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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CN101338452B
CN101338452B CN 200710076392 CN200710076392A CN101338452B CN 101338452 B CN101338452 B CN 101338452B CN 200710076392 CN200710076392 CN 200710076392 CN 200710076392 A CN200710076392 A CN 200710076392A CN 101338452 B CN101338452 B CN 101338452B
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array
carbon nanotube
carbon nanotubes
nanotube array
high
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CN101338452A (en
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刘亮
姜开利
张晓波
罗春香
范守善
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清华大学
鸿富锦精密工业(深圳)有限公司
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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

高密度碳纳米管阵列及其制备方法 High density array of carbon nanotubes and preparation method

技术领域 FIELD

[0001] 本发明涉及一种碳纳米管阵列及其制备方法,尤其涉及一种高密度碳管阵列及其制备方法。 [0001] The present invention relates to a method for preparing a carbon nanotube array and, in particular, relates to a high density of the carbon tube array and its preparation method.

背景技术 Background technique

[0002] 碳纳米管是九十年代初才发现的一种新型一维纳米材料。 [0002] Carbon nanotubes are a new type of one-dimensional nanomaterials discovered in the early nineties. 碳纳米管的特殊结构决定了其具有特殊的性质,如高抗张强度和高热稳定性;随着碳纳米管螺旋方式的变化,碳纳米管可呈现出金属性或半导体性等。 Special structure of the carbon nanotubes determined with special properties, such as high tensile strength and high thermal stability; carbon nanotubes in a spiral manner with the changes of the carbon nanotubes can exhibit semiconducting metal or the like. 由于碳纳米管具有理想的一维结构以及在力学、电学、 热学等领域优良的性质,其在材料科学、化学、物理学等交叉学科领域已展现出广阔的应用前景,在科学研究以及产业应用上也受到越来越多的关注。 Because carbon nanotubes have ideal one-dimensional structure and excellent properties in the areas of mechanical, electrical, thermal, etc., it has been demonstrated in a cross-disciplinary field of materials science, chemistry, physics and other out broad application prospects in scientific research and industrial applications on has also been more and more attention.

[0003] 目前比较成熟的制备碳纳米管的方法主要包括电弧放电法(Arcdischarge)、激光烧蚀法(Laser Ablation)及化学气相沉积法(Chemical VaporDeposition, CVD)。 [0003] relatively mature method for production of carbon nanotubes include arc-discharge method (Arcdischarge), a laser ablation method (Laser Ablation) and chemical vapor deposition (Chemical VaporDeposition, CVD). 其中, 化学气相沉积法和前两种方法相比具有产量高、可控性强、与现行的集成电路工艺相兼容等优点,便于工业上进行大规模合成,因此近几年备受关注。 Wherein, the chemical vapor deposition method and compared with the previous two methods have a high yield, control, and compatible with existing integrated circuit process, etc., to facilitate the large-scale industrial synthesis, so much attention in recent years.

[0004] 目前,采用CVD方法制备碳纳米管阵列的技术已经相当成熟,但是直接生长得到的碳纳米管阵列受CVD方法生长的限制,在其阵列中碳纳米管的密度基本上是确定的,无法任意调控。 [0004] Currently, techniques for preparing carbon nanotube array using the CVD method is already quite mature, but the carbon nanotube array obtained directly grown CVD method is limited by the growth, in which the density of carbon nanotubes in the array are substantially determined, It can not be any regulation. 此外,该方法直接生长的碳纳米管阵列中碳纳米管的密度在微观上看是较为松散的,碳纳米管之间的间距大于碳纳米管自身直径的数倍,所制备的碳纳米管阵列的密度最大也只在10_2克每立方厘米(g/cm3)量级上。 In addition, the density of the carbon nanotube array in the method of carbon nanotubes grown directly on a microscopic level is relatively loose, the spacing between the carbon nanotubes is greater than the multiple of its own diameter nanotubes, carbon nanotube arrays prepared the maximum density of only 10_2 in grams per cubic centimeter (g / cm3) of the order. 因此CVD方法直接生长的碳纳米管阵列中碳纳米管的密度较低。 Thus the CVD method is low carbon nanotube array of carbon nanotubes grown directly density. 这种密度较低的碳纳米管阵列在电子、导热等方面的性质还不能达到比较理想的要求。 Such properties of low density array of carbon nanotubes in electronic, thermal conductivity and the like can not achieve the ideal requirements. 这种低密度的碳纳米管阵列,由于其中的碳纳米管之间的间距通常较大,结合不够紧密,在一般的器具操作下很容易被破坏。 This low density carbon nanotube array, since the spacing between the carbon nanotubes which is usually large, tightly bound not, under normal operation of the appliance is easily broken.

