CN105692584A - Carbon nano tube clew and preparing method thereof - Google Patents

Carbon nano tube clew and preparing method thereof Download PDF

Info

Publication number
CN105692584A
CN105692584A CN 201610031119 CN201610031119A CN105692584A CN 105692584 A CN105692584 A CN 105692584A CN 201610031119 CN201610031119 CN 201610031119 CN 201610031119 A CN201610031119 A CN 201610031119A CN 105692584 A CN105692584 A CN 105692584A
Authority
CN
Grant status
Application
Patent type
Prior art keywords
nano
carbon
tubes
clew
tube
Prior art date
Application number
CN 201610031119
Other languages
Chinese (zh)
Other versions
CN105692584B (en )
Inventor
魏飞
朱振兴
谢欢欢
Original Assignee
清华大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention provides a carbon nano tube clew.The carbon nano tube clew is formed by irregularly winding one or more carbon nano tubes, the diameter of the carbon nano tubes is 0.6-5 nm, the length of the carbon nano tubes is 1-5 mm, the tile area of the carbon nano tube clew is 0.001-10 mm<2>, and the density is 1-200 CNTS/micrometers.The preparing method includes the steps that a catalyst is loaded on a growth substrate and then placed in a reactor, mixed inert gas is introduced to reduce the catalyst, and then mixed reaction gas is introduced to prepare super-long carbon nano tubes in a heating mode; sound waves are added into the reactor, so that the super-long carbon nano tubes are bent and wound in vortexes induced by the sound waves; after bending and winding are conducted for 10-20 min, mixed inert gas is introduced, the sound wave transmission is stopped, temperature is lowered to below 400 DEG C, and a product is taken out to obtain the carbon nano tube clew.The carbon nano tube clew is high in density, large in area and uniform in chirality, and the application area of the carbon nano tubes is broadened.

Description

一种碳纳米管线团及其制备方法 A carbon nanotube wire group and its preparation method

技术领域 FIELD

[0001]本发明涉及纳米材料制备技术领域,具体而言,涉及一种碳纳米管线团及其制备方法。 [0001] The present invention relates to the field of nano-materials preparation, particularly, to a carbon nanotube wire group and its preparation method.

背景技术 Background technique

[0002]碳纳米管是一种具有中空管状结构的高长径比特殊碳纳米材料,可以看作是由二维石墨烯沿一定方向卷曲而成,不同的旋转轴方向使得形成的碳纳米管具有不同旋光性和手性参数。 [0002] having a high aspect ratio of carbon nanotubes is a carbon nanomaterial special hollow tubular structure can be seen as a two-dimensional graphene crimped in a certain direction is made different from the rotation axis direction such that the carbon nanotubes and having different optically active chiral parameters. 凭借其独特的中空管状结构和优异的力学、热学、电学和光学性能,碳纳米管近些年来在超级电容器、锂硫电池、薄膜晶体管、橡胶轮胎等方面取得了令人瞩目的成就,并有望取代硅迎来碳基集成电路时代,最终实现制造高性能碳纳米管计算机的梦想。 With its unique hollow tubular structure and excellent mechanical, thermal, electrical and optical properties, carbon nanotubes in recent years has made a remarkable achievement in a super capacitor, a lithium-sulfur battery, a thin film transistor, rubber tires, etc., and is expected to silicon-substituted carbon-based integrated circuit ushered in the era, ultimately producing high performance carbon nanotube dream machine. 然而实现碳纳米管在集成电路方面应用的一个重要前提是实现特定结构碳纳米管的可控制备。 However, an important prerequisite for the application of carbon nanotubes in the preparation of integrated circuits is controlled to achieve a specific structure of carbon nanotubes. IBM指出新一代碳基集成电路对碳纳米管材料的要求是具有超高纯度的半导体选择性、高密度和完美结构,尽管近些年来针对单方面的材料条件要求取得了很大进展,但要想同时实现这几项要求还需要更长时间的探索。 IBM noted that generation of carbon-based integrated circuits requires the selective carbon nanotube material is a semiconductor, the perfect structure having a high density and ultra-high purity, although in recent years has made great progress for unilateral conditions require material, but At the same time it wants to achieve several requirements still need more time to explore.

[0003]结构决定性质,在碳纳米管生长过程中,出现任何结构缺陷都会降低碳纳米管实际应用性能。 [0003] The structure determines properties, the carbon nanotube growth process, any structural defect will reduce the performance of the practical application of carbon nanotubes. 在众多不同种类的碳纳米管中,超长碳纳米管具有全同手性的完美原子结构和宏观长度,实际性能与碳纳米管理论上应具有的超级性能最为接近。 Among the many different types of carbon nanotubes, long carbon nanotubes have identical chirality perfect atomic structure and macroscopic length, the actual performance of carbon nanotubes theoretically should have the closest super performance. 目前已报道的最长超长碳纳米管长度可以达到55cm,并且具有完美结构、全同手性和高半导体选择性,但其密度却仅有2〜3CNTs/100ym,严重限制了其在大规模光电器件方面的应用。 Have been reported in long carbon nanotubes can reach lengths of up to 55cm, and has a perfect structure, identical hand semiconductor and high selectivity, but its density is only 2~3CNTs / 100ym, severely limits its large-scale application of a photoelectric device according to aspects. 尽管近些年来针对提高碳纳米管密度有了很大进展,如采用“特洛伊”催化剂制备出密度高达130CNTsAim的碳纳米管阵列,以及借助石墨烯或S12纳米球减少催化剂聚并,提高超长碳纳米管阵列密度等方法,但所制备的碳纳米管阵列均无法满足高半导体选择性和完美结构的要求。 Although for improving the density of the carbon nanotubes made great progress in recent years, as a "Trojan" catalyst prepared densities up 130CNTsAim the carbon nanotube array, and by means of graphene or nanosphere S12 polyethylene and reducing catalyst, to improve the long carbon the method of the nanotube array density, but the carbon nanotube array was not prepared to meet the high selectivity and perfect semiconductor structure. 另一方面,通过优化催化剂设计,可以实现纯度达92%的手性为(12,6)的碳纳米管阵列制备,但其不具有半导体选择性,同时在密度和完美结构方面均无法满足应用条件。 On the other hand, by optimizing the design of the catalyst can be achieved purity of 92% of the chiral (12,6) for preparing carbon nanotube array, but it does not have selectivity semiconductor, while the density and structure are not perfectly meet the application condition.

