Nanotube-substrate interactions: distinguishing carbon nanotubes by the helical angle

We investigate the interaction of a carbon nanotube with a graphite substrate, using an interlayer potential that explicitly treats the registry dependence of the interaction. The carbon-carbon bond lengths in nanotubes differ slightly from those in flat graphite, so that the naively commensurate angular orientations for the tube with respect to the substrate lattice are destroyed. The interaction of a one-dimensional tube with a two-dimensional substrate then leads to an unusual registry phenomenon not visible in standard layer-on-layer growth: the system develops favorable orientations which clearly are incommensurate.     

Synthesis and growth mechanism of carbon nanotubes and nanofibers from ethanol flames

The ethanol flame was successfully used to synthesize highly graphitic hollow-cored carbon nanotubes (CNTs) and novel disorder solid-cored carbon nanofibers (CNFs). Their morphologies were characterized by using scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy and Raman spectroscopy. It was found that the mixture of CNTs and CNFs were grown on Ni-contained substrates, whereas only the CNFs were produced on carbon steel and low alloy steel substrates. It has been established that Ni and its compounds play a key role in CNTs growth and Fe and its compounds in CNFs growth. The models of 'hollow-cored mechanism' and 'solid-cored mechanism' were proposed to explain the present CNTs and CNFs formations, based on the theory that 'Fe has a strong affinity for carbon and Ni has a weak affinity for carbon'. It is expected that the present ethanol flame may provide a much simpler and more economic approach for mass-production of CNTs and CNFs by using large flame or multi-flames.     

Synthesis of multi-wall carbon nanotubes by simple pyrolysis

A new pyrolysis technique has been developed for the synthesis of multi-walled carbon nanotubes (MWCNTs). In this simple method diethyl ether and nickelocene is pyrolysized in a reaction quartz tube without using carrier gas. The samples are prepared at pyrolysis temperatures of 650 and 950 ^°C and the effect of temperature on the tube morphology investigated. Purification has been done following the standard oxidation and acid bath treatment. The as-synthesized and purified nanotubes have been characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA) and micro-Raman spectroscopy. The technique has great advantages such as low cost and easy operation for the production of CNTs.     

High-density and well-aligned carbon nanotubes formed by surface decomposition of SiC

The structure and diameter of the densely aligned carbon nanotubes (CNTs) by surface decomposition of C-face in vacuum were investigated by cross-sectional, plan-view transmission electron microscopy and electron diffraction methods. Zigzag-type CNTs were confirmed to be selectively formed and the formation mechanism was proposed from crystallographic analysis. Furthermore, the wall number of CNTs was found to be directly proportional to the diameter of CNTs. Comparing with the theoretical calculation, it was revealed that all of the carbon atoms remained on the surface after the selective evaporation of Si atoms by decomposition of each monolayer of , and then constructed the CNT walls with the minimum diffusion distance at the interface.     

Stable single helical C-and I-chains inside single-walled carbon nanotubes

The helicity of stable single helical carbon chains and iodine chains inside single-walled carbon nanotubes(SWCNTs)is studied by calculating the systematic van der Waals interaction energy.The results show that the optimal helical radius increases linearly with increasing tube radius,which produces a constant separation between the chain structure and the tube wall.The helical angle exhibits a ladder-like decrease with increasing tube radius,indicating that a large tube can produce a small helicity in the helical structures.     

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     

Synthesis of multi-wall carbon nanotubes by the pyrolysis of ethanol on Fe/MCM-41 mesoporous molecular sieves

Ordered hexagonal arrangement MCM-41 mesoporous molecular sieves were synthesized by the traditional hydrothermal method, and Fe-loaded MCM-41 mesoporous molecular sieves (Fe/MCM-41) were prepared by the wet impregnation method. Their mesoporous structures were testified by X-ray diffraction (XRD) and the N₂ physical adsorption technique. Carbon nanotubes (CNTs) were synthesized by the chemical vapor deposition (CVD) method via the pyrolysis of ethanol at atmospheric pressure using Fe/MCM-41 as a catalytic template. The effect of different reaction temperatures ranging from 600 to 800 ^°C on the formation of CNTs was investigated. The resulting carbon materials were characterized by various physicochemical techniques such as transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. The results show that multi-wall carbon nanotubes (MWCNTs) with an internal diameter of ca. 7.7 nm and an external diameter of ca. 16.9 nm were successfully obtained by the pyrolysis of ethanol at 800 ^°C utilizing Fe/MCM-41 as a catalytic template.     