[0005] Don N. Futaba 等A ( it # JAL “ Shape-engineerable and highly densely packedsingle-walled carbon nanotubes and their application as super-capacitorelectrodesDon N.Futaba et al. , Nature Materials, vol5, p987(2006))利用收缩效应把单壁碳纳米管收缩成高密度碳纳米管,且证实了其所制备的高密度单壁碳纳米管阵列,具有单个碳纳米管的例如大表面积、优异的柔韧性以及导电性等固有特性,以及其在可变形的加热器和在密闭能量存储器件的超级电容器的电极上的应用。但是该方法制备工序较复杂,且制备的碳纳米管阵列的密度也不可以任意调控。 [0005] Don N. Futaba et A (it # JAL "Shape-engineerable and highly densely packedsingle-walled carbon nanotubes and their application as super-capacitorelectrodesDon N.Futaba et al., Nature Materials, vol5, p987 (2006)) using contraction effect the shrinkage of SWNTs into high-density carbon nanotubes, and confirmed that a high density array of SWNTs made therefrom, having a large surface area, for example, excellent flexibility and a conductive individual carbon nanotubes and the like inherent characteristics, and its use in a heater and a deformable electrode ultracapacitor energy storage devices in a closed However the preparation process is complicated, and the density of the prepared carbon nanotube array can not arbitrarily regulated.

[0006] 因此,确有必要提供一种制备高密度碳纳米管阵列及其制备方法,该碳纳米管阵列中的碳纳米管结合紧密且具有较高密度,且,所述的制备方法工序简单,易于实际应用、 效率较高且制备的碳纳米管阵列的密度可以控制。 [0006] Thus, there is indeed a need to provide a high density array of carbon nanotubes and a preparation method for preparing a carbon nanotube array and tightly binding the carbon nanotubes having a higher density, and the preparation process is simple , easy to practice, high efficiency and density of the prepared carbon nanotube array can be controlled.

发明内容 SUMMARY

[0007] —种高密度碳纳米管阵列,该高密度碳纳米管阵列中的碳纳米管排列紧密,且定向排列,具有类一维单晶结构,密度为0. 1〜2. 2g/cm3。 [0007] - Type High-density array of carbon nanotubes, the carbon nanotubes are arranged in a high density array of carbon nanotubes closely aligned and having a one-dimensional type crystal structure, a density of 0. 1~2 2g / cm3. . [0008] 所述的高密度碳纳米管阵列包括单壁高密度碳纳米管阵列、双壁高密度碳纳米管阵列或多壁高密度碳纳米管阵列。 [0008] The high-density single-walled carbon nanotube array comprising a high density array of carbon nanotubes, double-walled or multi-walled carbon nanotube array of high density high density array of carbon nanotubes.

[0009] 一种高密度碳纳米管阵列制备方法,包括:提供一碳纳米管阵列形成于一基底; 沿着平行于基底的方向,施加压力挤压上述碳纳米管阵列,从而得到高密度碳纳米管阵列。 [0009] A method for preparing a high density array of carbon nanotubes, comprising: providing a carbon nanotube array formed on a substrate; direction parallel to the substrate, applying a pressure of pressing the carbon nanotube array to obtain a high density of the carbon nanotube array.

[0010] 所述的碳纳米管阵列的制备包括以下步骤:提供一平整基底;在基底表面形成一催化剂层;将上述形成有催化剂层的基底在空气中退火;将处理过的基底置于低压反应炉中加热,然后通入碳源气体反应,生长得到碳纳米管阵列。 The prepared carbon nanotube array [0010] comprising the steps of: providing a flat substrate; forming a catalyst layer on the surface of the substrate; the above-described substrate with the catalyst layer is annealed in air; The treated substrate was placed a low pressure heating the reaction furnace, the reaction gas is then introduced into a carbon source, growth of the carbon nanotube array.

[0011] 所述的施加压力是通过一挤压装置对碳纳米管阵列进行挤压。 [0011] The pressure applied to the carbon nanotube array is pressed by a pressing device.

[0012] 所述的挤压装置包括一下压板,一上压板,两个第一侧板与两个第二侧板设置于上压板和下压板之间,并在上压板和下压板之间的中心位置形成一空腔。 [0012] the pressing device comprises a lower platen, a top plate, two first and two second side plate disposed between the upper and lower platens, and between the upper and lower platens a cavity formed in the center position.

