CN1530320A - Carbon nanometer pipe material and preparing method thereof - Google Patents

Carbon nanometer pipe material and preparing method thereof Download PDF

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Publication number
CN1530320A
CN1530320A CNA031139299A CN03113929A CN1530320A CN 1530320 A CN1530320 A CN 1530320A CN A031139299 A CNA031139299 A CN A031139299A CN 03113929 A CN03113929 A CN 03113929A CN 1530320 A CN1530320 A CN 1530320A
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China
Prior art keywords
carbon nanotube
carbon
tube material
nano
nanotube
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CNA031139299A
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Chinese (zh)
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徐绍中
陈弥坚
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Priority to CNA031139299A priority Critical patent/CN1530320A/en
Publication of CN1530320A publication Critical patent/CN1530320A/en
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Abstract

A carbon nanotube material has multiple carbon nanotubes which are sequentially connected on a same plane, resulting in better contact between nanotubes and high electric and thermal conductivities. Its preparing process is also disclosed.

Description

A kind of carbon nano-tube material and preparation method thereof
[technical field]
The invention relates to a kind of carbon nano-tube material and preparation method thereof, particularly about a kind of carbon nano-tube material of a plurality of carbon nanotubes being made predetermined pattern or shape and preparation method thereof.
[background technology]
Carbon nanotube is a kind of new carbon, owing to it has particular structure and peculiar physics, chemical property and potential application prospect is subjected to people's attention.Carbon nanotube is the tubular material that is curled and to be formed by the graphite linings carbon atom, and its diameter is generally several nanometers to tens nanometers, and thickness only is several nanometers, and it and graphite, diamond be allotropic substance each other, generally can divide two kinds of Single Walled Carbon Nanotube and multi-walled carbon nano-tubes.Carbon nanotube is that Japanese scientist Iijima found in 1991, sees also " Helicalmicrotubules of graphitic carbon ", S Iijima, Nature, vol.354, p56 (1991).
Carbon nanotube has three kinds of different curling modes of Armchair, Zigzag and Chiral respectively, and the different carbon nanotubes that curl mode have different electroconductibility, and therefore, carbon nanotube both can show as good metal electroconductibility, also can show as semiconductive.Discover, the electroconductibility of metallic carbon nanotubes can compare favourably with best metallic substance, even it is better, and the carbon nanotube of semiconductive also can compare favourably with best semiconductor material, sees also " Single-Walled Carbon Nanotube Electronics ", IEEETransactions on Nanotechnology, vol.1, No.1 p78-85 (2002), therefore, carbon nanotube can be used as best metal or semiconductor material is applied in the electron device.
In addition, the heat conductivility excellence of carbon nanotube sees also " Unusually High ThermalConductivity of Carbon Nanotubes ", Savas Berber, Young-Kyun Kwon, andDavid Tom á nek, Phys.Rev.Lett.84,4613 (2000) one literary compositions.Therefore, carbon nanotube also can be used as good thermally conductive material.
The preparation method of carbon current nanotube mainly contains three kinds, arc discharge method, laser evaporation method and chemical Vapor deposition process.The carbon nanotube main drawback of arc discharge method and laser evaporation method gained is the carbon nano-tube bundle that product mostly is winding, woollen yarn knitting and chaotic, is difficult to directly use; Chemical Vapor deposition process is to make catalyzer with metal nanoparticle (as iron, cobalt, nickel or its oxide compound), and catalytic pyrolysis carbonaceous gas (as ethene or acetylene) grows carbon nanotube on catalyzer under 650 ℃～1000 ℃ temperature condition.The carbon nanotube that this method is produced is the carbon nano pipe array of arranged vertical, can directly apply to feds or atomic force microscope etc.But the length of this carbon nanotube only reaches micron order, is unfavorable for the application of large-size device.
People such as Brigitte Vigolo deliver a kind of method for preparing macroscopic carbon nano-tube fibre, specifically see also " Macroscopic Fibers and Ribbons of Oriented Carbon Nanotubes ", Science, Vol.290, P1331-1334 (2000) one literary compositions.This method at first is dispersed in carbon nanotube in the surfactant soln, by polymers soln it is condensed into the carbon nanotube mesh fabric then, at last this reticulated is made large-sized carbon nano-tube fibre.
But, the resulting carbon nano-tube fibre resistance of above-mentioned preparation method is very big, substantially be nonmetal character, its reason is that each carbon nanotube does not form good ordered arrangement, even the adjacent carbon nanotube pitch that has is very big, be not in contact with one another at all, thereby can not give full play to the good electric conductivity and the heat conductivility of carbon nanotube.Therefore, provide a kind of ordered arrangement, be in contact with one another good and to have a carbon nano-tube material of larger size range very necessary.
[summary of the invention]