[0004]有鉴于此,特提出本发明。 [0004] In view of this, the present invention proposed Japanese.

发明内容 SUMMARY

[0005]本发明的第一目的在于提供一种碳纳米管线团,所述碳纳米管线团高密度、结构完美且手性一致,拓宽了碳纳米管本身的应用领域,在微纳米电子器件及光电器件领域具有极大的应用潜力。 [0005] The first object of the present invention is to provide a carbon nanotube wire group, the group of high-density carbon nanotube wire, and the chiral structure of the perfect agreement, the carbon nanotubes themselves broaden the application field of electronic devices and micro-nano optoelectronic devices field has great potential.

[0006]本发明的第二目的在于提供一种碳纳米管线团的制备方法,所述方法前后步骤衔接紧密、设计合理,简单易行,操作条件温和,所涉及材料均可通过市面购买得到,且环保无污染,最终能够得到手性一致、结构完美、高密度且超长的纳米管线团。 [0006] The second object of the present invention is to provide a method for preparing carbon nanotube wire groups, before and after the method step convergence close, rational design, simple mild operating conditions, the materials involved can be obtained by purchase commercially, and environmental pollution, and ultimately be able to get consistent chiral, perfect structure, high density and ultra-long pipeline nano group.

[0007]为了实现本发明的上述目的,特采用以下技术方案: [0007] To achieve the above object of the present invention, especially the following technical solutions:

[0008]本发明实施例提供了一种碳纳米管线团,由单根或多根直径为0.6-5nm,长度为lmm-5m的碳纳米管无规则缠绕形成,该碳纳米管线团的平铺面积在0.0Ol-1Omm2之间,密度在卜200CNTsAim。 Embodiment [0008] The present invention provides a carbon nanotube wire group, a single or multiple diameter 0.6-5nm, a length of lmm-5m nanotubes formed irregular wound, the carbon nanotube wire tile group area between the 0.0Ol-1Omm2, density BU 200CNTsAim.

[0009]现有技术中对碳纳米管的研究可谓日新月异,主要的研究方向在于碳纳米管的手性结构、长度以及密度等方面,但是问题在于市面上还没有能够兼顾长度、密度以及手性结构等指标均较优的产品问世,因此如何研发出一种高密度、手性一致的碳纳米管材料是现有技术中主要的研究方向。 [0009] Study of the prior art carbon nanotubes with each passing day, the main aspect of the research that chiral carbon nanotube structure, length and density, but the problem is still not able to take into account the length of the market, and the density of the chiral structure and other indicators are superior products come out, how to develop a high-density, chiral carbon nanotube material is consistent with the prior art, the main research directions. 基于目前研究现状,本发明提供一种超长碳纳米管线团,是采用具有一定的直径以及长度要求的碳纳米管经过无规则缠绕形成,可原位获得高密度、、结构完美、手性一致的高半导体选择性超长碳纳米管线团,其显著的优点为其高密度的性能,是现有技术中任何一款产品所不可能比拟的。 Based on the current research situation, the present invention provides a long carbon nanotube wire group is to use carbon nanotubes having a certain diameter and length required is formed through the irregular wound, a high density can be obtained in situ, and perfect structure, consistent chiral the semiconductor carbon nanotube highly selective long coils which significant advantages for high density performance, any one of the prior art product can not be compared. 用其制作的场效应晶体管器件可以同时实现高电流密度和高开关比,在微纳米电子器件及光电器件领域具有极大的应用潜力。 With its production of the field effect transistor device can be realized while the high current density and a high on-off ratio, has great potential in the field of micro-electronics and nano optoelectronic devices.

[0010]本发明的碳纳米管线团,是采用具有特定的直径以及长度的碳纳米管无规则缠绕形成的,碳纳米管的直径需要在0.6-5nm之间,长度需要在lmm-5m,所以在进行选材时如果长度以及直径并不在本发明所揭示的方案范围之内,其是不可能形成具有本发明的这种高密度性能的碳纳米管线团的,另外形成的碳纳米管线团的各个参数指标也需要在适宜的范围内,平铺面积在0.0Ol-1Omm2之间,密度在l-200CNTs/ym,尤其是密度最高可以达到200CNTs/ym,相较于现有技术中的碳纳米管的密度,其完全属于高密度产品,还有其虽然缠绕的不具有规则性,但是其平铺开来所覆盖的面积可达到1mm2之多,正因为碳纳米管线团具有如此优异的性能,因此其在应用时也有更广阔的应用领域。 [0010] The carbon nanotube wire group according to the present invention, is to use a carbon nanotube having a specific diameter and length of the random winding is formed, the diameter of carbon nanotubes is required between 0.6-5nm, we need lmm-5m in length, so each carbon nanotube wire group selection is performed when additional carbon nanotube wire is formed if the length and diameter of the group is not within the scope of the disclosed embodiment of the present invention, it is possible to form such a high density performance of the present invention having parameter index also needs to be within an appropriate range, the area between the plated 0.0Ol-1Omm2, density of l-200CNTs / ym, in particular, the density can be up 200CNTs / ym, carbon nanotubes compared to the prior art density, which is a high-density product completely, though the wound as well as its no regularity, but laid out flat area can be covered to reach as much as 1mm2, because such a group having a carbon nanotube wire excellent performance, in its application also has broader applications.

[0011]在本发明中,每根碳纳米管的直径最好为0.7-4nm,长度最好为1-5m,直径还可以为0.8nm、3nm以及3.5nm等,长度还可以为2m、3m、4m以及4.5m等。 [0011] In the present invention, the diameter of each carbon nanotube is preferably 0.7-4nm, preferably 1-5m length, diameter may also be 0.8nm, 3.5nm and 3nm the like, may also be a length of 2m, 3m , 4m and 4.5m and so on. 形成的碳纳米管线团的平铺面积更优在0.l-8mm2之间,密度更优在100-150CNTs/ym之间,平铺面积还可以为9mm2、9.5謹2、8.51111112、71111112等,密度还可以为19(^见'8/4«11、1950见'8/4«11、1980见'8/4«11等。 Tiling area carbon nanotube wire group formed more preferably between 0.l-8mm2, more preferably a density between 100-150CNTs / ym, the area of ​​the tile and the like may also be 9mm2,9.5 2,8.51111112,71111112 wish, density may also be 19 (^ see '8/4 «11,1950 see' 8/4« 11,1980 see '8/4 «11 or the like.