[0013] 所述的上压板通过螺丝对称地固定于下压板上,上压板的面积与下压板相等。 [0013] The upper platen is fixed by screws symmetrically on the lower platen, the platen is equal to the area of ​​the lower platen.

[0014] 所述的两个第一侧板沿第一方向对称地分布在空腔的两侧,两个第二侧板沿第二方向对称地分布在空腔的另外两侧,第一方向与第二方向相互垂直。 [0014] The two first side plates are distributed symmetrically on both sides of the cavity in a first direction, and two second side plates are distributed symmetrically on both sides of the cavity further in the second direction, the first direction and second mutually perpendicular directions.

[0015] 所述的通过一挤压装置对碳纳米管阵列进行挤压包括以下步骤:用第一侧板沿着第一方向相对移动,对碳纳米管阵列进行挤压;之后,用第二侧板沿着第二方向相对移动, 对碳纳米管阵列进行挤压。 [0015] comprising the steps of extrusion of a carbon nanotube array by the pressing device: a first side panel along a first relative moving direction, extrusion of the carbon nanotube array; then, with a second relatively moving a second plate along a direction of pressing the carbon nanotube array.

[0016] 所述的用第一侧板沿着第一方向相对移动,对碳纳米管阵列进行挤压包括以下步骤:通过两个第二侧板固定碳纳米管阵列;通过两个第一侧板沿着第一方向相对移动,对碳纳米管进行挤压,随着挤压形变程度的增大,上述碳纳米管阵列的碳纳米管之间的间距在第一方向上减小。 According to [0016] a first side panel along a first relative moving direction, for pressing the carbon nanotube array comprising the steps of: fixing two second side plates carbon nanotube array; two first side movement along a first direction relative to the plate, carbon nanotubes extrusion, pressing with increasing degree of deformation, the distance between the above-described carbon nanotube carbon nanotube array in the first direction is reduced.

[0017] 所述的用第二侧板沿着第二方向相对移动,对碳纳米管阵列进行挤压包括以下步骤:通过两个第一侧板固定碳纳米管阵列;通过两个第二侧板沿着第二方向相对移动,对碳纳米管阵列进行挤压,随着挤压形变程度的增大,上述碳纳米管阵列的碳纳米管之间的间距在第二方向上减小。 According to [0017] a second plate relative movement along a second direction, for pressing the carbon nanotube array comprising the steps of: fixing the two first side plates carbon nanotube array; second side by two relatively moving a second plate along a direction of the carbon nanotube array was pressed with increasing degree of deformation of the pressing, the distance between the above-described carbon nanotube carbon nanotube array in the second direction is reduced.

[0018] 与现有技术相比较,所述的高密度碳纳米管阵列及其制备方法具有以下优点:其一,所述的高密度碳纳米管阵列排列紧密,且定向排列,具有类一维单晶结构,其密度达到了普通碳纳米管阵列密度的50〜100倍,因此,在电、热等方面都有较好的特性,可以在场发射、电子、导热、复合材料等方面用于测量或者器件组装;其二,所述的高密度碳纳米管阵列中的碳纳米管之间的间距较小,排列紧密,在普通器具操作时不太容易被破坏;其三,所述的制备方法工序简单,易于实际应用、效率较高且制备的碳纳米管阵列的密度可以控制。 [0018] Compared with the prior art, a high-density array of carbon nanotubes and method of preparation has the following advantages: First, the high density array of carbon nanotubes arranged closely, alignment and having a one-dimensional class single crystal structure, the density of which 50~100 times the normal density of the carbon nanotube array, and therefore, in terms of electricity, heat and other aspects of good characteristics can be field emission, electrons, thermal conductivity, composite materials and the like for measuring device or assembly; spacing between the second, high-density array of carbon nanotubes in the carbon nanotube is small, closely arranged, not easy to be destroyed during the normal operation of the appliance; Third, the method of preparation process is simple, easy to practice, and a more efficient density array of carbon nanotubes produced can be controlled.

附图说明 BRIEF DESCRIPTION

[0019] 图1是本发明实施例高密度碳纳米管阵列的制备方法的流程示意图。 [0019] FIG. 1 is a schematic flow chart of a method for making a high density array of carbon nanotubes embodiment of the present invention.

[0020] 图2是制备本发明实施例高密度碳纳米管阵列的挤压装置结构示意图。 [0020] FIG. 2 is a schematic view of the extrusion apparatus of the present invention is the preparation of a high density array of carbon nanotubes configuration example embodiment.

