CN101338452B - High-density carbon nanotube array and method for preparing same - Google Patents

High-density carbon nanotube array and method for preparing same Download PDF

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Publication number
CN101338452B
CN101338452B CN200710076392XA CN200710076392A CN101338452B CN 101338452 B CN101338452 B CN 101338452B CN 200710076392X A CN200710076392X A CN 200710076392XA CN 200710076392 A CN200710076392 A CN 200710076392A CN 101338452 B CN101338452 B CN 101338452B
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carbon nano
array
density
preparation
tube array
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CN101338452A (en
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罗春香
张晓波
姜开利
刘亮
范守善
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Abstract

The invention relates to a high-density CNTs array. In the high-density CNTs array, the CNTS are arranged tightly and the array is directed. The CNTs array has a single-dimension-like single crystal structure. Density is 0.1 to 2.2g/cm<3>. The invention also relates to a preparation method of the high-density CNTs array. The preparation method comprises the procedures as follows: the CNTs array is provided and formed at a substrate; and pressure is exerted on the CNTs array in the direction parallel to the substrate so that the high-density CNTs array is made. The preparation method has simple procedures and higher efficiency and is easy for practical application. In addition, the density of the prepared CNTs array is controllable.

Description

High-density carbon nano-tube array and preparation method thereof
Technical field
The present invention relates to a kind of carbon nano pipe array and preparation method thereof, relate in particular to a kind of high density carbon pipe array and preparation method thereof.
Background technology
Carbon nanotube is a kind of new one-dimensional nano material of just finding the early 1990s.The special construction of carbon nanotube has determined it to have special nature, as high-tensile and high thermal stability; Along with the variation of carbon nanotube spiral way, carbon nanotube can present metallicity or semiconductive etc.Because carbon nanotube has the ideal one-dimentional structure and in good character in field such as mechanics, electricity, calorifics, it has shown wide application prospect at interdisciplinary fields such as Materials science, chemistry, physics, also receives increasing concern in scientific research and industry application.
At present the method for preparing carbon nanotube of comparative maturity mainly comprise arc discharge method (Arcdischarge), laser ablation method (Laser Ablation) and chemical Vapor deposition process (Chemical VaporDeposition, CVD).Wherein, chemical Vapor deposition process compare with preceding two kinds of methods have the output height, controllability is strong, with existing integrated circuit technology advantage such as compatibility mutually, be convenient to industrially carry out syntheticly on a large scale, so received much concern in recent years.
At present, the technology that employing CVD method prepares carbon nano pipe array is quite ripe, but the carbon nano pipe array that direct growth obtains is subjected to the restriction of CVD method growth, and the density of carbon nanotube is determined basically in its array, can't regulate and control arbitrarily.In addition, the density of carbon nanotube sees it is comparatively loose in the carbon nano pipe array of this method direct growth on microcosmic, and the spacing between the carbon nanotube is greater than the several times of carbon nanotube self diameter, and the density maximum of prepared carbon nano pipe array is also only 10 -2Restrain every cubic centimetre of (g/cm 3) on the magnitude.Therefore the density of carbon nanotube is lower in the carbon nano pipe array of CVD method direct growth.The character that the carbon nano-pipe array that this density is lower is listed in aspects such as electronics, heat conduction can't reach more satisfactory requirement.This low-density carbon nano pipe array because the spacing between the carbon nanotube wherein is bigger usually, in conjunction with undertighten, is easy to destroyed under general utensil operation.
People such as Don N.Futaba (see also " Shape-engineerable and highly densely packedsingle-walled carbon nanotubes and their application as super-capacitorelectrodes ", Don N.Futaba et al., Nature Materials, vol5, p987 (2006)) utilize shrinking effect that Single Walled Carbon Nanotube is shrunk to high-density carbon nano-tube, and confirmed the high-density single-wall carbon nanotube array that it is prepared, for example high surface area with single carbon nanotube, natural characteristics such as excellent flexibility and electroconductibility, with and application on deformable well heater and electrode at the ultracapacitor of airtight energy storage device.But this method preparation section is complicated, and the density of the carbon nano pipe array of preparation also cannot be regulated and control arbitrarily.