[0012]对于碳纳米管线团还有一个比较重要的参数指标就是手性结构,而本发明的碳纳米管线团可以达到具有一致的手性结构,即单一的手性选择性可达100%,纯度100%,通过瑞利散射表征该碳纳米管线团也能证明其具有手性一致的结构,而且瑞利散射表征的方法本身可快速、准确区分不同手性的碳纳米管,筛分金属性碳纳米管和半导体性碳纳米管也可以直接判断出碳纳米管手性结构发生变化的具体位置,因此其表征结果具有很高的准确性。 [0012] For carbon nanotube wire group there is a more important parameter indicator is the chiral structure, and coils of the present invention the carbon nanotube can be achieved consistent with the chiral structure, i.e. a single chiral selectivity up to 100% purity 100%, the carbon nanotube characterized by Rayleigh scattering line groups can also able to demonstrate a consistent chiral structure, and Rayleigh scattering characterization per se can be quickly and accurately distinguish between different chiral carbon nanotubes, metallic screening carbon nanotubes and semiconductor carbon nanotubes may also directly determine the specific position of the chiral carbon nanotube structure changes, so the characterization results with high accuracy.

[0013]本发明实施例除了提供了一种碳纳米管线团,还提供了一种该碳纳米管线团的其中一种制备方法,当然现有技术中的其他制备方法只要得到本发明的碳纳米管线团产品均在本发明的保护范围内。 Embodiment [0013] In addition the present invention provides a carbon nanotube wire groups, which is also provided a method of preparing a carbon nanotube wire group, of course, prepared by other methods as long as the prior art of the present invention obtained carbon nano product line group are within the scope of the present invention.

[0014]本发明揭示的这种碳纳米管线团的制备方法主要包括如下步骤: [0014] The preparation of this carbon nanotube wire groups disclosed in the present invention mainly comprises the following steps:

[0015] (A)将催化剂负载于生长基底置于反应器中,通入惰性气体与氢气的混合惰性气体还原催化剂后,再通入碳源与氢气的混合反应气体并加热制备得到超长碳纳米管; [0015] (A) a catalyst supported on a growth substrate placed in a reactor, an inert gas and hydrogen into a mixture of inert gas reduction catalyst, and then passed into the reaction mixture with hydrogen gas and heated carbon prepared long carbon nanotube;

[0016] (B)向反应器中加入声波,使得超长碳纳米管在声波诱导的漩涡中发生屈曲缠绕,其中所述声波由频率控制在lOyHz-lOkHz之间,振幅控制在5mVPP-70VPP的电信号经电声转换形成; [0016] (B) was added to the reactor the acoustic wave, so that buckling occurs in wound long carbon nanotubes vortex induced acoustic wave, wherein the sound wave is controlled by a frequency between lOyHz-lOkHz, controlling the amplitude of 5mVPP-70VPP formed by the electroacoustic transducer electrical signal;

[0017] (C)10-20min改通入所述混合惰性气体并停止输送声波,降温至400°C以下后取出即得碳纳米管线团。 [0017] (C) 10-20min changed into the mixed gas and stopping the flow of inert acoustic wave, that was lowered to remove the carbon nanotube wire group to 400 ° C.

[0018]其中步骤(A)中,如何制备超长碳纳米管现有技术中本身已有揭示,这里不需要赘述,优选地,碳纳米管生长催化剂为Fe、Mo、Co、Cu、Ni等单一金属或金属合金,碳纳米管生长催化剂为纳米颗粒,催化剂负载方式为按压、光刻蚀、旋涂、蒸镀和管壁预沉积中至少一种,混合反应气应为应为高纯气且硫化物〈0.3yL/L,砷化物〈0.3yL/L;反应温度为800-1200°C并使温度波动范围<±1°C;反应全程为恒正压,压力波动范围<±lPa;反应气流为截面上均勾分布的稳定层流,径向扰动〈± 3mm。 [0018] wherein steps (A), the prior art how to prepare long carbon nanotubes has been disclosed per se, need not be repeated here, preferably, the carbon nanotubes are grown catalyst is Fe, Mo, Co, Cu, Ni, etc. single metal or a metal alloy, carbon nanotube growth catalyst nanoparticles, catalyst loading mode is pressed, light etching, spin coating, vapor deposition and depositing at least one pre-wall, the reaction gas mixture should be as high purity gas and sulfide <0.3yL / L, arsenide <0.3yL / L; the reaction temperature is 800-1200 ° C and the temperature fluctuation range of <± 1 ° C; for the constant pressure throughout the reaction, the pressure fluctuation range of <± lPa; the reaction steady laminar airflow on both hook-sectional profile, the radial perturbations <± 3mm.

[0019]本发明重点要保护的地方在于如何采用超长碳纳米管制备碳纳米管线团,即在反应后期,从反应器的入口、出口端或其它位置加入一定频率、一定振幅及方向的声波,只要能将声波输送至反应器中即可,以使声波经过反射和传播到达碳纳米管生长区,使反应器中层流气流在该声波作用下,形成Karman涡街,利用该涡街使气流导向作用下随动漂浮生长的碳纳米管发生屈曲缠绕,获得手性一致的超长碳纳米管线团,一般该涡街所缠绕的碳纳米管弯曲直径与KoImogorov最小祸尺寸相当,在10-20微米。 [0019] The focus of the present invention is how to protect the place of carbon nanotubes prepared using the carbon nanotubes long coils, i.e., the reaction in the late addition of a certain frequency from the inlet, the outlet end of the reactor, or other location, and direction of the constant amplitude acoustic so long as a sound wave can be delivered to the reactor, so that the acoustic wave propagating through reflection and reach the carbon nanotube growth zone of the reactor at the middle of the air flow sonication, Karman vortex formed by the vortex gas stream lower guide follower floating action of carbon nanotubes grown buckling wound to obtain consistent chiral carbon nanotube long line group, the vortex is generally wound with KoImogorov minimum bend diameter of the carbon nanotubes disaster comparable size, 10-20 m.