[0021] 图3是本发明实施例高密度碳纳米管阵列的制备过程中碳纳米管阵列的挤压形变的示意图。 [0021] FIG. 3 is a schematic view showing a high density array of carbon nanotubes The procedure of Example embodiment of the present invention, it deforms the carbon nanotube array.

[0022] 图4是本发明实施例挤压前的多壁碳纳米管阵列扫描电镜照片。 [0022] FIG. 4 is a multi-walled carbon nanotube array SEM image before pressing embodiment embodiment of the present invention.

[0023] 图5是本发明实施例挤压后的多壁碳纳米管阵列扫描电镜照片。 [0023] FIG. 5 is a rear pressing embodiment according to the present invention multi-wall carbon nanotube array scanning electron micrograph. 具体实施方式 Detailed ways

[0024] 以下将结合附图详细说明本实施例高密度碳纳米管阵列及其制备方法。 [0024] The following detailed description in conjunction with the high-density array of carbon nanotubes and a preparation method of the present embodiment to the accompanying drawings.

[0025] 请参阅图1,本实施例高密度碳纳米管阵列的制备方法主要包括以下步骤: [0025] Referring to FIG. 1, the present embodiment the method of Example high density array of carbon nanotubes includes the following steps:

[0026] 步骤一:提供一碳纳米管阵列,优选地,该阵列为超顺排碳纳米管阵列。 [0026] Step a: providing a carbon nanotube array, preferably the super-aligned array of carbon nanotube array.

[0027] 本实施例中,碳纳米管阵列的制备方法采用化学气相沉积法,其具体步骤包括: (a)提供一平整基底,该基底可选用P型或N型硅基底,或选用形成有氧化层的硅基底,本实施例优选为采用4英寸的硅基底;(b)在基底表面均勻形成一催化剂层,该催化剂层材料可选用铁(Fe)、钴(Co)、镍(Ni)或其任意组合的合金之一;(c)将上述形成有催化剂层的基底在700〜900°C的空气中退火约30分钟〜90分钟;(d)将处理过的基底置于低压反应炉中,大气压强约0. 2torr,在保护气体环境下加热到705°C,然后通入碳源气体反应约20分钟,生长得到碳纳米管阵列。 [0027] In this embodiment, carbon nanotube array prepared using a chemical vapor deposition method, the specific steps include: (a) providing a flat substrate, the substrate can be selected P-type or N-type silicon substrate, there is formed or use silicon substrate oxide layer, preferred embodiments of the present embodiment is a 4-inch silicon substrate; (b) uniformly forming a catalyst layer on the substrate surface, the catalyst layer material can be selected iron (Fe), cobalt (Co), nickel (Ni) one alloy or any combination thereof; (c) the above-described substrate with the catalyst layer is annealed in air at 700~900 ° C for about 30 minutes ~ 90 minutes; (d) the treated substrate was placed a low pressure reactor , the atmospheric pressure of about 0. 2torr, under protective gas atmosphere is heated to 705 ° C, and a carbon source gas into the reaction for about 20 minutes to grow a carbon nanotube array. 该碳纳米管阵列为多个彼此平行且垂直于基底生长的碳纳米管形成的纯碳纳米管阵列,由于生成的碳纳米管长度较长,部分碳纳米管会相互缠绕。 The carbon nanotube array is a plurality of parallel and perpendicular to the carbon nanotubes of pure carbon nanotube array formed on the growth substrate, since the longer the length of the carbon nanotubes generated, part of the carbon nanotubes will be entangled with each other. 通过控制上述生长条件,该超顺排碳纳米管阵列中基本不含有杂质,如无定型碳或残留的催化剂金属颗粒等。 By controlling the growth conditions, the super-aligned carbon nanotube array is substantially free of impurities, such as carbonaceous or residual catalyst particles and the like. 本实施例中碳源气可选用乙炔等化学性质较活泼的碳氢化合物,保护气体可选用氮气、氨气或惰性气体。 In this embodiment the choice of carbon source gas and acetylene hydrocarbon chemical properties more lively, choice of protective gas nitrogen, ammonia or an inert gas. 可以理解的是,本实施例提供的碳纳米管阵列不限于上述制备方法,所述的碳纳米管阵列包括单壁碳纳米管阵列、双壁碳纳米管阵列或多壁碳纳米管阵列中的一种。 It will be appreciated that the carbon nanotube array is provided in this embodiment is not limited to the above-described production method, the carbon nanotube array comprises an array of single-walled carbon nanotube array or multi-wall carbon nanotube array, double-walled carbon nanotubes one kind.

