Lower limit for single-wall carbon nanotube diameters from hydrocarbons and fullerenes

A theoretical model for the growth of single-wall carbon nanotubes produced by metal-catalyzed decomposition of hydrocarbons and fullerenes is presented. The growth process is treated as a thermodynamic equilibrium between carbon in the gas phase and carbon in the nanotube. The minimum possible nanotube diameters based on several published experimental conditions are calculated by combining the free energy of the reaction with an equation derived from elastic theory. The model predicts the possibility of generating nanotubes with extremely small diameters that are smaller than in the corresponding experiments. Received: 18 July 2001 / Accepted: 19 November 2001 / Published online: 4 March 2002     

Thinning and diluting aligned carbon nanotube films for uniform field emission

Aligned carbon nanotube (CNT) films are potential field emitters for large-area flat panel displays. However, the distribution of emission areas in the CNT films is quite non-uniform because of inhomogeneous nanotube growth, which is hard to avoid using the conventional chemical vapor deposition (CVD) method. Here we show that the emission uniformity of CNT films can be improved simply by reducing the film thickness (thinning) or the nanotube density (diluting). The thickness and density of CNT films could be controlled by controlling the CNT growth time and temperature. Received: 12 June 2001 / Accepted: 27 October 2001 / Published online: 23 January 2002     

Laser heating method for estimation of carbon nanotube purity

A new method of a carbon nanotube purity estimation has been developed on the basis of Raman spectroscopy. The spectra of carbon soot containing different amounts of nanotubes were registered under heating from a probing laser beam with a step-by-step increased power density. The material temperature in the laser spot was estimated from a position of the tangential Raman mode demonstrating a linear thermal shift (-0.012 cm^-1/K) from the position 1592 cm^-1 (at room temperature). The rate of the material temperature rise versus the laser power density (determining the slope of a corresponding graph) appeared to correlate strongly with the nanotube content in the soot. The influence of the experimental conditions on the slope value has been excluded via a simultaneous measurement of a reference sample with a high nanotube content (95 vol. %). After the calibration (done by a comparison of the Raman and the transmission electron microscopy data for the nanotube percentage in the same samples) the Raman-based method is able to provide a quantitative purity estimation for any nanotube-containing material. Received: 11 December 2001 / Accepted: 12 December 2001 / Published online: 4 March 2002     

Effect of gas pressure on the growth and structure of carbon nanotubes by chemical vapor deposition

The effect of gas pressure on the structure of carbon nanotubes (CNTs) has been systematically investigated in the chemical vapor deposition process. The yield of CNTs (defined as the weight ratio of CNTs vs. catalyst) increases significantly with the gas pressure, reaches 600% at 600 Torr, then decreases with further increase of gas pressure. At low reacting gas pressure the CNTs have completely hollow cores, whereas at high pressure the CNTs have a bamboo structure. The density of the compartments in the bamboo-structured CNTs increases dramatically with the increase of the gas pressure. This result shows that the structure and yield of carbon nanotubes are strongly affected by the growth gas pressure. Received: 10 May 2001 / Accepted: 10 May 2001 / Published online: 20 June 2001     

Fabrication and structure: a study of aligned carbon nanotube/carbon nanocomposites

Aligned carbon nanotube/carbon (Acnt/C) nanocomposites have been fabricated by densifying an Acnt preform with chemical vapour infiltration technology. Microstructure observations show that pyrocarbon in Acnt/C was mainly rough lamella type while pyrocarbon in carbon fiber reinforced carbon matrix (C/C) composites was typically smooth lamella type in spite of the same process. The thermal conductivity of these Acnt/C nanocomposites is about 4 times that of C/C composites. Their electrical conductivity of Acnt/C nanocomposites was anisotropic, i.e. approximately 1.61×10⁴ Ω⁻¹ m⁻¹ and 5.68×10³ Ω⁻¹ m⁻¹ in the direction parallel and vertical to the aligned carbon nanotubes, respectively.     

Copper nanocluster diffusion in carbon nanotube

The diffusion of copper nanocluster in carbon nanotube was investigated using a classical molecular dynamics simulation and three empirical potential functions. The results indicated a growth mechanism of the copper-filled ultra-thin carbon nanotubes: the copper nanoclusters inserted into carbon nanotubes swiftly migrate along the tube axis, and then the copper nanowires grow in the ultra-thin carbon nanotubes. Periodic energy barriers in the carbon nanotubes induced the directional movement of copper nanoclusters in the carbon nanotubes. The diffusion speeds of copper nanocluster in the carbon nanotube showed the Arrherius relation.     

