碳源流量对碳纳米管厚膜形貌和结构的影响

采用低压化学气相沉?积(LPCVD)在镍片上制备了厚度在400～1000μm范围的碳纳米管(CNTs)薄膜, 研究了碳源(乙炔)流量对碳纳米管薄膜形貌 和结构的影响. 随乙炔流量的增加, 碳纳米管薄膜厚度和产量增大. 电子显微镜和拉曼光谱研究结果表?明, 在乙炔流量为10sccm下制备的碳纳 米管直径分布范围最小(10～100nm), 石墨化程度最高, 缺陷密度最小, 晶形最完整. 随着乙炔流量的增大(30～90sccm), 碳纳米管的直径分布 范围增大(10～300nm), 石墨化程度降低, 缺陷密度增大, 非晶化程度增加. 因此, 通过碳源流量可以控制碳纳米管薄膜的形貌和结构.     

Microwave plasma enhanced chemical vapor deposition growth of few-walled carbon nanotubes using catalyst derived from an iron-containing block copolymer precursor

The microwave plasma enhanced chemical vapor deposition (MPECVD) method is now commonly used for directional and conformal growth of carbon nanotubes (CNTs) on supporting substrates. One of the shortcomings of the current process is the lack of control of the diameter and diameter distribution of the CNTs due to difficulties in synthesizing well-dispersed catalysts. Recently, block copolymer derived catalysts have been developed which offer the potential of fine control of both the size of and the spacing between the metal clusters. In this paper we report the successful growth of CNTs with narrow diameter distribution using polystyrene-block-polyferrocenylethylmethylsilane (PS-b-PFEMS) as the catalyst precursor. The study shows that higher growth pressure leads to better CNT growth. Besides the pressure, the effects on the growth of CNTs of the growth parameters, such as temperature and precursor gas ratio, are also studied.     

Effect of acetylene flow rate on morphology and structure of carbon nanotube thick films grown by thermal chemical vapor deposition

Carbon nanotube (CNT) films were grown on nickel foil substrates by thermal chemical vapor deposition (CVD) with acetylene and hydrogen as the precursors. The morphology and structure of CNTs depending on the acetylene flow rate were characterized by a scanning electron microscope (SEM), a transmission electron microscope (TEM) and a Raman spectrometer, respectively. The effect of acetylene flow rate on the morphology and structure of CNT films was investigated. By increasing the acetylene flow rate from 10 to 90 sccm (standard cubic centimeter per minute), the yield and the diameter of CNTs increase. Also, the defects and amorphous phase in CNT films increase with increasing acetylene flow rate. Translated from Journal of Inorganic Materials, 2006, 21(1): 75–80 [译自: 无机材料学报]     

Three dimensional single-walled carbon nanotubes

We report a simple fabrication method of creating a three-dimensional single-walled carbon nanotube (CNT) architecture in which suspended CNTs are aligned parallel to each other along the conventionally unused third dimension at lithographically defined locations. Combining top-down lithography with the bottom-up block copolymer self-assembly technique and utilizing the excellent film forming capability of polymeric materials, highly uniform catalyst nanoparticles with an average size of 2.0 nm have been deposited on sidewalls for generating CNTs with 1 nm diameter. This three-dimensional platform is useful for fundamental studies as well as technological exploration. The fabrication method described herein is applicable for the synthesis of other very small 1D nanomaterials using the catalytic vapor deposition technique.     

Synthesis and purification of bimetallic catalysed carbon nanotubes in a horizontal CVD reactor

Carbon nanotubes (CNTs) were synthesised by a conventional chemical vapour deposition (CVD) method using acetylene as carbon source and a bimetallic catalyst of Fe–Co supported on a CaCO₃ support. The CNTs were characterised by transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy (RS), energy dispersive X-ray spectroscopy (EDS) and thermogravimetric analysis (TGA). The TEM images show clustered CNTs and reveal the outer and inner diameters of these nanomaterials. The XRD analysis shows the characteristic broad peak of graphitised carbon; the RS indicates that these materials have a high degree of crystallinity while the TGA shows the high thermal stability of the materials. EDS analysis also indicates that the purification method employed was able to remove the impurities in the CNT samples.     