[0020 ] 声波是由频率控制在I ΟμΗζ -1 OkHz之间,振幅控制在5mVPP_7 O Vpp的电信号经电声转换形成的,更优的,电信号的频率还可以为1-1OkHz之间,振幅控制在20-70VPP之间,例如频率还可以是2kHz、3kHz、4kHz、5kHz,振幅还可以是25VPP、30VPP、35VPP、40VPP等。 [0020] In the acoustic wave is controlled by the frequency I ΟμΗζ between -1 OkHz, amplitude control electrical signals in 5mVPP_7 O electroacoustic conversion Vpp formation, better, between the frequency of the electrical signal may also be 1-1OkHz, amplitude control between 20-70VPP, for example, frequency may also be 2kHz, 3kHz, 4kHz, 5kHz, the amplitude can be 25VPP, 30VPP, 35VPP, 40VPP like. 电声转化一般采用的是转换器得以实现,转换器可以选择扬声器、旋笛、压电式换能器以及磁致伸缩式换能器中的其中一种,实际操作时声波转化后经聚能器集中并放大能量,放大后的声波从反应器入口,出口端或其他位置进入,聚能器为变幅杆或具有变口径特征的连接装置。 Electro-acoustic conversion is generally used in the converter is achieved, the converter may select the speaker, spin flute, piezoelectric transducers and magnetostrictive transducers in one, the actual operation after conversion by the acoustic concentrators and amplification energy is concentrated, the amplified sound waves from the reactor inlet, into the outlet end or other location, as concentrators connecting means having a horn or a diameter varying characteristics.

[0021 ]步骤(C)中,在反应器中输送声波10-20min后,碳纳米管线团基本成型,此时可以开始冷却降温,因为此时反应器的温度高达900°C以上,由通入混合反应气体改为通入惰性混合气体,并停止输送声波,此时需要注意的操作在于一定在通着惰性混合气体的同时再停止输送声波,因为碳纳米管线团在降温的过程中会发生烧蚀现象,为了避免这种现象的发生,需要通入惰性混合气体进行保护,也可以在通入保护气一段时间后大概0.5-2h使得碳纳米管线团的性能更加稳定时再停止加入声波,反应停止,当反应器中的温度降温至400°(:以下后取出即得碳纳米管线团,取出样品进行后续表征。需要注意的是,在加入声波时超长碳纳米管也还在不断生长,也就是说碳纳米管是一边生长一边发生屈曲缠绕的。 [0021] Step (C) in the reaction vessel after transporting acoustic 10-20min, substantially shaped carbon nanotube wire group, can begin to cool down at this time, because the temperature of the reactor up to 900 ° C, into a through the reaction mixture into an inert gas to the mixed gas and stopping the flow of the acoustic wave, at this time must be noted that the operation in an inert gas mixture through the same time and then stopping the flow of the acoustic wave, since the carbon nanotube cooling coils during burning occurs cavitation, in order to avoid the occurrence of this phenomenon, an inert gas mixture into the need for protection, so that the performance may be about 0.5-2h carbon nanotube wire group after a period of time into the protective gas added then stop when the acoustic wave is more stable, the reaction stopped, when the temperature in the reactor is lowered to 400 ° (: group removed to give the carbon nanotube wire after the samples were removed for subsequent characterization should be noted that, when added to the acoustic wave long carbon nanotubes can still continue to grow. that is the side of the growth of carbon nanotubes while buckling wound.

[0022]制备得到的纳米管线团如进一步增加其密度,可将纳米管线团浸于表面活性剂中,如乙二醇、甘油、聚乙二醇、乙醇等。 [0022] prepared as nano line groups to further increase its density, nano line group may be immersed in a surfactant, such as ethylene glycol, glycerol, polyethylene glycol, ethanol and the like.

[0023]现有技术相比,本发明的有益效果为: [0023] compared to the prior art, the beneficial effects of the present invention are:

[0024] (I)本发明的碳纳米管线团,高密度、结构完美且手性一致,其显著的优点为其高密度的性能。 [0024] The coils of the present invention is the carbon nanotube, a high-density, structural perfection and chiral consistent, significant advantages for its performance (I) a high density. 用其制作的场效应晶体管器件可以同时实现高电流密度和高开关比,在微纳米电子器件及光电器件领域具有极大的应用潜力; With its production of the field effect transistor device can be realized while the high current density and a high on-off ratio, has great potential in the field of micro and nano optoelectronic devices and electronic devices;

[0025] (2)本发明的碳纳米管线团的制备方法,前后步骤衔接紧密、设计合理,简单易行,操作条件温和,所涉及材料均可通过市面购买得到,且环保无污染,只要严格按照本发明的操作步骤一步步的进行,制备出的碳纳米管线团完全符合本发明的各项参数标准,具有一致的手性结构。 [0025] (2) Method for preparing carbon nanotube wire group according to the present invention, before and after the step of convergence close, rational design, simple and mild operating conditions, the materials involved can be obtained by commercially purchased, and environmental pollution, as long as strict carried out step by step in accordance with the procedure of the present invention, the carbon nanotube wire group prepared in full compliance with the standard parameters of the present invention, the structure having a uniform chirality.

附图说明 BRIEF DESCRIPTION

[0026]为了更清楚地说明本发明实施例或现有技术中的技术方案,以下将对实施例或现有技术描述中所需要使用的附图作简单地介绍。 [0026] In order to more clearly illustrate the technical solutions in the embodiments or the prior art embodiment of the present invention, the following embodiments or the accompanying drawings required for describing the prior art will be used in the embodiments are introduced briefly.

[0027]图1为本发明实施例一的制备方法得到的超长碳纳米管的SEM表征图谱; [0027] FIG. 1 SEM characterization map prepared in Example long carbon nanotubes obtained in an embodiment of the present invention;

[0028]图2为本发明实施例一的制备方法得到的超长碳纳米管的瑞利表征图谱; Rayleigh [0028] FIG. 2 long carbon nanotubes obtained in an Example of the present embodiment of the invention the characterization map;

[0029]图3为本发明实施例一的制备方法中使用的装置结构示意图,其中,I为用于提供电信号的函数信号发生器;2为用于生长碳纳米管的基底;3为用于催化生长碳纳米管的催化剂;4为用于汇聚声波能量的聚能器;5为用于将电信号转换为声波振动的转换器;6为在声波干扰下基底表面漂浮生长的不同形态碳纳米管;7为反应过程通入的碳源和氢气的混合反应气体; [0029] FIG. 3 is a schematic diagram of a device configuration of the production method used in the embodiment of the present invention, wherein, the I signal generator providing an electrical signal as a function; 2 substrate for growing carbon nanotubes; with 3 the catalyst in the catalytic carbon nanotube growth; 4 is a concentrator for concentrating the sound wave energy; 5 for converting electrical signals to acoustic vibrations of the transducer; floating on the surface of the substrate 6 is grown under the different forms of carbon acoustic interference nanotubes; 7 is a mixed reaction gas introduced into the reaction of carbon and hydrogen;

[0030]图4为本发明实施例一的制备方法获得的不同形态碳纳米管线团的扫描电镜(SEM)表征图谱; [0030] Figure 4 a scanning electron microscope of different forms of carbon nanotubes prepared in Example line groups obtained by a (SEM) Characterization of Atlas embodiment of the invention;

[0031]图5为本发明实施例二的制备方法获得的碳纳米管线团的拉曼散射表征数据图表; [0031] FIG. 5 Raman scattering characterization data table prepared carbon nanotube wire group obtained according to the second embodiment of the invention;

[0032]图6为本发明实施例三的制备方法获得的碳纳米管线团的瑞利散射表征数据图表。 [0032] FIG. 6 Rayleigh scattering characterization data table prepared carbon nanotube wire group according to a third embodiment of the present invention is obtained.