The object of the present invention is to provide a kind of ordered arrangement, be in contact with one another well and have carbon nano-tube material than length.
Another object of the present invention is to provide the preparation method of aforementioned carbon nano-tube material.
The invention provides a kind of carbon nano-tube material, comprise many carbon nanotubes, wherein, each carbon nanotube is arranged at grade, and the adjacent carbons nanotube joins end to end substantially, thereby makes that contact is good between the carbon nanotube.
The preparation method of this carbon nano-tube material comprises the following steps: to provide a vacuum chamber, and a plurality of carbon nanotubes are provided, and wherein an end of each carbon nanotube contains the nano particle of Ferrious material or its oxide compound; In this vacuum chamber, continue to discharge an amount of carbon nanotube, apply a action of a magnetic field simultaneously in this carbon nanotube; In vacuum chamber, one carbon nanotube collection device movably is set at a distance of this carbon nanotube point of release a distance, and orders about this collection device and move along a pre-determined direction along this carbon nanotube direction of motion; Carbon nanotube moves to this collection device, and becomes predetermined pattern or shape along the horizontal ordered arrangement of pre-determined direction.
Compared with prior art, each carbon nanotube of carbon nano-tube material of the present invention is arranged in order, and the contact of adjacent carbons nanotube is good, can give full play to carbon nanotube favorable conductive and thermal conductivity.
[description of drawings]
Fig. 1 is a carbon nano-tube material preparation method schema of the present invention.
Fig. 2 is the carbon nano pipe array synoptic diagram with the chemical Vapor deposition process preparation.
Fig. 3 is the carbon nanotube enlarged view of Fig. 2.
Fig. 4 is preparation method's synoptic diagram of first embodiment of the invention.
Fig. 5 is the synoptic diagram of first embodiment of the invention.
Fig. 6 is the synoptic diagram of second embodiment of the invention.
[embodiment]
Seeing also Fig. 1, is carbon nano-tube material preparation method schema of the present invention.It comprises the following steps:
Step 1 provides carbon nanotube and carries out pre-treatment.The carbon nanotube that provides required for the present invention, require an end to comprise Ferrious material or its oxide nano particles, in general, with Ferrious material or its oxide compound is that the prepared carbon nanotube of Preparation of catalysts method all can satisfy this requirement, for example the carbon nano pipe array of chemical vapor deposition (CVD) method preparation.General CVD method is to make catalyzer with Ferrious material (comprising iron, cobalt, nickel) or its oxide compound, on silicon or substrate of glass, form the nano level metal particle through chemical process, feed carbon-source gas (as ethene or acetylene) again, thermo-cracking carbon source gas in 700～1000 ℃ of temperature ranges, thereby synthesizing carbon nanotubes array on granules of catalyst, common carbon nano tube growth are put an end and are comprised the remaining granules of catalyst of reaction.The carbon nano pipe array of aforementioned gained still is abutting orientation, has Intermolecular Forces between the adjacent carbons nanotube, is difficult to disperse, and needs through pre-treatment it is separated, and can add tensio-active agent usually and carries out ultrasonic separation and reach purpose.
Step 2 provides a vacuum chamber, and movably collector is set in vacuum chamber.This vacuum chamber is the container of a vacuum, and it can avoid the resistance of air, because the volume of carbon nanotube and quality are very little, therefore, the resistance of air be can not ignore.In addition, a predetermined position is provided with a movably collector in vacuum chamber, is used for collecting carbon nanotube, and this collector can be the substrate that silicon or other material form.This collector can move in horizontal plane or rotate.
Step 3 discharges through pretreated carbon nanotube in vacuum chamber, applies the action of a magnetic field power simultaneously.To place in the vacuum chamber through pretreated carbon nanotube, discharge an amount of carbon nanotube, because of its gravitate is done the movement of falling object, the action of a magnetic field power that applies is simultaneously given the carbon nanotube that discharges, and the action of a magnetic field is on the Ferrious material of carbon nanotube one end, with its magnetization, thereby produce the reactive force that inhale mutually in different in nature magnetic field, make this carbon nanotube accelerated motion, thereby in moving process, carbon nanotube is adjusted into vertical state by the action of a magnetic field from state at random.
Step 4, mobile collectors receives carbon nanotube.When carbon nanotube after the action of a magnetic field is adjusted into the motion of vertical state, its end that contains Ferrious material at first lands on the surface of collector, because of collector is kept in motion, thus the carbon nanotube after landing because of inertia effect, its other end is toppled over to the reverse direction of collector motion.If keep the direction of motion of collector constant, can make the different carbon nanotubes of the collector surface of landing successively keep identical toppling direction, thereby reach the purpose that the carbon nanotube same way as is arranged; If change the direction of motion of collector, the toppling direction of carbon nanotube is changed, thereby change the arrangement mode of carbon nanotube.