Synthesis of multi-wall carbon nanotubes by copper vapor laser

Synthesis of multi-wall carbon nanotubes in a 1473 K furnace using a copper vapor laser (CVL) is reported. The operating parameters of this laser, i.e. a high fluence at the focal point and an extremely high frequency of 10 kHz, distinguished it from common laser sources in the synthesis of CNTs. Therefore, the unexpected experimental findings, the formation of MWNTs instead of the generally reported SWNTs, would be verified by these two notable parameters. Electron microscopy beside Raman spectroscopy illustrates the presence of multi-wall carbon nanotubes in the resulting product.     

Synthesis of carbon nanotubes by CVD: Effect of acetylene pressure on nanotubes characteristics

The effect of acetylene partial pressure on the structural and morphological properties of multi-walled carbon nanotubes (MWCNTs) synthesized by CVD on iron nanoparticles dispersed in a SiO₂ matrix as catalyst was investigated. The general growing conditions were: 110 cm³/min flow rate, 690 °C synthesis temperature, 180 Torr over pressure and two gas compositions: 2.5% and 10% C₂H₂/N₂. The catalyst and nanotubes were characterized by HR-TEM, SEM and DRX. TGA and DTA were also carried out to study degradation stages of synthesized CNTs. MWCNTs synthesized with low acetylene concentration are more regular and with a lower amount of amorphous carbon than those synthesized with a high concentration. During the synthesis of CNTs, amorphous carbon nanoparticles nucleate on the external wall of the nanotubes. At high acetylene concentration carbon nanoparticles grow, covering all CNTs’ surface, forming a compact coating. The combination of CNTs with this coating of amorphous carbon nanoparticles lead to a material with high decomposition temperature.     

Fabrication of aligned carbon nanotubes on Cu catalyst by dc plasma-enhanced catalytic decomposition

Aligned multi-walled carbon nanotubes (ACNTs) are deposited using copper (Cu) catalyst on Chromium (Cr)-coated substrate by plasma-enhanced chemical vapor deposition at temperature of 700 °C. Acetylene gas has been used as the carbon source while ammonia is used for diluting and etching. The thicknesses of Cu films on Cr-coated Si (100) substrates are controlled by deposition time of magnetron sputtering. The growth behaviors and quality of ACNTs are investigated by scanning electron microscopy (SEM) and transmission electron microscopy. The different performance of ACNTs on various Cu films is explained by referring to the graphitic order as detected by Raman spectroscopy. The results indicate that the ACNTs are formed in tip-growth model where Cu is used as a novel catalyst, and the thickness of Cu films is responsible to the diameter and quality of synthesized CNTs.     

Synthesis of carbon nanotubes by ECR plasma-assisted chemical vapor deposition

Carbon nanotubes have been grown using an electron cyclotron resonance (ECR) plasma source at a substrate temperature of 500 °C. Methane has been used as the source gas. A network of carbon nanotubes has been observed in scanning electron microscopy. Transmission electron microscopy revealed that the structure consists of straight, Y-junction and ring-like nanotubes. Further, electron diffraction of the nanotubes confirms a graphite crystal structure. PACS 81.16.He; 68.37.Lp; 68.37.Hk; 85.35.Kt; 75.75.+a     

Synthesis and characterization of carbon nanotubes on carbon microfibers by floating catalyst method