具体实施方式 detailed description

[0033]下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限制本发明的范围。 [0033] The following embodiments in conjunction with embodiments of the present invention will be described in detail, those skilled in the art will appreciate that the following examples merely illustrate the invention and should not be considered as limiting the scope of the invention. 实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。 Examples are the specific conditions are not specified embodiment, in accordance with conventional conditions or conditions recommended by the manufacturer. 所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。 The reagents or equipment not specified by the manufacturer, both can be purchased conventional products obtained through a commercial.

[0034] 实施例1 [0034] Example 1

[0035] I)将按压有0.lmol/L FeCl3催化剂的乙醇溶液的硅片基底放置在基板或石英舟中,置于加热炉反应器内; [0035] I) have pressing 0.lmol / L FeCl3 catalyst in ethanol silicon substrate is placed on a substrate or a quartz boat and placed in a reactor furnace;

[0036] 2)向反应器内通入200sccm的氩气和氢气的混合惰性气(Ar: H2 = 1:2,v/v)作为保护性气体,并开始升温,当温度升至900-101(TC后,恒温20min。接着进入反应阶段,通入ISOsccm甲烷和氢气混合反应气(H2:CH4 = 2:1,V/V),开始超长碳纳米管制备反应,反应时间10min-2h,得到的单根超长碳纳米管样品扫描电镜表征结果如图1所示,瑞利表征图谱如图2所示,图片右下角标注的为长度标准,经检测碳纳米管的直径为0.6-5nm,长度为 [0036] 2) 200sccm into the reactor to argon and hydrogen mixture of an inert gas (Ar: H2 = 1: 2, v / v) as the protective gas, and the temperature was raised when the temperature was raised to 900-101 . (after TC, thermostat 20min and then into the reaction stage, into the reaction mixture ISOsccm methane and hydrogen gas (H2: CH4 = 2: 1, V / V), prepared by the reaction began long carbon nanotubes, the reaction time of 10min-2h, the resulting single long sample of carbon nanotubes SEM characterization results shown in Figure 1, the Rayleigh spectrum characterize 2, the lower right corner of the labeled standard length, nanotube diameter detected 0.6-5nm a length of

[0037] 3)当反应后期,向反应器中加入声波,声波经过电声转换装置形成,电声转换装置的搭建如图3所示,I为用于提供电信号的函数信号发生器,2为用于生长碳纳米管的基底,3为用于催化生长碳纳米管的催化剂,4为用于汇聚声波能量的聚能器,5为用于将电信号转换为声波振动的转换器,6为在声波干扰下基底表面漂浮生长的不同形态碳纳米管,7为反应过程通入的碳源和氢气的混合反应气体。 [0037] 3) When the post-reaction function generator, was added to the reactor the acoustic wave, the acoustic wave is formed through the electro-acoustic converter, the electro-acoustic converter structures shown in Figure 3, to provide an electrical signal for the I, 2 substrate for growing carbon nanotubes, 3 as catalyst for growing carbon nanotubes, 4 for converging acoustic energy concentrator, 5 for converting electrical signals to acoustic vibrations of the transducer, 6 to different forms of interference in the substrate floating on the surface acoustic wave of growing carbon nanotubes, the mixed reaction gas 7 is introduced into the reaction process of carbon and hydrogen. 其中,I与5之间通过一根双夹线导线连接,聚能器与转换器之间采用硅胶或其他不干胶粘性密合。 Wherein, between I and 5 are connected by one pair of conductor clamp used between the transducer and the poly converter viscous gel or other adhesive adhesion. 电信号的频率控制在lOyHz-lOkHz之间,振幅控制在5mVPP-70VPP,由聚能器的出口端输出一定频率及振幅的声波,从反应器的入口传播到碳纳米管生长区,压缩反应气流,使气流导向作用下随动漂浮生长的单根超长碳纳米管发生屈曲缠绕,获得超长碳纳米管线团;其中,声波为连续的正弦波,转换器为扬声器; Controlling the frequency of electrical signals between lOyHz-lOkHz, controlling the amplitude 5mVPP-70VPP, a constant frequency and amplitude sound wave output from the exit end of the concentrator, transmission from the inlet of the reactor to the carbon nanotube growth zone, compressing the reaction gas stream , under the action of the air flow guide follower floating long nanotubes grown single buckling wound coils to obtain long nanotubes; wherein the acoustic wave is a continuous sine wave converter to a speaker;

[0038] 4)10-20min后改通入200sccm的氩气和氢气的混合惰性气(Ar:H2 = l:2,v/v)以防止碳管在降温过程被烧蚀,同时关闭声波发生装置,当温度降至400°C以下后,取出样品进行后续表征,表征结果见图4所示,而且碳纳米管长度越长,形成的碳纳米管线团密度越高,面积越大,经检测其面积可达0.0Ol-1Omm2之间,密度在l-200CNTsAim,具有一致的手性结构。 [0038] After changing into 200sccm 4) 10-20min argon and hydrogen mixture of an inert gas (Ar: H2 = l: 2, v / v) to prevent carbon tubes in the cooling process is ablated, while closing the sound wave generating means, when the temperature was lowered to 400 ° C, samples were removed for subsequent characterization, characterization results shown in Figure 4, and the longer the tube length, the higher the density of the carbon nanotubes formed clew, the larger the area, the detection up to the area between 0.0Ol-1Omm2, density of l-200CNTsAim, chiral structures having consistent.