Below will describe embodiments of the present invention in detail with specific embodiment.
See also Fig. 2 and Fig. 3, be to reach wherein carbon nanotube enlarged view with the carbon nano pipe array synoptic diagram that the CVD method prepares, a plurality of carbon nanotubes 13 of same length are vertically arranged the surface that forming array is formed on substrate 11, wherein vegetative point one end of each carbon nanotube 13 comprises metal nanoparticle 14, this metal nanoparticle 14 is the remaining granules of catalyst of reaction, be generally iron, cobalt, nickel or its oxide compound, its particle diameter diameter general and carbon nanotube 13 is suitable, is 1～50 nanometer.
This carbon nano pipe array taken off carry out pre-treatment and make it to separate, for example, dissolve in the solution that contains tensio-active agent, through ultrasonication and after separating, dry getting final product.
Seeing also Fig. 4, is preparation method's synoptic diagram of first embodiment of the invention.Vacuum chamber 20 inside are provided with a container 30 and a collector 22, and wherein, this collector 22 and container 30 be at a distance of certain distance, and collector 22 can drive and be moved by driving wheel 24, and other has a magnet 26 to place under the collector 22, can produce magnetic field.Container 30 is built-in with a plurality of carbon nanotubes 13 of same length, and this carbon nanotube 13 is through the separated attitude of pre-treatment, and each carbon nanotube 13 1 end contains metal nanoparticle 14, as the ferrous metal nano particle.Discharge certain quantity of carbon nanometer pipe 13, then its gravitate and the movement of falling object, simultaneously, magnet 26 under the collector 22 produces the action of a magnetic field on the metal nanoparticle 14 of this carbon nanotube 13, by the action of a magnetic field, quicken carbon nanotube 13 motions, and adjust carbon nanotube 13 to vertical shape, when carbon nanotube 13 moved to collector 22, an end that contains metal nanoparticle 14 at first landed on the surface of collector 22.Because collector 22 is driven wheel 24 and drives, collector 22 moves along a fixed-direction, and the end that carbon nanotube 13 contains metal nanoparticle 14 lands on collector 22 surfaces, and the other end is toppled over to collector reverse movement direction.Follow-up carbon nanotube 13 repeats this process, be arranged in the surface of collector 22 in the same manner, movement velocity by the release rate and the collector 22 of controlling carbon nanotube 13, it is the spacing of may command adjacent carbons nanotube 13, thereby, select suitable carbon nanotube 13 release rate and the movement velocity of collector 22, adjacent carbons nanotube 13 is joined end to end, keep in touch good.In addition, for keeping the firm combination of carbon nanotube 13, carbon nanotube 13 bondings that can utilize binding agent (not shown) to finish alignment processes are fixed.
Seeing also Fig. 5, is the carbon nano-tube material synoptic diagram of first embodiment of the invention method preparation, and wherein carbon nanotube 13 is arranged in collector 22 surfaces along equidirectional, and adjacent carbons nanotube 13 roughly joins end to end, and keeps well contact.
Seeing also Fig. 6, is the synoptic diagram of second embodiment of the invention.Present embodiment and first each step of embodiment implementation method are roughly the same, difference is that collector 22 is made circumferential motion around its center in the present embodiment, it is circular-arc that the result makes that carbon nanotube 13 is arranged in, and each carbon nanotube 13 still joins end to end, and keeps well contact.
Third embodiment of the invention is with the first embodiment difference, makes collector 22 first moving linearlies, remakes circumferential motion, and carbon nano-tube material with the circular arc combined shaped can obtain being arranged in a straight line.
Fourth embodiment of the invention, be with the first embodiment difference, in carbon nanotube 13 sepn processes, the process of control ultrasonication, make many (as 2～200) carbon nanotubes 13 still be combined into a carbon nano-tube bundle, so a plurality of carbon nano-tube bundles are prepared into the carbon nanotube beam material of predetermined shape or pattern by the step of first embodiment.
Carbon nano-tube material provided by the present invention, wherein each carbon nanotube is arranged in order, and the contact of adjacent carbons nanotube is good, can give full play to carbon nanotube favorable conductive and thermal conductivity, thereby is suitable for preparing carbon nanotube conducting or thermally conductive material or device exploitation.
Carbon nano-tube material of the present invention and preparation method thereof can also have other to change design, for example for adapting to actual needs, the mode of motion that can change collector 22 is straight line, broken line, circumferential motion or its combination, thereby forms the carbon nano-tube material of different spread geometries or pattern; Or with the 13 formation carbon nano-tube bundles releases of many carbon nanotubes, a plurality of carbon nano-tube bundles are arranged and are formed carbon nano-tube material or the like, all belong to the variation that the present invention allows.