The effect of temperature on the growth of carbon nanotubes on copper foil using a nickel thin film as catalyst

Growth of carbon nanotubes (CNTs) on bulk copper foil substrates has been achieved by sputtering a nickel thin film on Cu substrates followed by thermal chemical vapor deposition. The characteristics of the nanotubes are strongly dependent on the Ni film thickness and reaction temperature. Specifically, a correlation between the thin film nickel catalyst thickness and the CNT diameter was found. Two hydrocarbon sources investigated were methane and acetylene to determine the best conditions for growth of CNTs on copper. These results demonstrate the effectiveness of this simple method of directly integrating CNTs with highly conductive substrates for use in applications where a conductive CNT network is desirable.     

A facile procedure to shorten multiwalled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) with > 95% purity were synthesized over a Fe-Co/CaCO3 catalyst using chemical vapour deposition (CVD). Both the CNT yield and the outer diameters increased with time on line in the presence of acetylene. More significantly, the tubes were reduced in length and became stub-like with time. TEM analysis revealed that the CNTs commenced shortening after 2 h of reaction time. Reagent residues (e.g., Ca, CaO, OH/COOH groups and Fe-Co oxides) were found not to influence the CNT bond breaking reaction. CNT growth over Fe-Co supported on silica or CaCO3-Ca3(PO4)2 gave similar results. Further, MWCNTs produced by a floating catalyst method, carbon helices produced from Fe-Co-In/A2O3, and N doped CNTs also revealed tube shortening as a function of reaction time under a flow of acetylene. It is thus apparent that MWCNTs can readily be shortened by the facile procedure of depositing carbon from excess C2H2 on the outer walls of CNTs.     

Carbon nanotube growth on cobalt-sprayed substrates by thermal CVD

We present a very simple spray-coating method for depositing cobalt catalyst over quartz substrates that can be efficiently utilized in the production of carbon nanotubes (CNTs) by thermal chemical vapor deposition (CVD). Very uniform multi-walled carbon nanotubes (MWNTs) have been grown from cobalt catalyst over large surfaces by thermal CVD using mixtures of acetylene and ammonia. The effect of catalyst pretreatments and CNT growth temperature on the CNT diameter has been studied and discussed.     

Carbon nanotubes loaded with magnetic particles

We describe a simple and versatile technique to produce magnetic tubes by filling carbon nanotubes (CNTs) with paramagnetic iron oxide particles ( approximately 10 nm diameter). Commercial ferrofluids were used to fill CNTs with an average outer diameter of 300 nm made via chemical vapor deposition into alumina membranes. Transmission electron microscopy study shows a high density of particles inside the CNT. Experiments using external magnetic fields demonstrate that almost 100% of the nanotubes become magnetic and can be easily manipulated in magnetic field. These one-dimensional magnetic nanostructures can find numerous applications in nanotechnology, memory devices, optical transducers for wearable electronics, and in medicine.     

The toxicity to plants of the sewage sludges containing multiwalled carbon nanotubes

The aim of this study was to evaluate the toxicity of sewage sludges containing multiwalled carbon nanotubes (CNTs) with an outer diameter <10 nm (CNT10) or 40-60 nm (CNT60) to Lepidium sativum (cress), Sorghum saccharatum (sorgo), Solanum lycopersicon (tomato), Raphanus sativus (radish) and Cucumis sativus (cucumber). CNTs were also incubated in sewage sludge for 7 or 31 days to determine the effect of CNT aging on sewage sludge phytotoxicity. The influence of CNTs on 4 different sewage sludges was tested. The CNTs' influence on sludge toxicity varied with respect to the CNTs' outer diameter, type of sewage sludges and the plants tested. No significant influence of CNT concentration on phytotoxicity was noted. In the case of two sludges, a positive influence of CNTs on seed germination and root growth was observed. Depending on the CNTs' outer diameter, CNT aging decreased (CNT10) or increased (CNT60) sewage sludge phytotoxicity.     

Growth and characterization of bamboo-shaped carbon nanotubes using nanocluster-assembled ZnO:Co thin films as catalyst

Bamboo-shaped carbon nanotubes (CNTs) had been successfully fabricated by a plasma enhanced chemical vapor deposition method, in which nanocluster-assembled ZnO:Co thin film was used as catalyst. It was found that bamboo-shaped CNTs were generally grown in a direction perpendicularly to the substrate surface with the tops of CNTs dominated by the droplet-like catalyst covered by the carbon layer. The diameter of CNTs was ranged from 20-50 nm. High resolution of TEM image showed that the typical CNT had a multi-walled structure with an inner core presented. The ordered graphite layers were inclined to an axis of CNT about 18 degrees and the interlayer space of a CNT was about 0.35 nm. Two peaks in Raman spectrum at 1586 cm(-1) and 1372 cm(-1) were identified as G-band and D-band for graphite, respectively. The results showed that catalyst based on ZnO:Co thin films could be used for the growth of CNTs with bamboo-shaped structure.     