In this paper, carbon nanotubes were synthesized on carbon microfibers by floating catalyst method with the pretreatment of carbon microfibers at the temperature of 1023 K, using C₂H₂ as carbon source and N₂ as carrier gas. The morphology and microstructure of carbon nanotubes were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The composition of carbon nanotubes was determined by energy dispersive X-ray spectroscopy (EDX). The results showed that the surface of treated carbon microfibers was thickly covered by carbon nanotubes with diameters of about 50 nm. EDX image indicated that the composition of carbon nanotubes was carbon. In comparison with the sample grown on untreated carbon microfibers surface, it was found that after carbon microfibers were boiled in the solution of sulfur acid and nitric acid (VH₂SO₄:VHNO₃ = 1:3) and immersed in the solution of iron nitrate and xylene, carbon nanotubes with uniform density can be grown on carbon microfibers surface. Based on the results, we concluded that the pretreatment of carbon microfibers had great effect on the growth of carbon nanotubes by floating catalyst method.     

Synthesis and characterization of nitrogen-doped carbon nanotubes by pyrolysis of melamine

Femtosecond laser material processing as micromachining and nanoparticles fabrication require a careful control of the fluences deposited on the samples. In many cases, best results are obtained by using fluences slightly above the Laser Ablation Threshold (LAT), therefore its accurate determination is an important requirement. LAT can be obtained by measuring the intensity of the acoustic signal generated during the ablation process as a function of the laser fluence. In this work femtosecond laser ablation thresholds of commercially polished stainless steel plates, white high impact polystyrene, frosted glass, antique rag papers and silicon oxynitride thin films were determined by using laser ablation induced photoacoustics (LAIP). Results were compared with similar data previously obtained by using a nanosecond Nd:YAG laser.     

Synthesis of carbon nanotubes by catalytic vapor decomposition (CVD) method: Optimization of various parameters for the maximum yield

This paper describes an effect of flow rate, carrier gas (H₂, N₂ and Ar) composition, and amount of benzene on the quality and the yield of carbon nanotubes (CNTs) formed by catalytical vapour dcomposition (CVD) method. The flow and mass control of gases and precursor vapors respectively were found to be interdependent and therefore crucial in deciding the quality and yield of CNTs. We have achieved this by modified soap bubble flowmeter, which controlled the flow rates of two gases, simultaneously. With the help of this set-up, CNTs could be prepared in any common laboratory. Raman spectroscopy indicated the possibilities of formation of single-walled carbon nanotubes (SWNTs). From scanning electron microscopy (SEM) measurements, an average diameter of the tube/bundle was estimated to be about 70 nm. The elemental analysis using energy dispersion spectrum (EDS) suggested 96 at.wt.% carbon along with ca. 4 at.wt.% iron in the as-prepared sample. Maximum yield and best quality CNTs were obtained using H₂ as the carrier gas.      

Electrochemical sensor for rutin detection based on Au nanoparticle-loaded helical carbon nanotubes

The key step in the fabrication of highly active electrochemical sensors is seeking multifunctional nanocomposites as electrode modified materials. In this study, the gold nanoparticle-decorated helical carbon nanotube nanocomposites (AuNPs-HCNTs) were fabricated for rutin detection because of its superior sensitivity, the chemical stability of AuNPs, and the superior conductivity and unique 3D–helical structure of helical carbon nanotubes. Results showed the prepared nanocomposites exhibited superior electrocatalytic activity towards rutin due to the synergetic effects of AuNPs and HCNTs. Under the optimized conditions, the developed sensor exhibited a linear response range from 0.1 to 31 μmol/L for rutin with a low detectable limit of 81 nmol/L. The proposed method might offer a possibility for electrochemical analysis of rutin in Chinese medical analysis or serum monitoring owing to its low cost, simplicity, high sensitivity, good stability, and few interferences against common coexisting ions in real samples.     