[0028] 步骤二:提供一挤压装置,将上述碳纳米管阵列连同基底放置于挤压装置的空腔中。 [0028] Step Two: providing a pressing means, together with the above-described carbon nanotube array substrate is placed in the cavity of the extrusion apparatus.

[0029] 请参阅图2,本实施例中所述的挤压装置100包括一上压板10,一下压板20,两个第一侧板30,两个第二侧板40。 [0029] Referring to FIG. 2, the pressing device 100 of this embodiment includes an upper platen 10 embodiment, a lower platen 20, two first side plate 30, two second side panel 40. 上述的两个第一侧板30与上述的两个第二侧板设置于上压板10和下压板20之间,并在上压板和下压板之间的中心位置形成一空腔50。 The above-described two first side plate 30 and the above-described two second side plates disposed between the upper platen 10 and lower platen 20, and the center position between the platen and lower platen forming a cavity 50. 上压板10 通过螺丝60对称地固定于下压板20上,上压板10的面积与下压板20相等。 On the pressure plate 10 by screws 60 symmetrically fixed to the lower plate 20, the area of ​​the lower platen 10. The upper platen 20 is equal. 进一步地,两个第一侧板30沿第一方向对称地分布在空腔50的两侧;两个第二侧板40沿第二方向对称地分布在空腔50的另外两侧,其中,上述的第一方向与第二方向相互垂直。 Further, two first side panel 30 along a first direction, symmetrically distributed on both sides of cavity 50; distributed symmetrically on both sides of the cavity 50 two further second side panel 40 along a second direction, wherein said first and second directions perpendicular to each other.

[0030] 将一碳纳米管阵列80连同基底70直接放置于上述挤压装置100的空腔50中,具体的,先将上述的两个第一侧板30和两个第二侧板40放置在下压板10上,在下压板10的中心位置形成一空腔50,再将碳纳米管阵列80连同基底10直接放置到上述的空腔50中, 之后,再将上压板20固定到下压板10上。 [0030] The carbon nanotube array 80 together with a base 70 placed directly in the cavity 50 of the pressing apparatus 100, specifically, the first side plate 30 above the two first and two second side plates 40 is placed on the lower platen 10, the center position of the lower platen 10 of a cavity 50 is formed, then together with the carbon nanotube array 80 to the substrate 10 is placed directly above the cavity 50, after which the upper platen 20 and then secured to the lower platen 10.

[0031] 可以理解,上述将碳纳米管阵列80连同基底70放置于空腔50中的方式或步骤不限于上述的方式或步骤,例如,也可以首先将上压板20通过螺丝60以一定间隔固定于下压板10上,然后将碳纳米管阵列80连同基底70以及两个第一侧板30和两个第二侧板40依次设置于上压板20和下压板10之间,只需确保碳纳米管阵列80连同基底70放置于空腔50中。 [0031] It will be appreciated, the above carbon nanotube array 80 together with the substrate 70 is placed in the cavity 50 is not limited to the above-described embodiment or the step or steps of the embodiment, for example, may be the first platen 20 is fixed by a screw 60 at regular intervals on the lower platen 10, and then the carbon nanotube array 70 and the substrate 80 together with the two first side plates 30 and two second side plates 40 are sequentially disposed between the upper platen 20 and lower platen 10, simply ensure that the carbon nano tube array 80 together with the substrate 70 is placed in the cavity 50.

[0032] 步骤三:对已放置于挤压装置100的空腔50中的碳纳米管阵列80通过上述的第一侧板30和第二侧板40的移动进行机械压缩,以获得高密度碳纳米管阵列。 [0032] Step Three: carbon nanotube array have been placed in the cavity 50 of the extrusion apparatus 100 by 80 mechanical compression movement of the first side plate 30 and second side 40, to obtain a high density of the carbon nanotube array.

[0033] 请参阅图3,所述的通过上述的第一侧板30和第二侧板40的移动进行机械压缩的挤压方式包括:用第一侧板沿着第一方向相对移动,对碳纳米管阵列进行挤压;之后,用第二侧板沿着第二方向相对移动,对碳纳米管阵列进行挤压。 [0033] Referring to FIG. 3, the mechanical compression is performed by pressing the above-described embodiment includes a first side plate 30 and the second side 40 of the mobile: a first plate with a first direction along the relative movement of extruding the carbon nanotube array; then, by relatively moving a second plate along a second direction, extrusion of the carbon nanotube array. [0034] 所述的用第一侧板沿着第一方向相对移动,对碳纳米管阵列进行挤压,包括以下步骤:首先通过两个第二侧板40固定设置在挤压装置100的空腔50中的碳纳米管阵列80, 之后通过两个第一侧板30沿着第一方向相对移动,对碳纳米管阵列80进行挤压,随着挤压形变程度的增大,上述碳纳米管阵列80中的碳纳米管之间的间距在第一方向上减小。 [0034] The first side panel with a relatively movable along a first direction, for pressing the carbon nanotube array, comprising the steps of: firstly fixed to the extrusion apparatus 100 empty second side panel 40 by two carbon nanotube array 80 in the chamber 50, a first side plate 30 after passing through two relatively movable along a first direction, for pressing the carbon nanotube array 80, with an increase in pressing degree of deformation, the carbon nano the spacing between the tube array 80 to reduce the carbon nanotube in the first direction.