Therefore, the necessary a kind of preparation high-density carbon nano-tube array and preparation method thereof that provides, carbon nanotube in this carbon nano pipe array is in conjunction with closely and have a higher density, and, described preparation method's operation is simple, is easy to practical application, efficient is higher and the density of carbon nano pipe array of preparation can be controlled.
Summary of the invention
A kind of high-density carbon nano-tube array, the carbon nanotube in this high-density carbon nano-tube array is arranged closely, and aligns, and has the kind one-dimensional single crystal structure, and density is 0.1~2.2g/cm 3
Described high-density carbon nano-tube array comprises single wall high-density carbon nano-tube array, double-walled high-density carbon nano-tube array or many walls high-density carbon nano-tube array.
A kind of high-density carbon nano-tube array preparation method comprises: provide a carbon nano pipe array to be formed at a substrate; Along the direction that is parallel to substrate, the above-mentioned carbon nano pipe array of extruding of exerting pressure, thus obtain high-density carbon nano-tube array.
The preparation of described carbon nano pipe array may further comprise the steps: a smooth substrate is provided; Form a catalyst layer at substrate surface; The above-mentioned substrate that is formed with catalyst layer is annealed in air; Place the low pressure reaction stove to heat the substrate of handling, feed the carbon-source gas reaction then, growth obtains carbon nano pipe array.
Described exerting pressure is by a squeezing device carbon nano pipe array to be pushed.
Described squeezing device comprises a press table, a top board, and two first side plates and two second side plates are arranged between top board and the press table, and the central position between top board and press table forms a cavity.
Described top board is fixed on the press table symmetrically by screw, and the area of top board equates with press table.
Described two first side plates are distributed in the both sides of cavity symmetrically along first direction, and two second side plates are distributed in the other both sides of cavity symmetrically along second direction, and first direction is vertical mutually with second direction.
Described carbon nano pipe array the extruding by a squeezing device may further comprise the steps: relatively move along first direction with first side plate, carbon nano pipe array is pushed; Afterwards, relatively move along second direction, carbon nano pipe array is pushed with second side plate.
Described usefulness first side plate relatively moves along first direction, carbon nano pipe array is pushed may further comprise the steps: by two second side plate fixed carbon nano-tube arrays; Relatively move along first direction by two first side plates, carbon nanotube is pushed, along with the increase of compressional deformation degree, the spacing between the carbon nanotube of above-mentioned carbon nano pipe array reduces on first direction.
Described usefulness second side plate relatively moves along second direction, carbon nano pipe array is pushed may further comprise the steps: by two first side plate fixed carbon nano-tube arrays; Relatively move along second direction by two second side plates, carbon nano pipe array is pushed, along with the increase of compressional deformation degree, the spacing between the carbon nanotube of above-mentioned carbon nano pipe array reduces on second direction.
Compared with prior art, described high-density carbon nano-tube array and preparation method thereof has the following advantages: one, described high-density carbon nano-tube array is arranged closely, and align, have the kind one-dimensional single crystal structure, its density has reached 50~100 times of common carbon nano pipe array density, therefore, at aspects such as electricity, heat characteristic is preferably arranged all, can on the scenely launch, aspects such as electronics, heat conduction, matrix material are used for measuring or the device assembling; Its two, the spacing between the carbon nanotube in the described high-density carbon nano-tube array is less, arranges closely, and is destroyed not too easily when appliance common is operated; Its three, described preparation method's operation is simple, is easy to practical application, efficient is higher and the density of carbon nano pipe array of preparation can be controlled.
Description of drawings
Fig. 1 is the preparation method's of embodiment of the invention high-density carbon nano-tube array a schematic flow sheet.
Fig. 2 is the squeezing device structural representation of preparation embodiment of the invention high-density carbon nano-tube array.
Fig. 3 is the synoptic diagram of the compressional deformation of carbon nano pipe array in the preparation process of embodiment of the invention high-density carbon nano-tube array.
Fig. 4 is the array of multi-walled carbon nanotubes stereoscan photograph before the embodiment of the invention extruding.
Fig. 5 is the array of multi-walled carbon nanotubes stereoscan photograph after the embodiment of the invention extruding.
Embodiment
Describe present embodiment high-density carbon nano-tube array and preparation method thereof in detail below with reference to accompanying drawing.
See also Fig. 1, the preparation method of present embodiment high-density carbon nano-tube array mainly may further comprise the steps:
Step 1: a carbon nano pipe array is provided, and preferably, this array is super in-line arrangement carbon nano pipe array.