Influence of oxygen on the growth of carbon nanotubes by the SiC surface decomposition method

The influence of oxygen on the development of carbon nanotubes (CNTs) during the annealing process of the surface decomposition method on SiC(000−1) surfaces was investigated. In the case of annealing a SiC substrate under ultra-high vacuum conditions, carbon nanofibers (CNFs) form between the CNT layer and the substrate. However, CNTs form without CNFs by annealing the substrate in an oxygen atmosphere. The mean length of CNTs is longer than those formed without an oxygen atmosphere. From cross-sectional transmission electron microscopy images, it was found that oxygen plays an important role in CNT growth by the surface composition method.     

Synthesis of multiwall carbon nanotubes by chemical vapor deposition of ferrocene alone

Multiwall carbon nanotubes (MWNTs) filled with Fe nanoparticles (NPs) have been synthesized by thermal chemical vapor deposition of ferrocene alone as the precursor. The MWNTs were grown at different temperatures: 980 and 800 ^°C. Characterization of as-prepared MWNTs was done by scanning and transmission electron microscopy, and X-ray diffraction. The transmission electron microscopy study revealed that Fe NPs encapsulated in MWNTs grown at 980 and 800 ^°C are spherical and rod shaped, respectively. Room-temperature vibrating sample magnetometer studies were done on the two samples up to a field of 1 T. The magnetization versus magnetic field loop reveals that the saturation magnetization for the two samples varies considerably, almost by a factor of 4.6. This indicates that Fe is present in different amounts in the MWNTs grown at the two different temperatures.     

Synthesis of well-aligned carbon nanotubes by inductively coupled plasma chemical vapor deposition

Uniform and well-aligned carbon nanotubes (CNTs) have been grown using a high density inductively coupled plasma chemical vapor deposition (ICP-CVD) system. A gas mixture of methane-hydrogen was used as the source and Ni as the catalyst for the CNT growth. The effect of process parameters, such as inductive RF power, DC bias voltage and CH₄/H₂ ratio, on the growth characteristics of CNTs was investigated. It was found that both plasma intensity and ion flux to the substrate, as controlled by the inductive RF power and DC bias voltage, respectively, can greatly affect the growth of CNTs. The relative importance of the generation of ions and the subsequent transport of ions to the substrate as serial process steps are considered as the two underlying factors in determining the growth characteristics of CNTs. PACS 81.05.Uw; 81.07.De; 81.15.Gh     

Synthesis and crystallinity of carbon nanotubes produced by a vapor-phase growth method

We have studied the effect of temperature on the growth and crystallinity of carbon nanotubes (CNTs), synthesized by a vapor-phase growth method using a catalytic reaction of iron pentacarbonyl (Fe(CO)₅) and acetylene (C₂H₂) gas. By increasing the growth temperature from 750 °C to 950 °C, both the growth rate and the diameter of the CNTs increase. Moreover, the crystallinity of the graphite sheets improves progressively with increasing growth temperature. Adjustment of the growth temperature gives potential for controlled growth of CNTs in a large-scale synthesis of CNTs. PACS 61.46.+w; 68.37.-d; 81.07.De     

Bamboo-shaped carbon nanotubes generated by methane thermal decomposition using Ni nanoparticles synthesized in water-oil emulsions

Ni nanoparticles were synthesized using two water-in-oil emulsions formulated with different surfactants and using n-heptane as the organic phase and aqueous nickel acetate as the catalytic metallic precursor. Characterization by transmission electron microscopy showed that the Ni nanoparticles have diameters ranging from 3 to 12 nm, and that the surface is lightly oxidized. The decomposition of diluted methane catalyzed by the as-prepared Ni nanoparticles was studied in a thermogravimetric analyzer (TGA), operated in the 25–930 °C range. The weight gains measured during the analysis showed that the Ni nanoparticles decomposed methane above 480 °C, producing similar g.C/g.cat ratios (6–7) at the end of the tests. High resolution transmission electron microscopy (HRTEM) confirmed that the carbons collected at 930 °C were bamboo-shaped carbon nanotubes (BSCNTs) with well defined conical compartments. The average outside diameter of the tubes was between 30 and 60 nm.