[0035] 所述的用第二侧板沿着第二方向相对移动,对碳纳米管阵列进行挤压,包括以下步骤:用两个第一侧板30把上述经过第一侧板30挤压后的碳纳米管阵列80固定,通过两个第二侧板40沿着第二方向相对移动,对上述挤压后的碳纳米管阵列80进行挤压,随着挤压形变程度的增大,上述挤压后的碳纳米管阵列80中的碳纳米管之间的间距在第二方向上减小。 [0035] with a second side of the relative movement in the second direction, extrusion of the carbon nanotube array, comprising the steps of: a first side plate 30 with the above-described two first side plate 30 through the pressing after the carbon nanotube array 80 is fixed relative movement along a second direction by the two second side plates 40, for pressing the carbon nanotube array 80 after extrusion, pressing with increasing degree of deformation, the spacing between the carbon nanotubes 80 in the carbon nanotube array is reduced after the pressing in the second direction.

[0036] 可以理解,碳纳米管阵列80中的碳纳米管之间的间距随着挤压形变的增大而减小;碳纳米管阵列80的密度随着挤压形变的增大而增加。 [0036] It will be appreciated, the spacing between the carbon nanotubes in the pressed carbon nanotube array 80 increases as the deformation decreases; density of the carbon nanotube array 80 is pressed with increasing deformation increases. 因此,本实施例可通过控制对碳纳米管阵列80施加的挤压形变的程度的大小,进而控制所述的高密度碳纳米管阵列90的 Accordingly, the present embodiment may be controlled by the size of the deformation degree of pressing the carbon nanotube array 80 is applied, thereby controlling the high-density array of carbon nanotubes 90

也/又。 Also / and.

[0037] 本实施例中获得的高密度碳纳米管阵列90,该高密度碳纳米管阵列90中的碳纳米管排列紧密,且定向排列,具有类一维单晶结构,密度为0. 1〜2. 2g/cm3。 [0037] The present embodiment the high density array of carbon nanotubes obtained in the embodiment 90, the high density of carbon nanotubes in the carbon nanotube array 90 are arranged closely, and alignment, with one-dimensional crystal structure class, a density of 0.1 ~2. 2g / cm3.

[0038] 可以理解,本实施例所制备得到的高密度碳纳米管阵列90包括单壁高密度碳纳米管阵列、双壁高密度碳纳米管阵列或多壁高密度碳纳米管阵列中的一种。 [0038] It will be appreciated, the present embodiment the high density array of carbon nanotubes prepared in Example 90 obtained comprises a single-wall carbon nanotubes of high density arrays, high density double-walled or multi-walled carbon nanotube array in the high density array of carbon nanotubes species.

[0039] 另外,本发明中所采用的挤压装置100并不限于采用图2所示的结构,进一步,本发明高密度碳纳米管阵列90的制备并不限于采用特定的挤压装置100压缩的方式,其关键在于能沿着平行于基底的方向对碳纳米管阵列80施加一机械压力,通过挤压使碳纳米管阵列80中的碳纳米管之间的间距减小,密度增大,从而获得高密度碳纳米管阵列90,因此依据本发明精神对本发明所述挤压装置作其它非实质性变化,都应包含在本发明所要求的保护范围内。 [0039] Further, the pressing means employed in the present invention is not limited to the structure shown 100 in FIG. 2, and further, a high density array of carbon nanotubes prepared according to the present invention 90 is not limited to a particular pressing means 100 using compressed manner, the key lies in a direction parallel to the substrate capable of applying a mechanical pressure to the carbon nanotube array 80, by pressing the carbon nanotube array to reduce the spacing between the carbon nanotubes 80, the density is increased, thereby obtaining high density array of carbon nanotubes 90, and therefore the present invention according to the spirit of the present invention, apparatus for pressing said other insubstantial variations be included within the scope of the claimed invention.