Application of scanning force microscopy in nanotube science

Recent developments in the application of scanning force microscopy in nanotube science are reviewed. The non-destructive character of this technique allows the structural characterisation of (chemically modified) single- and multi-wall nanotubes deposited on substrates for further investigations such as electrical transport measurements. Furthermore, SFM is now an established tool for manipulation of nanotubes, which allows position control and determination of elastic constants such as the Young’s modulus. Finally it is shown that very sharp and stable probes for scanning force microscopy can be made from nanotubes due to their excellent stability and aspect ratio. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 29 July 1999     

Synthesis, characterization and electrochemical behavior of polypyrrole/carbon nanotube composites using organometallic-functionalized carbon nanotubes

Thorn-like, organometallic-functionalized carbon nanotubes were successfully developed via a novel microwave hydrothermal route. The organometallic complex with methyl orange and iron (III) chloride served as reactive seed template, resulting in the oriented polymerization of pyrrole on the modified carbon nanotubes without the assistance of other oxidants. Morphological and structural characterizations of the carbon nanotube/methyl orange-iron (III) chloride and polypyrrole/carbon nanotube composites were examined using transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), infrared spectroscopy and X-ray diffraction (XRD). The electrochemical property of the polypyrrole/carbon nanotube composite was elucidated by cyclic voltammetry and galvanostatic charge-discharge. A specific capacitance of 304 F g⁻¹ was obtained within the potential range of −0.5-0.5 V in 1 M KCl solution.     

Preparation and characterization of multiwall carbon nanotube/polypyrrole coaxial fibrils

Multiwall carbon nanotube (MWNT)/polypyrrole (PPy) fibrils were fabricated by template-free in situ electrochemical deposition of PPy over MWNTs, and characterized by electron microscopy and electrical measurements. Scanning and transmission electron microscopy studies reveal that PPy coating on the surface of nanotube is quite uniform throughout the length, with the possibility of forming unique Y-junctions. Current (I)-voltage (V) characteristics at various temperatures show nonlinearity due to tunneling and hopping contributions to transport across the barriers. AC conductivity measurements (300-4.2 K) show that the onset frequency scales with temperature, and the nanoscale connectivity in MWNT/PPy fibrils decreases with the lowering of temperature.     

Silicon enhanced carbon nanotube growth on nickel films by chemical vapor deposition

Silicon enhances carbon nanotube growth on nickel films by chemical vapor deposition using methane and hydrogen. Nanotube growth characteristic is significantly improved on nickel films patterned by argon plasma etching on silicon oxide layers. Auger electron spectroscopy shows that a reduced silicon phase forms in the surface silicon oxide layer by Ar ion bombardment used for patterning. The enhanced growth of carbon nanotubes could be ascribed to an oxygen removal effect by silicon in the process of synthesis.     

碳纳米管复合吸波涂层微波吸收性能的模拟计算

如何利用碳纳米管复合吸波涂层的参数进行吸波性能优化是电磁屏蔽研究的热点之一.涂层参数对吸波性能影响的研究主要停留在实验探索阶段,而碳纳米管的结构参数对吸波性能影响的研究鲜有报道.因此,从微观结构层次研究涂层参数对吸波性能的影响有重要意义.基于多壁碳纳米管的等效电路,利用碳纳米管结构参数与等效电路各元件参数的关系,研究了碳纳米管损耗微波的机理,建立了碳纳米管结构参数与微波反射率的关系式.根据此关系式,利用Matlab软件模拟计算了碳纳米管管长、管径、涂层中碳纳米管的含量以及涂层厚度对微波反射率的影响.模拟计算结果表明:涂层的微波反射率随碳纳米管含量变化的模拟曲线与实验结果符合;碳纳米管含量和厚度是影响吸收峰位置和吸收强度的重要参量,而碳纳米管直径和长度是主要影响吸收峰强度的参量.     

Fine-structured field emission images originating from coherently scattering of electrons within a multi-walled carbon nanotube

High resolution field emission image of a single multi-walled carbon nanotube was studied by field emission microscopy. The images contain patterns consisting of rather ordered bright fringes. We propose a model based on coherent electron scattering to explain the observed field emission image. The emitted electrons will undergo coherent scattering within the cap region of a multi-wall carbon nanotube, which may be viewed as elastic scattering by a polycrystalline structure with an infinite size. This study is helpful for understanding the physical mechanism of field emission of carbon nanotube.     

Charge-carrier dynamics in single-wall carbon nanotube bundles: a time-domain study

We present a real-time investigation of ultra-fast carrier dynamics in single-wall carbon nanotube bundles using femtosecond time-resolved photoelectron spectroscopy. The experiments allow us to study the processes governing the sub-picosecond and the picosecond dynamics of non-equilibrium charge carriers. On the sub-picosecond time scale the dynamics are dominated by ultra-fast electron–electron scattering processes, which lead to internal thermalization of the laser-excited electron gas. We find that quasiparticle lifetimes decrease strongly as a function of their energy up to 2.38 eV above the Fermi level – the highest energy studied experimentally. The subsequent cooling of the laser-heated electron gas to the lattice temperature by electron–phonon interaction occurs on the picosecond time scale and allows us to determine the electron–phonon mass-enhancement parameter λ. The latter is found to be over an order of magnitude smaller if compared, for example, with that of a good conductor such as copper. Received: 4 March 2002 / Accepted: 7 March 2002 / Published online: 3 June 2002     