Claims (10)

1. a carbon nano-tube material comprises many carbon nanotubes, it is characterized in that these many carbon nanotubes are arranged in on the one side, and the head and the tail of at least one carbon nanotube connects other adjacent carbon nanotube respectively.
2. carbon nano-tube material as claimed in claim 1, it is characterized in that these many carbon nanotubes along same direction parallel arrangement on this plane.
3. carbon nano-tube material as claimed in claim 1 is characterized in that the head and the tail of each carbon nanotube connect other adjacent carbon nanotube respectively.
4. carbon nano-tube material as claimed in claim 3, it is characterized in that these many carbon nanotubes on this plane, arrange form circular.
5. the preparation method of a carbon nano-tube material, it comprises the following steps:
(a) provide a vacuum chamber, and many carbon nanotubes are provided, wherein an end of each carbon nanotube contains the nano particle of Ferrious material or its oxide compound;
(b) in this vacuum chamber, continue to discharge an amount of carbon nanotube, apply a action of a magnetic field simultaneously at this carbon nanotube;
(c) in vacuum chamber, one carbon nanotube collection device movably is set at a distance of this carbon nanotube point of release a distance, and orders about this collection device and do a predetermined motion along this carbon nanotube direction of motion;
(d) carbon nanotube moves to this collection device, and becomes predetermined pattern or shape along the horizontal ordered arrangement of pre-determined direction.
6. the preparation method of carbon nano-tube material as claimed in claim 5, it is characterized in that this step (b) can further comprise the burst size of adjusting carbon nanotube, it is continuous substantially to make that carbon nanotube can satisfy adjacent carbons nanotube head and the tail when being subjected to the action of a magnetic field to move to this collection device.
7. the preparation method of carbon nano-tube material as claimed in claim 5 is characterized in that this Ferrious material comprises iron, cobalt, nickel.
8. the preparation method of carbon nano-tube material as claimed in claim 5 is characterized in that this collection device moves along a straight line.
9. the preparation method of carbon nano-tube material as claimed in claim 5 is characterized in that this collection device riding.
10. the preparation method of carbon nano-tube material as claimed in claim 5 is characterized in that this method comprises that further the carbon nanotube bonding of utilizing binding agent will finish alignment processes is fixing.
CNA031139299A 2003-03-13 2003-03-13 Carbon nanometer pipe material and preparing method thereof Pending CN1530320A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7872408B2 (en) 2007-05-11 2011-01-18 Tsinghua University Field-emission-based flat light source
CN101290857B (en) * 2007-04-20 2011-06-22 清华大学 Field emitted cathode and preparing method thereof
CN101540251B (en) * 2008-03-19 2012-03-28 清华大学 Field-emission electron source
CN102394204A (en) * 2008-03-19 2012-03-28 清华大学 Field electron emission source
JP7442565B2 (en) 2017-11-17 2024-03-04 リンテック・オブ・アメリカ・インコーポレイテッド Carbon nanotube artificial muscle valve and connection

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101290857B (en) * 2007-04-20 2011-06-22 清华大学 Field emitted cathode and preparing method thereof
US7872408B2 (en) 2007-05-11 2011-01-18 Tsinghua University Field-emission-based flat light source
CN101540251B (en) * 2008-03-19 2012-03-28 清华大学 Field-emission electron source
CN102394204A (en) * 2008-03-19 2012-03-28 清华大学 Field electron emission source
CN102394204B (en) * 2008-03-19 2014-10-08 清华大学 Field electron emission source
JP7442565B2 (en) 2017-11-17 2024-03-04 リンテック・オブ・アメリカ・インコーポレイテッド Carbon nanotube artificial muscle valve and connection

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