[0040] 请参阅图4,为本发明实施例挤压前的多壁碳纳米管阵列80的扫描电镜照片,该图中的碳纳米管之间的间隙较大,排列不紧密,而且碳纳米管的定向排列不是很好,部分碳纳米管缠绕到一起。 [0040] Referring to FIG 4, a scanning electron micrograph of MWCNT array 80 before pressing embodiment according to the present invention, the gap between the carbon nanotubes of FIG large, are not arranged closely, and carbon nano orientation of the tube arrangement is not very good, part of the carbon nanotubes is wound together.

[0041] 请参阅图5,为本发明实施例挤压后的多壁碳纳米管阵列90的扫描电镜照片,该图中的碳纳米管之间的间隙较小,排列紧密,且定向排列,缠绕到一起的碳纳米管的数量明显减少,该图中显示的经挤压后的多壁碳纳米管阵列90具有类一维单晶结构,密度为0. 8g/cm3。 [0041] Referring to FIG 5, a scanning electron micrograph of MWCNT array 90 according to the embodiment of the present invention the extrusion, a small gap between the carbon nanotubes in FIG closely arranged, and aligned, wound around the carbon nanotube with the number decreased, after the MWCNT array extruded shown in the figure 90 class of one-dimensional crystal structure having a density of 0. 8g / cm3.

[0042] 本实施例中高密度碳纳米管阵列及其制备方法具有以下优点:其一,所述的高密度碳纳米管阵列排列紧密,且定向排列,具有类一维单晶结构,其密度达到了普通碳纳米管阵列密度的50〜100倍,因此,在电、热等方面都有较好的特性,可以在场发射、电子、导热、 复合材料等方面用于测量或者器件组装;其二,所述的高密度碳纳米管阵列中的碳纳米管之间的间距较小,排列紧密,在普通器具操作时不太容易被破坏;其三,所述的制备方法工序简单,易于实际应用、效率较高且制备的碳纳米管阵列的密度可以控制。 [0042] This high-density array of carbon nanotubes and the method of Example embodiment has the following advantages: First, the high density array of carbon nanotubes arranged closely, alignment and having a one-dimensional crystal structure class, which density ordinary carbon nanotube array density 50~100 times, and therefore, electrical, thermal, etc. have good characteristics can be field emission, electronics, thermal conductivity, composite materials, or device for measuring assembly; Second, the spacing between the carbon nanotubes with high density in the carbon nanotube array of small, closely arranged, not easy to be destroyed during the normal operation of the appliance; Third, the preparation process is simple, easy to practice, higher efficiency and the density of the prepared carbon nanotube array can be controlled.

[0043] 另外,本领域技术人员还可在本发明精神内作其它变化,当然这些依据本发明精神所作的变化,都应包含在本发明所要求保护的范围内。 [0043] Additionally, one skilled in the art may also be used for other variations within the spirit of the present invention, of course, vary depending on the spirit of the invention made by the present invention is intended to be included within the scope of the claims.

6 6

Claims (11)