[0039] 实施例2 [0039] Example 2

[0040] I)将按压有0.lmol/L FeCl3催化剂的乙醇溶液的硅片基底放置在基板或石英舟中,置于加热炉反应器内; [0040] I) have pressing 0.lmol / L FeCl3 catalyst in ethanol silicon substrate is placed on a substrate or a quartz boat and placed in a reactor furnace;

[0041 ] 2)向反应器内通入200sccm的氩气和氢气的混合惰性气(Ar: H2 = 1:2,v/v)作为保护性气体,并开始升温,当温度升至900-101(TC后,恒温20min。接着进入反应阶段,通入ISOsccm甲烷和氢气混合反应气(H2:CH4 = 2:1,V/V),开始超长碳纳米管制备反应,反应时间10min-2h,得到的超长碳纳米管,经检测直径为0.7_4nm,长度为l_5m; [0041] 2) 200sccm into the reactor to argon and hydrogen mixture of an inert gas (Ar: H2 = 1: 2, v / v) as the protective gas, and the temperature was raised when the temperature was raised to 900-101 . (after TC, thermostat 20min and then into the reaction stage, into the reaction mixture ISOsccm methane and hydrogen gas (H2: CH4 = 2: 1, V / V), prepared by the reaction began long carbon nanotubes, the reaction time of 10min-2h, long carbon nanotubes obtained by detecting a diameter of 0.7_4nm, length l_5m;

[0042] 3)当反应后期,向反应器中加入声波,声波经过电声转换装置形成,电声转换装置米用实施例1的搭建方法进行搭建。 [0042] 3) When the end of the reaction, was added to the reactor the acoustic wave, the acoustic wave is formed through the electro-acoustic conversion means, electro-acoustic converter built with a meter for building method of Example 1. 电ί目号的频率控制在I_10kHz之间,振幅控制在20-70VPP,由聚能器的出口端输出一定频率及振幅的声波,从反应器的出口传播到碳纳米管生长区,压缩反应气流,使气流导向作用下随动漂浮生长的多根碳纳米管发生屈曲缠绕,获得超长碳纳米管线团;其中,声波为间断的锯齿波,转换器为压电式换能器; Frequency of the electrical control ί mesh number between I_10kHz, controlling the amplitude 20-70VPP, a constant frequency and amplitude sound wave output from the exit end of the concentrator, transmission from the outlet of the reactor to the carbon nanotube growth zone, compressing the reaction gas stream , under the action of the air flow guide follower floating a plurality of carbon nanotubes grown buckling wound coils to obtain long nanotubes; wherein the sound wave is interrupted sawtooth converter is a piezoelectric transducer;

[0043] 4) 10_20min后改通入200sccm的氩气和氢气的混合气(Ar:H2 = 1: 2,v/v)以防止碳管在降温过程被烧蚀,Ih后关闭声波发生装置,当温度降至400°C以下后,取出样品浸于乙二醇中以增加其密度,随后进行后续表征,图5为对实施例2获得的碳纳米管线团样品上四个不同位置进行拉曼表征的数据图像结果。 [0043] 4) 200sccm 10_20min changed into argon and hydrogen mixed gas (Ar: H2 = 1: 2, v / v) to prevent carbon tubes in the cooling process to be ablated, after Ih closed wave generating means, after the temperature was lowered to 400 ° C, samples were taken immersed in ethylene glycol to increase its density, followed by subsequent characterization, for the FIG. 5 embodiment four different positions on the sample 2 carbon nanotube wire group obtained in Example Raman the results of the characterization data of the image. 碳纳米管的特征峰位于1500-1600cm—I称为G峰,位移在UOO-HOOcm—1的特征峰称为D峰,一般常用D峰与G峰峰强度的比值来反映碳纳米管结构缺陷程度,比值越大,缺陷程度越高。 Wherein the carbon nanotube peak at 1500-1600cm-I peak called G, the displacement characteristic peak UOO-HOOcm-1 is called D peak and D peak is generally used a ratio of peak intensity of the carbon nanotube structure to reflect the defect G degree, the larger the ratio, the higher the degree of the defect. 从图5中的拉曼峰数据结果可以看出,碳纳米管线团上不同位置在WOO-HOOcm—1处几乎都没有D峰,说明所制备的碳纳米管线团具有完美结构,手性一致。 Raman peaks can be seen from the data results in Figure 5, the carbon nanotube wire groups at different positions WOO-HOOcm-1 at a D almost no peaks, indicating that the carbon nanotube wire group which is prepared with perfect structure, uniform chirality. 另一方面,一般常用G峰的峰形表示碳纳米管的金属性和半导体性,半导体性碳纳米管的G峰尖锐,而金属性碳纳米管的G峰展宽,从图5中的峰形可以判断所制备的碳纳米管线团为半导体性,经检测其面积可达0.1_8mm2之间,密度在100-150CNTsAim,具有一致的手性结构。 On the other hand, the peak shape used generally G peak represents metallic and semiconducting carbon nanotubes, semiconducting carbon nanotube peak G sharp and G show metallic carbon nanotube peak width, peak shape from FIG. 5 Analyzing can be prepared semiconducting carbon nanotube wire group is, up to the area between the detected 0.1_8mm2, density 100-150CNTsAim, structures having uniform chirality.

[0044] 实施例3 [0044] Example 3

[0045] I)将按压有0.lmol/L FeCl3催化剂的乙醇溶液的硅片基底放置在基板或石英舟中,置于加热炉反应器内; [0045] I) have pressing 0.lmol / L FeCl3 catalyst in ethanol silicon substrate is placed on a substrate or a quartz boat and placed in a reactor furnace;

[0046] 2)向反应器内通入200sccm的氩气和氢气的混合惰性气(Ar: H2 = 1:2,v/v)作为保护性气体,并开始升温,当温度升至100tC后,恒温20min。 [0046] 2) 200sccm into the reactor to argon and hydrogen mixture of an inert gas (Ar: H2 = 1: 2, v / v) as the protective gas, and the temperature was raised when the temperature rises to 100tC, constant temperature 20min. 接着进入反应阶段,通入ISOsccm甲烷和氢气混合反应气(H2:CH4 = 2:1,V/V),开始超长碳纳米管制备反应,反应时间1min-2h,得到的超长碳纳米管,经检测直径为5nm,长度为5m; Then into the reaction stage, into the reaction mixture ISOsccm methane and hydrogen gas (H2: CH4 = 2: 1, V / V), long carbon nanotubes start the reaction, the reaction time of 1min-2h, long carbon nanotubes obtained , by detecting a diameter of 5 nm, a length of 5m;