In the present embodiment, the preparation method of carbon nano pipe array adopts chemical Vapor deposition process, and its concrete steps comprise: a smooth substrate (a) is provided, and this substrate can be selected P type or N type silicon base for use, or select for use the silicon base that is formed with zone of oxidation, present embodiment to be preferably and adopt 4 inches silicon base; (b) evenly form a catalyst layer at substrate surface, this catalyst layer material can be selected one of alloy of iron (Fe), cobalt (Co), nickel (Ni) or its arbitrary combination for use; (c) the above-mentioned substrate that is formed with catalyst layer was annealed in 700~900 ℃ air about 30 minutes~90 minutes; (d) substrate that will handle places the low pressure reaction stove, and the about 0.2torr of atmospheric pressure is heated to 705 ℃ under the shielding gas environment, feeds carbon-source gas then and reacts about 20 minutes, and growth obtains carbon nano pipe array.This carbon nano-pipe array is classified a plurality of pure nano-carbon tube arrays parallel to each other and that form perpendicular to the carbon nanotube of substrate grown as, because the length of carbon nanotube that generates is longer, the part carbon nanotube can twine mutually.By controlling above-mentioned growth conditions, do not contain impurity substantially in this super in-line arrangement carbon nano pipe array, as agraphitic carbon or residual catalyst metal particles etc.Carbon source gas can be selected the more active hydrocarbon polymers of chemical property such as acetylene for use in the present embodiment, and shielding gas can be selected nitrogen, ammonia or rare gas element for use.Be understandable that the carbon nano pipe array that present embodiment provides is not limited to above-mentioned preparation method, described carbon nano pipe array comprises a kind of in single-wall carbon nanotube array, double-walled carbon nano-tube array or the array of multi-walled carbon nanotubes.
Step 2 a: squeezing device is provided, above-mentioned carbon nano pipe array is positioned in the cavity of squeezing device together with substrate.
See also Fig. 2, the squeezing device 100 described in the present embodiment comprises 30, two second side plates 40 of 20, two first side plates of a top board 10, one press tables.Above-mentioned two first side plates 30 and above-mentioned two second side plates are arranged between top board 10 and the press table 20, and the central position between top board and press table forms a cavity 50.Top board 10 is fixed on the press table 20 symmetrically by screw 60, and the area of top board 10 equates with press table 20.Further, two first side plates 30 are distributed in the both sides of cavity 50 symmetrically along first direction; Two second side plates 40 are distributed in the other both sides of cavity 50 symmetrically along second direction, and wherein, above-mentioned first direction is vertical mutually with second direction.
Directly be positioned over a carbon nano pipe array 80 in the cavity 50 of above-mentioned squeezing device 100 together with substrate 70, concrete, earlier above-mentioned two first side plates 30 and two second side plates 40 are placed on the press table 10, form a cavity 50 in the central position of press table 10, again carbon nano pipe array 80 is placed directly in the above-mentioned cavity 50 together with substrate 10, afterwards, again top board 20 is fixed on the press table 10.
Be appreciated that, above-mentioned carbon nano pipe array 80 is not limited to above-mentioned mode or step together with mode or the step that substrate 70 is positioned in the cavity 50, for example, also can at first top board 20 be fixed on the press table 10 at certain intervals by screw 60, then carbon nano pipe array 80 is set in turn between top board 20 and the press table 10 together with substrate 70 and two first side plates 30 and two second side plates 40, only need guarantees that carbon nano pipe array 80 is positioned in the cavity 50 together with substrate 70.
Step 3: to mobile the carry out mechanically compress of the carbon nano pipe array 80 in the cavity 50 that is positioned over squeezing device 100, to obtain high-density carbon nano-tube array by the first above-mentioned side plate 30 and second side plate 40.
See also Fig. 3, the described mobile fashion of extrusion that carries out mechanically compress by the first above-mentioned side plate 30 and second side plate 40 comprises: relatively move along first direction with first side plate, carbon nano pipe array is pushed; Afterwards, relatively move along second direction, carbon nano pipe array is pushed with second side plate.
