Synthesis of multiwall carbon nanotubes by electric arc discharge in liquid environments

This work reports the experimental results from the production of multiwall carbon nanotubes (MWCN) synthesized by an electric arc discharge performed in liquid environments between pure graphite electrodes. Both liquid nitrogen and deionised water were suitable for a successful synthesis of this form of carbon aggregation. We report a successful synthesis of MWCN by arc discharge submerged in deionised water. Electron microscopy observations of both the reaction products and the surface of the as-synthesized raw material showed the presence of structural degradation of the MWCN, which probably operates after their growth at the cathode. The degradation is tentatively ascribed to a combination of overheating and high current density experienced by the as-synthesized MWNT, which can be caused by the loose structure of the as-deposited material. The damage appeared to be less severe in water environments, probably owing to the better cooling capacity of water relative to liquid nitrogen.     

Microscopic mechanisms for the catalyst assisted growth of single-wall carbon nanotubes

Whatever the synthesis technique used, the growth of ropes of single-wall carbon nanotubes requires the assistance of a metallic catalyst. In this paper, the role played by the catalyst is studied both experimentally and theoretically. Experimentally, the similarities between the samples synthesized from different techniques suggest a common growth mechanism proceeding via the precipitation of excess carbon on metallic nanoparticles. In this paper, the correlation between ropes and catalytic particles is investigated in detail in the case of the Ni-Y catalyst used in the arc discharge technique by combining high resolution transmission electron microscopy, X-ray and electron energy loss spectroscopy. It is shown that the ropes are always found attached to metallic particles about ten times larger than the tube diameter. A further remarkable proof of this relationship is provided by the chemical analyses of the metallic particles. These are found to be free of carbon and to always display the same Ni:Y composition range, whatever the initial Ni:Y composition of the catalyst mixture used in the synthesis, whereas the composition of other particles is highly dispersed. These experimental results support a mechanism of formation based on a vapor-liquid-solid model, in which the tubes of a given bundle nucleate in a cooperative manner and grow at the surface of a same metallic particle. This phenomenological scheme is supported by quantum molecular dynamics simulations which show that carbon atoms are incorporated at the root of a growing tube by a diffusion-segregation process occurring at the surface of the catalytic particle.     

Synthesis of narrow-diameter carbon nanotubes from acetylene decomposition over an iron-nickel catalyst supported on alumina

Carbon nanotubes (CNTs) were synthesized by the catalytic decomposition of acetylene over 40Fe:60Al₂O₃, 40Ni:60Al₂O₃ and 20Fe:20Ni:60Al₂O₃ catalysts. High density CNTs of 20 nm diameter were grown over the 20Fe:20Ni:60Al₂O₃ catalyst, whereas low growth density CNTs of 40 and 50 nm diameter were found over 40Fe:60Al₂O₃ and 40Ni:60Al₂O₃ catalysts. Smaller catalyst particles enabled the synthesis of highly dense, long and narrow-diameter CNTs. It was found that a homogeneous dispersion of the catalyst was an essential factor in achieving high growth density. The carbon yield and the quality of CNTs increased with increasing temperature. For the 20Fe:20Ni:60Al₂O₃ catalyst, the carbon yield reached 121% after 90 min at 700 °C. The CNTs were grown according to the tip growth mode. Based on reports regarding hydrocarbon adsorption and decomposition over different faces of Ni and Fe, the growth mechanism of CNTs over the 20Fe:20Ni:60Al₂O₃ catalyst are discussed.     

Synthesis and characterization of double-walled carbon nanotubes from multi-walled carbon nanotubes by hydrogen-arc discharge

Double-walled carbon nanotubes (DWNTs) were synthesized in a large scale by a hydrogen arc discharge method using graphite powders or multi-walled carbon nanotubes/carbon nanofibers (MWNTs/CNFs) as carbon feedstock. The yield of DWNTs reached about 4 g/h. We found that the DWNT product synthesized from MWNTs/CNFs has higher purity than that from graphite powders. The results from high-resolution transmission electron microscopy observations revealed that more than 80% of the carbon nanotubes were DWNTs and the rest were single-walled carbon nanotubes (SWNTs), and their outer and inner diameters ranged from 1.75 to 4.87 nm and 1.06 to 3.93 nm, respectively. It was observed that the ends of the isolated DWNTs were uncapped and it was also found that cobalt as the dominant composition of the catalyst played a vital role in the growth of DWNTs by this method. In addition, the pore structures of the DWNTs obtained were investigated by cryogenic nitrogen adsorption measurements.     