[0047] 3)当反应后期,向反应器中加入声波,声波经过电声转换装置形成,电声转换装置米用实施例1的搭建方法进行搭建。 [0047] 3) When the end of the reaction, was added to the reactor the acoustic wave, the acoustic wave is formed through the electro-acoustic conversion means, electro-acoustic converter built with a meter for building method of Example 1. 电ί目号的频率控制在I_10kHz之间,振幅控制在20-70VPP,由聚能器的出口端输出一定频率及振幅的声波,从反应器的出口传播到碳纳米管生长区,压缩反应气流,使气流导向作用下随动漂浮生长的碳纳米管发生屈曲缠绕,获得超长碳纳米管线团;其中,声波为间断的方波,转换器为磁致伸缩式换能器; Frequency of the electrical control ί mesh number between I_10kHz, controlling the amplitude 20-70VPP, a constant frequency and amplitude sound wave output from the exit end of the concentrator, transmission from the outlet of the reactor to the carbon nanotube growth zone, compressing the reaction gas stream the air guide under the action of carbon nanotubes grown floating follower buckling wound coils to obtain long nanotubes; wherein the intermittent acoustic square wave converter is a magnetostrictive transducer;

[0048] 4)10-20min后改通入200sccm的氩气和氢气的混合惰性气(Ar:H2 = l:2,v/v)以防止碳管在降温过程被烧蚀,30min后关闭声波发生装置,当温度降至400°C以下后,取出样品浸于甘油中以增强其密度,随后进行后续表征,图6为对实施例3获得的碳纳米管线团样品上四个不同位置进行瑞利表征的数据图像结果。 [0048] After changing into 200sccm 4) 10-20min argon and hydrogen mixture of an inert gas (Ar: H2 = l: 2, v / v) to prevent carbon tubes in the cooling process to be ablated, after 30min acoustic closed generating means, when the temperature was lowered to 400 ° C, immersed in glycerin samples were taken to enhance the density thereof, followed by a subsequent characterization, FIG. 6 for the embodiment four different positions on the sample 3 obtained in Example nanotube wire group for Swiss characterization data of the image result of interest. 瑞利表征可以直观地判断手性结构是否一致,若不同位置手性结构一致,则在瑞利峰图像上会有相同的峰形和峰位置。 Characterization of Rayleigh can visually determine whether or not chiral structure consistent, uniform if the chiral structure at different positions, will have the same peak shape and the position of the image on the Ruili Feng. 从图6获取的瑞利峰图像数据看,四个不同位置的峰形和峰位置基本相同,说明具有一致的手性结构,经检测,其面积可达9mm2,密度在190CNTsAxm。 Ruili Feng from the image data acquired see FIG. 6, peak shape and position of the four different positions is substantially the same, indicating that chirality has a uniform structure, by detecting an area of ​​up to 9mm2, density 190CNTsAxm.

[0049]尽管已用具体实施例来说明和描述了本发明,然而应意识到,在不背离本发明的精神和范围的情况下可以作出许多其它的更改和修改。 [0049] Although the embodiments specifically illustrated and described by the present invention, it should be appreciated that many other changes may be made and modifications without departing from the spirit and scope of the invention. 因此,这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。 Thus, this means comprises in the appended claims all such changes and modifications belong to the scope of the invention.

Claims (10)

  1. 1.一种碳纳米管线团,其特征在于,由单根或多根直径为0.6-5nm,长度为lmm-5m的碳纳米管无规则缠绕形成,该碳纳米管线团的平铺面积在0.0Ol-1Omm2之间,密度在1-200CNTs/ymo A carbon nanotube wire group, wherein the single or multiple diameter 0.6-5nm, a length of lmm-5m is formed of carbon nanotubes randomly wound, the area of ​​the tile group in the carbon nanotube wires 0.0 between Ol-1Omm2, density 1-200CNTs / ymo
  2. 2.根据权利要求1所述的一种碳纳米管线团,其特征在于,每根碳纳米管的直径为0.7-4]1111,长度为1-5111。 A carbon nanotube according to claim 1 of the line group, characterized in that the diameter of each carbon nanotube is 0.7 to 4] 1111, a length of 1-5111.
  3. 3.根据权利要求1所述的一种碳纳米管线团,其特征在于,所述碳纳米管线团的平铺面积在0.1-8mm2之间,密度在100-150CNTsAxm。 A carbon nanotube according to claim 1 of the wire group, wherein the carbon nanotube tiled area between coils 0.1-8mm2, density 100-150CNTsAxm.
  4. 4.根据权利要求1-3任一项所述的一种碳纳米管线团,其特征在于,该碳纳米管线团具有一致的手性结构。 A carbon nanotube according to claim any one of claims coils 1-3, characterized in that, the carbon nanotube wire group has a chiral structure uniform.
  5. 5.权利要求1-4任一项所述的碳纳米管线团的制备方法,其特征在于,包括如下步骤: (A)将催化剂负载于生长基底置于反应器中,通入惰性气体与氢气的混合惰性气体还原催化剂后,再通入碳源与氢气的混合反应气体并加热制备得到超长碳纳米管; (B)向反应器中加入声波,使得超长碳纳米管在声波诱导的漩涡中发生屈曲缠绕,其中所述声波由频率控制在lOyHz-lOkHz之间,振幅控制在5mVPP-70VPI^电信号经电声转换形成; (C) 10-20min改通入所述混合惰性气体并停止输送声波,降温至400°C以下后取出即得碳纳米管线团。 The method of preparing carbon nanotube wire group according to any one of claims 1-4 claim 1, characterized in that it comprises the steps of: (A) a catalyst supported on a growth substrate placed in a reactor, an inert gas and hydrogen into mixing an inert gas reduction catalyst, the reaction gas is mixed with hydrogen and then introduced into a carbon source and heated to obtain long nanotubes prepared; (B) reactor was added to the acoustic wave, so that the long nanotubes in the acoustic wave-induced vortex the buckling is wound, wherein the sound wave is controlled by a frequency between lOyHz-lOkHz, controlling the amplitude 5mVPP-70VPI ^ form a electrical electroacoustic transducer; (C) 10-20min modified mixed into the inert gas is stopped and conveying the acoustic wave, to remove the cooling coils to obtain the carbon nanotube to 400 ° C.
  6. 6.根据权利要求5所述的碳纳米管线团的制备方法,其特征在于,所述步骤(B)中,所述声波为连续的或间断的正弦波、锯齿波、方波中的其中一种,优选为正弦波。 6. A method for preparing carbon nanotube wire group according to claim 5, wherein one of said step (B), the sound wave is a continuous or discontinuous sine wave, sawtooth wave, square waves species, preferably a sine wave.
  7. 7.根据权利要求5所述的碳纳米管线团的制备方法,其特征在于,所述步骤(B)中,采用转换器实现电声转换,所述转换器为扬声器、旋笛、压电式换能器以及磁致伸缩式换能器中的其中一种。 The production method of claim 5 carbon nanotube wire group claim, wherein said step (B), a converter implemented using electroacoustic transducer, the transducer is a speaker, a spin flute, piezoelectric and wherein the transducer magnetostrictive transducer of.
  8. 8.根据权利要求7所述的碳纳米管线团的制备方法,其特征在于,所述步骤(B)中,电声转化后经聚能器集中并放大能量,再向反应器中加入声波。 8. The preparation method of carbon nanotube wires 7 groups according to claim, characterized in that, in the electro-acoustic conversion through the concentrator focus and amplify the energy of the step (B), an acoustic wave is added to the reaction vessel.
  9. 9.根据权利要求5所述的碳纳米管线团的制备方法,其特征在于,所述步骤(B)中,电信号的频率控制在1-1OkHz之间,振幅控制在20-70VPP之间。 9. A method of preparing the carbon nanotube wire group claim, wherein said step (B), the frequency of the electrical signal between the control 1-1OkHz, amplitude control between 20-70VPP.
  10. 10.根据权利要求5所述的碳纳米管线团的制备方法,其特征在于,所述步骤(C)中,改通入所述混合惰性气体后,经过0.5-2h再停止加入声波; 优选地,所述步骤(C)中,将制备得到的纳米管线团浸泡于表面活性剂中以增大纳米管线团的密度,所述表面活性剂为乙二醇、甘油、聚乙二醇、乙醇中的其中一种。 10. A method for preparing carbon nanotube wire group according to claim 5, wherein said step (C) is, after the inert gas into the mixture, and then was stopped after 0.5-2h acoustic wave; preferably said step (C), the prepared nano line group soaked in a surfactant to increase the density of the nano-line group, the surfactant is ethylene glycol, glycerol, polyethylene glycol, ethanol It is one of them.
CN 201610031119 2016-01-18 2016-01-18 A carbon nanotube wire group and its preparation method CN105692584B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201610031119 CN105692584B (en) 2016-01-18 2016-01-18 A carbon nanotube wire group and its preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201610031119 CN105692584B (en) 2016-01-18 2016-01-18 A carbon nanotube wire group and its preparation method