1. 一种高密度碳纳米管阵列,包括多个碳纳米管,其特征在于,该高密度碳纳米管阵列中的碳纳米管排列紧密,且定向排列,具有类一维单晶结构,密度大于等于0. 8g/cm3,且小于等于2. 2g/cm3。 A high density array of carbon nanotubes, comprising a plurality of carbon nanotubes, wherein the carbon nanotubes aligned carbon nanotube array in the high-density compact, and alignment, with one-dimensional crystal structure type, density greater than or equal 0. 8g / cm3, and less than or equal to 2. 2g / cm3.
2.如权利要求1所述的高密度碳纳米管阵列,其特征在于,所述的高密度碳纳米管阵列包括单壁高密度碳纳米管阵列、双壁高密度碳纳米管阵列或多壁高密度碳纳米管阵列中的一种。 2. The high density array of carbon nanotubes according to claim 1, wherein said high density array of carbon nanotubes include single wall carbon nanotubes of high density arrays, high density double-walled or multi-walled carbon nanotube array a high density in the carbon nanotube array.
3. 一种高密度碳纳米管阵列的制备方法,包括以下步骤:提供一碳纳米管阵列形成于一基底;沿着平行于基底的方向,施加压力挤压上述碳纳米管阵列,从而得到高密度碳纳米管阵列。 3. A method for preparing a high density array of carbon nanotubes, comprising the steps of: providing a carbon nanotube array formed on a substrate; direction parallel to the substrate, applying a pressure of pressing the carbon nanotube array, resulting in high density array of carbon nanotubes.
4.如权利要求3所述的高密度碳纳米管阵列的制备方法,其特征在于,所述的碳纳米管阵列的制备包括以下步骤:提供一平整基底;在基底表面形成一催化剂层;将上述形成有催化剂层的基底在空气中退火;将处理过的基底置于低压反应炉中加热,然后通入碳源气体反应,生长得到碳纳米管阵列。 4. A method for preparing a high density array of carbon nanotubes according to claim 3, wherein said carbon nanotube array is prepared comprising the steps of: providing a flat substrate; forming a catalyst layer on the substrate surface; the above-described substrate with the catalyst layer is annealed in air; the treated substrate is placed in a low-pressure reactor was heated, and the carbon source gas into the reaction, the growth of the carbon nanotube array.
5.如权利要求3所述的高密度碳纳米管阵列的制备方法,其特征在于,所述的施加压力是通过一挤压装置对碳纳米管阵列进行挤压。 5. A method for preparing a high density array of carbon nanotubes according to claim 3, wherein said pressure is applied to the carbon nanotube array is pressed by a pressing device.
6.如权利要求5所述的高密度碳纳米管阵列的制备方法,其特征在于,所述的挤压装置包括一下压板,一上压板,两个第一侧板与两个第二侧板设置于上压板和下压板之间,并在上压板和下压板之间的中心位置形成一空腔。 6. A method for preparing a high density array of carbon nanotubes as claimed in claim 5, wherein said pressing means comprises a lower platen, a top plate, two first and two second side plate disposed between the upper and lower platens, and the center position between the platen and lower platen forming a cavity.
7.如权利要求6所述的的高密度碳纳米管阵列的制备方法,其特征在于,所述的上压板通过螺丝对称地固定于下压板上,上压板的面积与下压板相等。 The method of preparing a high-density array of carbon nanotubes as claimed in claim 6, characterized in that said upper platen is fixed by screws symmetrically on the lower platen, the platen is equal to the area of ​​the lower platen.
8.如权利要求7所述的的高密度碳纳米管阵列的制备方法,其特征在于,所述的两个第一侧板沿第一方向对称地分布于空腔的两侧,两个第二侧板沿第二方向对称地分布于空腔的另外两侧,其中,第一方向与第二方向相互垂直。 The method of preparing a high-density array of carbon nanotubes of claim 7 claims, characterized in that said two first side plates are distributed symmetrically on both sides of the cavity in the first direction, the first two two side plates are symmetrically distributed in the second direction to the other two sides of the cavity, wherein the first and second directions perpendicular to each other.
9.如权利要求8所述的高密度碳纳米管阵列的制备方法,其特征在于,所述的通过一挤压装置对碳纳米管阵列进行挤压包括以下步骤:用第一侧板沿着第一方向相对移动,对碳纳米管阵列进行挤压;之后,用第二侧板沿着第二方向相对移动,对碳纳米管阵列进行挤压。 The method of preparing a high-density array of carbon nanotubes as claimed in claim 8, wherein said extrusion comprises the steps of a carbon nanotube array by the pressing device: a first side panel along with relative movement in the first direction, extrusion of the carbon nanotube array; then, by relatively moving a second plate along a second direction, extrusion of the carbon nanotube array.
10.如权利要求9所述的高密度碳纳米管阵列的制备方法,其特征在于,所述的用第一侧板沿着第一方向相对移动,对碳纳米管阵列进行挤压包括以下步骤:通过两个第二侧板固定碳纳米管阵列;通过两个第一侧板沿第一方向相对移动,对碳纳米管阵列进行挤压。 The method of preparing a high-density array of carbon nanotubes as claimed in claim 9, wherein said relative movement with the first side panel along a first direction, for pressing the carbon nanotube array comprising the steps of : two second side plates by fixing the carbon nanotube array; two first side panels relative movement in a first direction for pressing the carbon nanotube array.
11.如权利要求9所述的高密度碳纳米管阵列的制备方法,其特征在于,所述的用第二侧板沿着第二方向相对移动,对碳纳米管阵列进行挤压包括以下步骤:通过两个第一侧板固定碳纳米管阵列;通过两个第二侧板沿第二方向相对移动,对碳纳米管进行挤压。 The method of preparing a high-density array of carbon nanotubes as claimed in claim 9, wherein said second side plate with the relative movement in the second direction, for pressing the carbon nanotube array comprising the steps of : by fixing the two first side plates carbon nanotube array; side by two second relative movement in the second direction, pressing of carbon nanotubes.
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