调变Ni／Mo／MgO催化剂中Ni／Mo比例可控合成薄壁碳纳米管

采用摩尔分数1%Ni及负载少量Mo的Ni/MO/MgO催化剂裂解甲烷合成薄壁碳纳米管.通过SEM、TEM、XRD和Raman光谱表征方法研究了碳纳米管直径和催化剂中Ni/Mo比例关系.实验发现:通过控制Ni/Mo比例可以调变催化剂颗粒大小以及活性相.TEM及XRD表征发现,随着Ni/Mo比例的降低,金属Mo相逐渐从NiMo合金相中析出.NiMo合金相对应的活性组分颗粒很小,容易催化裂解甲烷形成薄壁碳纳米管;而后析出的Mo相则主要形成了大管径厚壁的碳纳米管.当Ni/Mo比例为6时可以高选择性地获得窄分布,内径为1.3nm,外径为3.0nm的溥壁碳纳米管.Raman光谱进一步验证了碳纳米管含有较少的缺陷.薄壁碳纳米管形成的关键因素主要体现为碳在其表而的快速扩散以及小颗粒的碳纳米管催化剂活性相控制.     

Direct growth of horizontally aligned carbon nanotubes between electrodes and its application to field-effect transistors

This paper presents direct growth of horizontally-aligned carbon nanotubes (CNTs) between two predefined various inter-spacing up to tens of microns of electrodes (pads) and its use as CNT field-effect transistors (CNT-FETs). Using the conventional photolithography technique followed by thin film evaporation and lift off, the catalytic electrodes (pads) were prepared, consisting of Pt, Al and Fe triple layers on SiO2/Si substrate. The grown CNTs were horizontally-aligned across the catalytic electrodes on the modified gold image furnace hot stage (thermal CVD) at 800 degrees C by using an alcohol vapor as the carbon source. Scanning and transmission electron microcopies (SEM/TEM) were used to observe the structure, growth direction and density of CNTs, while Raman spectrum analysis was used to indicate the degree of amorphous impurity and diameter of CNTs. Both single- and multi-wall CNTs with diameters of 1.1-2.2 nm were obtained and the CNT density was controlled by thickness of Fe catalytic layer. Following horizontally-aligned growth of CNTs, the electrical properties of back-gate CNT-FETs were measured and showd p-type conduction behaviors of FET.     

Confined palladium colloids in mesoporous frameworks for carbon nanotube growth

Palladium colloidal nanoparticles with an average size of approximately 2.4 nm have been incorporated into mesoporous inorganic thin films following a multistep approach. This involves the deposition of mesoporous titania thin films with a thickness of 200 nm by spin-coating on titanium plates with a superhydrophilic titania outer layer and activation by calcination in a vacuum furnace at 573 K. Nanoparticles have been confined within the porous titania network by dip-coating noble metal suspensions onto these mesoporous thin films. Finally, the resulting nanoconfined systems were used as substrates for the growth of oriented carbon nanotubes (CNTs) using plasma-enhanced chemical vapour deposition at 923 K in order to enhance their surface area. These CNTs were tested in the hydrogenation of phenylacetylene by hydrogen in a batch reactor. The initial reaction rate observed on a CNT/TiO₂ structured catalyst was considerably higher than that on 1 wt% Pd/TiO₂ thin films.     

Processing and tensile characterization of composites composed of carbon nanotube-grown carbon fibers

The growth of carbon nanotubes (CNTs) on carbon fibers was conducted via chemical vapor deposition. A solution approach has been used to distribute nickel particles on the fiber, and the carbon source was a methane gas. The resulting CNTs are about 10 μm in length and 50 nm in outer diameter. After CNT growth, a fiber bundle was impregnated with an epoxy resin to form a unidirectional composite. Tensile tests were carried out, and the induced fracture surface was examined by microscopes. Three types of CNT fracture during fiber pullout are discussed. The results show that fracture in the CNT/fiber joint is the major mode. Pullout of CNTs was also observed. While pullout of fibers leaves micro-scale holes, pullout of CNTs leaves nano-scale holes. The multi-scale fracture behavior generates new parameters for material design and processing. Some concepts regarding the microstructural design for this special composite are discussed.     

