海珀里昂催化国际有限公司 | Rigid porous carbon structure, method of making, method of using and products contg. same |
| CN1344674A (en) * | 2000-09-26 | 2002-04-17 | 天津南开戈德集团有限公司 | Prepn of nano-carbon tube |
| EP1413551A1 (en) * | 2002-10-22 | 2004-04-28 | Toyota Jidosha Kabushiki Kaisha | Methods for Manufacturing Multi-Wall Carbon Nanotubes |
| JP2004142967A (en) * | 2002-10-22 | 2004-05-20 | Toyota Motor Corp | Method for manufacturing multi-pipe carbon nanotube |
| CN1417829A (en) * | 2002-12-30 | 2003-05-14 | 中国电子科技集团公司第十二研究所 | Grid controlled carbon nanotube/carbon fiber field emitting array cathode and its making process |
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