Publications (2)

Publication Number Publication Date
CN105692584A true true CN105692584A (en) 2016-06-22
CN105692584B CN105692584B (en) 2018-03-06

Family

ID=56227418

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201610031119 CN105692584B (en) 2016-01-18 2016-01-18 A carbon nanotube wire group and its preparation method

Country Status (1)

Country Link
CN (1) CN105692584B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101582302A (en) * 2008-05-14 2009-11-18 清华大学;鸿富锦精密工业(深圳)有限公司 Carbon nano tube/conductive polymer composite material
US20140057097A1 (en) * 2012-08-22 2014-02-27 National Defense University Method for fabricating coiled nano carbon material, coiled nano carbon layered substrate and coiled nano carbon material thereof
CN104903391A (en) * 2012-12-07 2015-09-09 韩华石油化学株式会社 Rubber composite composition for highly thermally conductive bladder comprising carbon nanotubes and production method for same
CN104986753A (en) * 2015-06-25 2015-10-21 清华大学 Super-long carbon nano tube and preparing method and device thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101582302A (en) * 2008-05-14 2009-11-18 清华大学;鸿富锦精密工业(深圳)有限公司 Carbon nano tube/conductive polymer composite material
US20140057097A1 (en) * 2012-08-22 2014-02-27 National Defense University Method for fabricating coiled nano carbon material, coiled nano carbon layered substrate and coiled nano carbon material thereof
CN104903391A (en) * 2012-12-07 2015-09-09 韩华石油化学株式会社 Rubber composite composition for highly thermally conductive bladder comprising carbon nanotubes and production method for same
CN104986753A (en) * 2015-06-25 2015-10-21 清华大学 Super-long carbon nano tube and preparing method and device thereof

Also Published As

Publication number Publication date Type
CN105692584B (en) 2018-03-06 grant

Similar Documents

Publication Publication Date Title
Cha et al. Sound‐driven piezoelectric nanowire‐based nanogenerators
Tong et al. Growth of ZnO nanostructures with different morphologies by using hydrothermal technique
Hughes et al. Formation of piezoelectric single-crystal nanorings and nanobows
Kang et al. One-step water-assisted synthesis of high-quality carbon nanotubes directly from graphite
Piscanec et al. Raman spectroscopy of silicon nanowires
Yan et al. Chemical vapor deposition of graphene single crystals
US20080299031A1 (en) Method for making a carbon nanotube film
Kim et al. High performance of cup-stacked-type carbon nanotubes as a Pt–Ru catalyst support for fuel cell applications
Kim et al. Activation energy paths for graphene nucleation and growth on Cu
Giermann et al. Solid-state dewetting for ordered arrays of crystallographically oriented metal particles
US20040058153A1 (en) Density controlled carbon nanotube array electrodes
Yang et al. Electrochemical route to the synthesis of ultrathin ZnO nanorod/nanobelt arrays on zinc substrate
Yang et al. Dual Raman features of double coaxial carbon nanotubes with N-doped and B-doped multiwalls
US7408186B2 (en) Controlled alignment catalytically grown nanostructures
Wirth et al. Diffusion-and reaction-limited growth of carbon nanotube forests
US20080236804A1 (en) Electrothermal interface material enhancer
Hofmann et al. In situ observations of catalyst dynamics during surface-bound carbon nanotube nucleation
Wang et al. Noncontact thermal characterization of multiwall carbon nanotubes
US8068626B2 (en) Thermoacoustic device
Pelletier et al. Aluminum nanowire polarizing grids: Fabrication and analysis
Denysenko et al. Ion-assisted precursor dissociation and surface diffusion: Enabling rapid, low-temperature growth of carbon nanofibers
Imura et al. Photoluminescence from gold nanoplates induced by near-field two-photon absorption
Xiang et al. Acetylene-accelerated alcohol catalytic chemical vapor deposition growth of vertically aligned single-walled carbon nanotubes
Reina et al. Growth mechanism of long and horizontally aligned carbon nanotubes by chemical vapor deposition
Wang et al. Free-standing subnanometer graphite sheets

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
GR01