Described usefulness first side plate relatively moves along first direction, carbon nano pipe array is pushed, may further comprise the steps: at first be fixedly installed on carbon nano pipe array 80 in the cavity 50 of squeezing device 100 by two second side plates 40, relatively move along first direction by two first side plates 30 afterwards, carbon nano pipe array 80 is pushed, along with the increase of compressional deformation degree, the spacing between the carbon nanotube in the above-mentioned carbon nano pipe array 80 reduces on first direction.
Described usefulness second side plate relatively moves along second direction, carbon nano pipe array is pushed, may further comprise the steps: fix through the carbon nano pipe array 80 after 30 extruding of first side plate above-mentioned with two first side plates 30, relatively move along second direction by two second side plates 40, carbon nano pipe array after the above-mentioned extruding 80 is pushed, along with the increase of compressional deformation degree, the spacing between the carbon nanotube in the carbon nano pipe array 80 after the above-mentioned extruding reduces on second direction.
Be appreciated that the spacing between the carbon nanotube in the carbon nano pipe array 80 reduces along with the increase of compressional deformation; The density of carbon nano pipe array 80 increases along with the increase of compressional deformation.Therefore, the size of the degree of the compressional deformation that present embodiment can apply carbon nano pipe array 80 by control, and then control the density of described high-density carbon nano-tube array 90.
The high-density carbon nano-tube array 90 that obtains in the present embodiment, the carbon nanotube in this high-density carbon nano-tube array 90 is arranged closely, and aligns, and has the kind one-dimensional single crystal structure, and density is 0.1~2.2g/cm 3
Be appreciated that the preparation-obtained high-density carbon nano-tube array 90 of present embodiment comprises a kind of in single wall high-density carbon nano-tube array, double-walled high-density carbon nano-tube array or the many walls high-density carbon nano-tube array.
In addition; the squeezing device 100 that is adopted among the present invention is not limited to adopt structure shown in Figure 2; further; the preparation of high-density carbon nano-tube array 90 of the present invention is not limited to adopt the mode of specific squeezing device 100 compressions; its key is and can applies a mechanical pressure to carbon nano pipe array 80 along the direction that is parallel to substrate; by extruding the spacing between the carbon nanotube in the carbon nano pipe array 80 is reduced; density increases; thereby obtain high-density carbon nano-tube array 90; therefore according to spirit of the present invention squeezing device of the present invention is made other unsubstantiality and change, all should be included in the protection domain of the presently claimed invention.
See also Fig. 4, be the stereoscan photograph of the array of multi-walled carbon nanotubes 80 before the embodiment of the invention extruding, the gap between the carbon nanotube among this figure is bigger, arranges not tight, and aligning of carbon nanotube be not fine, and the part carbon nanotube is wound into together.
See also Fig. 5, stereoscan photograph for the array of multi-walled carbon nanotubes 90 after the embodiment of the invention extruding, gap between the carbon nanotube among this figure is less, arrange closely, and align, the quantity that is wound into carbon nanotube together obviously reduces, and the array of multi-walled carbon nanotubes 90 after extruding that shows among this figure has the kind one-dimensional single crystal structure, and density is 0.8g/cm 3
Present embodiment middle-high density carbon nano pipe array and preparation method thereof has the following advantages: one, described high-density carbon nano-tube array is arranged closely, and align, has the kind one-dimensional single crystal structure, its density has reached 50~100 times of common carbon nano pipe array density, therefore, characteristic is preferably all arranged, can on the scenely launch, aspects such as electronics, heat conduction, matrix material are used for measuring or the device assembling at aspects such as electricity, heat; Its two, the spacing between the carbon nanotube in the described high-density carbon nano-tube array is less, arranges closely, and is destroyed not too easily when appliance common is operated; Its three, described preparation method's operation is simple, is easy to practical application, efficient is higher and the density of carbon nano pipe array of preparation can be controlled.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and these variations of doing according to spirit of the present invention certainly all should be included in the present invention's scope required for protection.

Claims (11)

1. a high-density carbon nano-tube array comprises a plurality of carbon nanotubes, it is characterized in that, the carbon nanotube in this high-density carbon nano-tube array is arranged closely, and aligns, and has the kind one-dimensional single crystal structure, and density is more than or equal to 0.8g/cm 3, and smaller or equal to 2.2g/cm 3
2. high-density carbon nano-tube array as claimed in claim 1 is characterized in that, described high-density carbon nano-tube array comprises a kind of in single wall high-density carbon nano-tube array, double-walled high-density carbon nano-tube array or the many walls high-density carbon nano-tube array.