Image analysis characterization of multi-walled carbon nanotubes

An original image analysis method is presented to characterize multi-walled carbon nanotubes from transmission electron microscopy images. The analysis is performed in three steps: (i) image preprocessing in order to isolate the nanotubes from the background, (ii) image segmentation, aiming at keeping only the measurable sections of nanotubes, and finally (iii) tube characteristics measurement. The measurement is based on a Lambert-like electron absorption law and is performed on the original gray level image itself. Two geometrical and one physical characteristics are determined for each tube, namely, its outer and inner radius and a linear electron absorption coefficient. The method is illustrated by comparing a pristine and an annealed carbon nanotube samples. The compaction of the tube walls during annealing is shown to result from a lowering of the external radius while the inner radius is left unchanged.     

Plasma torch production of macroscopic carbon nanotube structures

Analysis of the many studies of carbon nanotube formation in high-temperature ovens clearly indicates the key requirements of nanotube formation are an ‘atomic’ carbon source and a source of nanometal particles. We adapted this formulation to the high temperature (>3000 K) environment found in a low-power (<1000 W) atmospheric pressure, microwave plasma torch, by simultaneously feeding carbon monoxide (carbon source), and (presumably) iron carbonyl (source of metal catalyst particles) through an argon stabilized plasma flame. This technique led to the relatively rapid (25 mg/h) formation of carbon nanotubes of a unique form: macro-sized ‘woven’ threads. Scanning electron microscopy and high-resolution transmission electron microscopy studies revealed that the woven threads consist entirely of carbon nanotubes (primarily carbon single-wall nanotube) and associated nano-iron particles. The structures appear ‘fractal’ in that each woven thread appears to be constructed of smaller threads that in turn are formed of yet smaller woven threads. Simple mechanical tests show the threads can be bent without breaking, and the thread will spring to its original shape when the force holding it is released. Threads of the size produced can be woven together to form actual cloth or ropes and thus this result represents a step toward the ultimate application of carbon nanotubes for super strong/light structures.     

Synthesis of carbon nanocapsules containing Fe, Ni or Co by arc discharge in aqueous solution

A simple, inexpensive and one-step synthesis method of metal-containing carbon nanocapsules using an arc discharge in aqueous solution is reported. It was found that Ni, Co and Fe nanoparticles could be in situ encapsulated in carbon shells when the arc was performed respectively in aqueous solutions of NiSO₄, CoSO₄ and FeSO₄. Transmission electron microscopy, energy dispersive X-ray spectroscopy and electron diffraction patterns of selected areas were used to determine the crystalline phase of the metal cores. To explain the formation mechanism of metal-containing carbon nanocapsules, a model of discharge in solution is proposed. This result presents a simply controllable way to synthesize metal-containing carbon nanocapsules.     

Field emission from the film of the finely dispersed arc discharge black core material

We have studied, for the first time, the field emission from the film, prepared by a spray method, of the finely dispersed black core material, including multi-walled carbon nanotubes (MWNTs), fabricated by arc discharge. We dispersed the black core material by using an ultrasonic processor and found that the dispersed ones were much finer than those observed when treated with a ball mill and normal ultra-sonic bath. By SEM, HRTEM and Raman analyses, the MWNTs were almost not deformed and damaged during ultra-sonication. The field emission current density measured from the film of the dispersed black core material was about 15 mA/cm² at an applied field of 8 V/μm, which was about 23 times higher than that found by a ball mill. A current density of 1 mA/cm², which is required basically for flat panel display, has been obtained at 5.3 V/μm. The lifetime test of the dispersed black core material showed that the current density was almost unchanged while the field was applied. Therefore, it is concluded that a black core material fabricated by arc discharge could be used to flat panel displays as field emitters by dispersing with an ultrasonic processor, without further treatment like extraction or purification.     

In-situ formation of carbon nanotubes in an alumina-nanotube composite by spray pyrolysis

Alumina (Al₂O₃)-carbon nanotube composite materials were synthesized by spraying a slurry of ferrocene (Fe(C₅H₅)₂) and alumina in xylene, at 1000±50 °C, using argon (≤1.5 bar) as carrier gas. The as-prepared materials were formed in large flakes (ca. 2 cm) and consist of nanotubes intricately matted in a glassy alumina matrix. Based on the structural and microstructural investigations done by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM), a possible growth mechanism has been suggested.     

BETA zeolite nanowire synthesis under non-hydrothermal conditions using carbon nanotubes as template

The properties of carbon nanotubes, used as a nanometric template and as a reactor for the synthesis of BETA zeolite, have been investigated. The confinement effect of the carbon nanotubes, induced by the high aspect ratio of the tubes could be effectively used for the synthesis of one-dimensional nanowire zeolitic materials under non-hydrothermal macroscopic conditions. Zeolite material is easily recovered by combustion of the nanotubes. The average sizes of the zeolite particles are about 20 nm. The BETA zeolite was successfully used as a catalyst for benzoylation of anisol. The zeolite catalyst exhibits a high activity compared to a commercial BETA, essentially due to its high external surface area.