Growth mechanisms for single-wall carbon nanotubes in a laser-ablation process

Mechanisms proposed in the literature are compared with a current scenario for the formation of single-wall carbon nanotubes in the laser-ablation process that is based on our spectral emission and laser-induced fluorescence measurements. It is suggested that the carbon which serves as feedstock for nanotube formation not only comes from the direct ablation of the target, but also from carbon particles suspended in the reaction zone. Fullerenes formed in the reaction zone may be photo-dissociated into C₂ and other low molecular weight species, and also may serve as feedstock for nanotube growth. Confinement of the nanotubes in the reaction zone within the laser beam allows the nanotubes to be ‘purified’ and annealed during the formation process by laser heating. Received: 2 November 2000 / Accepted: 3 November 2000 / Published online: 23 March 2001     

Microstructure and wear property of carbon nanotube carburizing carbon steel by laser surface remelting

Carbon nanotube was used to carburize the surface of medium carbon steel and mild steel, respectively, by means of laser surface remelting. The slurry of carbon nanotube of ethanol was coated on the surface of the materials prior to laser irradiation. Microstructures, microhardness and wear property of the surface layers treated by different laser performance parameters were studied. Graphite coating was also used for carburizing. The results showed that both carbon nanotube and graphite were dissolved in the surface molten layer, leading a carburized hardening layer on the surface of the substrate. However, different microstructures formed in the carburizing layers, depending mainly on the type of carburization materials, carbon nanotube or graphite. The carbon nanotube hardening layer exhibits a little higher hardness than the graphite hardening layer. The carburized layer greatly increases the wear resistance of the base material.     

Synthesis, integration, and electrical properties of individual single-walled carbon nanotubes

High-quality single-walled carbon nanotubes (SWNTs) are synthesized by chemical vapor deposition (CVD) of methane on silicon-dioxide substrates at controlled locations using patterned catalytic islands. With the synthesized nanotube chips, microfabrication techniques are used to reliably contact individual SWNTs and obtain low contact resistance. The combined chemical synthesis and microfabrication approaches enable systematic characterization of electron transport properties of a large number of individual SWNTs. Results of electrical properties of representative semiconducting and metallic SWNTs are presented. The lowest two-terminal resistance for individual metallic SWNTs (≈5 μm long) is ≈16.5 kΩ measured at 4.2 K. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 14 July 1999     

New synthesis of multi-walled carbon nanotubes using an arc discharge technique under organic molecular atmospheres

We have synthesized multi-walled carbon nanotubes (MWNTs) using a DC arc discharge method under organic molecular atmospheres. This method allows us to synthesize about five times more MWNTs than are synthesized using the usual arc discharge method, using discharge conditions of 100 A and 20 V. We have examined the synthetic yield of MWNTs at various pressures under different organic atmospheres. The yield of MWNTs increases with the number of carbon atoms in the organic molecule. Received: 21 September 2000 / Accepted: 18 December 2000 / Published online: 26 April 2001     

Adjustable thermal conductivity in carbon nanotube nanofluids

Homogeneous and stable nanofluids have been produced by suspending well dispersible multi-walled carbon nanotubes (CNTs) into ethylene glycol base fluid. CNT nanofluids have enhanced thermal conductivity and the enhancement ratios increase with the nanotube loading and the temperature. Thermal conductivity enhancement was adjusted by ball milling and cutting the treated CNTs suspended in the nanofluids to relatively straight CNTs with an appropriate length distribution. Our findings indicate that the straightness ratio, aspect ratio, and aggregation have collective influence on the thermal conductivity of CNT nanofluids.     

Synthesis of aligned carbon nanotubes

Carbon nanomaterials seem to be most attractive because of their fascinating features. Carbon nanotubes emerged recently as unique nanostructures with remarkable mechanical and electronic properties. Future applications will require a fabrication method capable of producing uniform carbon nanotubes with well-defined and controllable reproducibility of their properties. In this review, recent results addressing rational and efficient methods to obtain aligned arrays of these one-dimensional carbon nanomaterials will be discussed. Received: 3 November 2000 / Accepted: 30 May 2001 / Published online: 30 August 2001     

Mechanical properties of carbon nanotubes

A variety of outstanding experimental results on the elucidation of the elastic properties of carbon nanotubes are fast appearing. These are based mainly on the techniques of high-resolution transmission electron microscopy (HRTEM) and atomic force microscopy (AFM) to determine the Young’s moduli of single-wall nanotube bundles and multi-walled nanotubes, prepared by a number of methods. These results are confirming the theoretical predictions that carbon nanotubes have high strength plus extraordinary flexibility and resilience. As well as summarising the most notable achievements of theory and experiment in the last few years, this paper explains the properties of nanotubes in the wider context of materials science and highlights the contribution of our research group in this rapidly expanding field. A deeper understanding of the relationship between the structural order of the nanotubes and their mechanical properties will be necessary for the development of carbon-nanotube-based composites. Our research to date illustrates a qualitative relationship between the Young’s modulus of a nanotube and the amount of disorder in the atomic structure of the walls. Other exciting results indicate that composites will benefit from the exceptional mechanical properties of carbon nanotubes, but that the major outstanding problem of load transfer efficiency must be overcome before suitable engineering materials can be produced. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 29 July 1999