3. the preparation method of a high-density carbon nano-tube array may further comprise the steps: provide a carbon nano pipe array to be formed at a substrate; Along the direction that is parallel to substrate, the above-mentioned carbon nano pipe array of extruding of exerting pressure, thus obtain high-density carbon nano-tube array.
4. the preparation method of high-density carbon nano-tube array as claimed in claim 3 is characterized in that, the preparation of described carbon nano pipe array may further comprise the steps: a smooth substrate is provided; Form a catalyst layer at substrate surface; The above-mentioned substrate that is formed with catalyst layer is annealed in air; Place the low pressure reaction stove to heat the substrate of handling, feed the carbon-source gas reaction then, growth obtains carbon nano pipe array.
5. the preparation method of high-density carbon nano-tube array as claimed in claim 3 is characterized in that, described exerting pressure is by a squeezing device carbon nano pipe array to be pushed.
6. the preparation method of high-density carbon nano-tube array as claimed in claim 5, it is characterized in that, described squeezing device comprises a press table, one top board, two first side plates and two second side plates are arranged between top board and the press table, and the central position between top board and press table forms a cavity.
7. the preparation method of high-density carbon nano-tube array as claimed in claim 6 is characterized in that, described top board is fixed on the press table symmetrically by screw, and the area of top board equates with press table.
8. the preparation method of high-density carbon nano-tube array as claimed in claim 7, it is characterized in that, described two first side plates are distributed in the both sides of cavity symmetrically along first direction, two second side plates are distributed in the other both sides of cavity symmetrically along second direction, wherein, first direction is vertical mutually with second direction.
9. the preparation method of high-density carbon nano-tube array as claimed in claim 8, it is characterized in that, described carbon nano pipe array the extruding by a squeezing device may further comprise the steps: relatively move along first direction with first side plate, carbon nano pipe array is pushed; Afterwards, relatively move along second direction, carbon nano pipe array is pushed with second side plate.
10. the preparation method of high-density carbon nano-tube array as claimed in claim 9, it is characterized in that, described usefulness first side plate relatively moves along first direction, carbon nano pipe array is pushed may further comprise the steps: by two second side plate fixed carbon nano-tube arrays; Relatively move along first direction by two first side plates, carbon nano pipe array is pushed.
11. the preparation method of high-density carbon nano-tube array as claimed in claim 9, it is characterized in that, described usefulness second side plate relatively moves along second direction, carbon nano pipe array is pushed may further comprise the steps: by two first side plate fixed carbon nano-tube arrays; Relatively move along second direction by two second side plates, carbon nanotube is pushed.
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CN103964413B (en) * 2014-04-17 2016-04-27 北京大学 A kind of method improving carbon nanotube parallel array density
JP6459407B2 (en) * 2014-11-05 2019-01-30 富士通株式会社 Sheet-like member, manufacturing method thereof, substrate unit, and electronic device
KR102026816B1 (en) * 2015-02-27 2019-09-30 히다치 조센 가부시키가이샤 High-density carbon nanotube aggregate and method of producing high-density carbon nanotube aggregate
WO2016136826A1 (en) * 2015-02-27 2016-09-01 日立造船株式会社 Carbon nanotube high-density assembly and method for producing carbon nanotube high-density assembly
JP2017094412A (en) * 2015-11-19 2017-06-01 日東電工株式会社 Component holding device
US10981789B2 (en) 2016-05-18 2021-04-20 Hitachi Zosen Corporation Method for drawing carbon nanotube web, method for manufacturing carbon nanotube yarn, method for manufacturing carbon nanotube sheet, and device for drawing carbon nanotube web
CN106158552B (en) * 2016-08-15 2018-07-06 国家纳米科学中心 A kind of carbon nano pipe array and the compound field emitting electronic source of light absorbent
CN110002431B (en) * 2019-03-27 2020-12-18 华中科技大学 Carbon nanotube film and preparation method thereof
CN112242277B (en) * 2019-07-16 2022-03-18 清华大学 Field emission neutralizer
CN112242281B (en) * 2019-07-16 2022-03-22 清华大学 Carbon nanotube field emitter and preparation method thereof

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