Synthesis of carbon nanotubes by swirled floating catalyst chemical vapour deposition method

A series of developments have been made in synthesizing Carbon Nanotubes (CNTs) by Catalytic Vapour Deposition (CVD) methods since its discovery as a possible route to the large scale and high quality production of CNTs. In this study, CNTs were synthesized continuously in a swirled floating catalytic chemical vapour deposition reactor using acetylene as carbon source, ferrocene as catalyst, with argon and hydrogen as carrier gases within the temperature range of 900-1050 degrees C. The effects of pyrolysis temperature, acetylene flow rate, hydrogen flow rate, and ratio of flow of acetylene to hydrogen on the rate of production of CNTs were investigated. The CNTs produced were purified with dilute nitric acid and the nature and quality of the CNTs were analysed by TEM, Raman spectrometer, EDX, and TGA. Results obtained revealed that a mixture of single and multi wall carbon nanotubes were produced continuously with a maximum yield rate of 0.31 g/min at 1000 degrees C and a flow ratio of acetylene to hydrogen of one to five.     

Ordered fullerene nanocylinders in large-diameter carbon nanotubes

A new ordered fullerene phase encapsulated by large-diameter CNTs is systematically investigated by combining a growth technique by chemical vapour deposition, high-resolution transmission electron microscopy and molecular-dynamics simulations. In contrast to fullerenes in smaller (1-2?nm) diameter CNTs, where fullerenes are packed in linear or helical chains, fullerenes form a nanoscale cylinder in double-walled CNTs with diameters of ～4?nm. The fullerenes were shown to form a nanocylinder with a side wall that resembled the (111) plane of solid C(60). This ordered phase is different from peapods or fullerene solids known so far, and a result of the interaction between the CNT wall and fullerenes. This finding will open up a new field of fullerene science.     

采用局部加热法选择性制备碳纳米管和纳米金刚石晶体

通过局部加热系统中的化学气相沉积法（chemical vapor deposition,CVD）实现了碳纳米管（carbon nanotube,CNT）和金刚石晶体的选择性生长加热系统只加热硅衬底而对反应过程及担载气体没有加热作用．在衬底温度为700℃时,没有生成CNT或明显的金刚石颗粒当温度升到740℃时,仍没有CNT生成,但是在模样化的铁膜上生成许多尺寸为几十纳米的金刚石颗粒温度为770℃时,在铁膜的中央部位生成许多尺寸为几十到几百纳米的金刚石颗粒,而在铁膜的边缘部位可同时观测到一些CNT的生成．当温度达到850℃时,CNT的生长区域扩大而纳米金刚石的平均尺寸和生成密度减小.在910℃的高温下,生成了大量的CNT,其平均直径为20nm,和通常的热CVD法生成的cNT相同在较低的衬底温度下,表面催化反应占主导地位而可能诱导具有sp^3结构的纳米金刚石的生成随着衬底温度的增加,围绕在衬底周围的气体被加热,在达到其气相自聚合温度后形成不饱和碳氢链,这些生成的碳氢链在sp^2结构CNT的生成中起到了重要的作用．     

The production of high purity carbon nanotubes with high yield using cobalt formate catalyst on carbon black

Carbon nanotubes (CNTs) were synthesized by catalytic chemical vapour deposition of acetylene diluted with nitrogen. Cobalt formate supported on carbon black was used as the catalyst. The synthesis was carried out at 700 °C in a quartz reactor for 30 min. Thermal analysis was used to determine the CNT yield. The purity of the nanotubes in the deposit was 96% and the yield was 1940% of the weight of the catalyst. Transmission electron microscopic images of as synthesized and oxidized nanotubes supported the thermogravimetric observations regarding the oxidation of CNT. The purity and the yield obtained are one of the highest reported.     

Modeling of the carbon nanotube chemical vapor deposition process using methane and acetylene precursor gases

Chemical vapor deposition of carbon nanotubes (CNTs) in a horizontal tube-flow reactor has been investigated with a fully coupled reactor-scale computational model. The model combined conservation of mass, momentum, and energy equations with gas-phase and surface chemical reactions to describe the evolution of a hydrogen and hydrocarbon feed-stream as it underwent heating and reactions throughout the reactor. Investigation was directed toward steady state deposition onto iron nanoparticles via methane and hydrogen as well as feed-streams consisting of acetylene and hydrogen. The model determines gas-phase velocity, temperature, and concentration profiles as well as surface concentrations of adsorbed species and CNT growth rate along the entire length of the reactor. The results of this work determine deposition limiting regimes for growth via methane and acetylene, demonstrate the need to tune reactor wall temperature to specific inlet molar ratios to achieve optimal CNT growth, and demonstrate the large effect that active site specification can have on calculated growth rate.