Review of the arc process modeling for fullerene and nanotube production.

The arc process remains the easiest and cheapest technique to obtain significant quantities of single wall carbon nanotubes (SWCNTs) with excellent structural properties. These nanotubes are quite straight and present few topological defects. However, the major inconvenience of this process remains the difficult in situ control of the final material's purity and physical properties. The first NASA/Rice workshop on growth mechanisms was devoted to addressing some specific questions on how and where the nanotubes are formed in several processes including the arc. Further advancement requires a detailed understanding of the growth mechanisms of fullerene, nanotubes and soot and their connection with process parameters. This approach is not highly developed today because of the coupling made by non-equilibrium plasma with the nonlinear chemical system makes, in which rate coefficients and reactions are not well known and this makes modeling difficult. This article is an attempt to analyze the effect of the individual arc parameters yielding guidelines for building a mechanistic understanding of carbon based nanomaterial growth in the arc discharge.

A model for nucleation and growth of single wall carbon nanotubes via the HiPcO process: a catalyst concentration study.

Using the High Pressure carbon monoxide (HiPco) reactor we conducted an experiment on the effects of changing the catalyst concentration. With each catalyst concentration tested the resulting raw HiPco material was characterized for average SWNT lengths, SWNT diameters, residual iron particle size, and large fullerene content. We were able to determine trends in each of these characteristics as the catalyst concentration was changed. As the catalyst concentration was decreased SWNT lengths increased, SWNT diameters increased, the residual iron particle size increased, and the large fullerene content decreased. From these trends we have developed a Competitive Growth model for nucleation and growth of SWNTs via the HiPco process.

A parametric study of single-wall carbon nanotube growth by laser ablation.

Results of a parametric study of carbon nanotube production by the double-pulse laser oven process are presented. The effect of various operating parameters on the production of single-wall carbon nanotubes (SWCNTs) is estimated by characterizing the nanotube material using analytical techniques, including scanning electron microscopy, transmission electron microscopy, thermo gravimetric analysis and Raman spectroscopy. The study included changing the sequence of the laser pulses, laser energy, pulse separation, type of buffer gas used, operating pressure, flow rate, inner tube diameter, as well as its material, and oven temperature. It was found that the material quality and quantity improve with deviation from normal operation parameters such as laser energy density higher than 1.5 J/cm2, pressure lower than 67 kPa, and flow rates higher than 100 sccm. Use of helium produced mainly small diameter tubes and a lower yield. The diameter of SWCNTs decreases with decreasing oven temperature and lower flow rates.

Chemical models for simulating single-walled nanotube production in arc vaporization and laser ablation processes.

Chemical kinetic models for the nucleation and growth of clusters and single-walled carbon nanotube (SWNT) growth are developed for numerical simulations of the production of SWNTs. Two models that involve evaporation and condensation of carbon and metal catalysts, a full model involving all carbon clusters up to C80, and a reduced model are discussed. The full model is based on a fullerene model, but nickel and carbon/nickel cluster reactions are added to form SWNTs from soot and fullerenes. The full model has a large number of species--so large that to incorporate them into a flow field computation for simulating laser ablation and arc processes requires that they be simplified. The model is reduced by defining large clusters that represent many various sized clusters. Comparisons are given between these models for cases that may be applicable to arc and laser ablation production. Solutions to the system of chemical rate equations of these models for a ramped temperature profile show that production of various species, including SWNTs, agree to within about 50% for a fast ramp, and within 10% for a slower temperature decay time.

Arc process parameters for single-walled carbon nanotube growth and production: experiments and modeling.

Collarets rich in single-walled carbon nanotubes (SWCNTs) have been grown using a direct current arc method. Arc process parameters such as current, pressure, and anode to cathode distance were varied experimentally and by modeling to provide an optimal working window. The best collaret yields were obtained when helium was used as a buffer gas. Mixing helium with argon in the buffer permits controlling nanotube diameters. In addition to an experimental study, a modeling approach was developed assuming local thermal equilibrium and homogenous and heterogeneous neutral chemistry. The gas-phase chemical model involves 81 neutral carbon species (C1, C2, . . ., C79, C60F, C70F) and 554 reactions with rates taken from data of Krestinin and Moravsky. Axial profiles of temperature, C atom, C2 radical, and fullerene distributions in the reactor are predicted as a function of process parameters. Carbon nanotube growth is considered by a set of surface reactions simulating open nanotube growth. Because nanotube surface chemistry is controlled by the local terminated bond and not by the bulk nanotube bond, a mechanistic approach based on the formal resemblance between the bonding and the structure of open nanotube and other carbon surfaces is proposed to explain nanotube growth. Predicted growth rates are in the range of 100 to 1000 microm/min.

Computational fluid dynamics simulation of laser-ablated carbon plume propagation in varying background gases for single-walled nanotube synthesis.

A computational fluid dynamics study was conducted to model the plume resulting from the laser ablation of a carbon target in a laser ablation oven for the production of carbon single-walled nanotubes (SWNTs). The goal is to gain understanding into the fluid dynamics and thermodynamics of the plume to ultimately improve SWNT production techniques. The simulations were carried out with a 12-species, 14-reaction chemistry model that included carbon species from C to C6. Metal catalysts in the carbon target were ignored for these simulations. Simulation times ranged from immediate ablation onset to 8 ms past the initial onset of ablation. A secondary goal of the study was to compare computational results with experimental results for three different background gases in the laser ablation oven-argon, helium, and nitrogen. Computational results indicated that lighter carbon species were more quickly diffused into the background gas for helium and nitrogen, resulting in lower localized mass fractions of carbon nanotube "feedstock." The expectation is that this effect will reduce the production of carbon nanotubes, which has been confirmed by experimental evidence. From this investigation, a possible "indicator species" for the production of SWNT appears to be C5.

Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor.

The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

Effects of carbonyl bond, metal cluster dissociation, and evaporation rates on predictions of nanotube production in high-pressure carbon monoxide.

The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNTs) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the conformation of CO2. It is shown that the production of CO2 is significantly greater for FeCO because of its lower bond energy as compared with that of NiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.