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.
The behavior of ablated plumes produced by nanosecond scale multiple laser pulses typical for carbon ablation is studied in order to understand the plume expansion dynamics and shielding effect of plume with special interest to ionization of plumes. The patterns of a planar plume (typical for channel cutting) and an axisymmetric plume (typical for hole drilling) appear to be quite different. Ionization in carbon plume is estimated using the Saha equation. An iterative procedure is developed to determine the local equilibrium temperature affected by ionization. It is shown that though shielding due to the presence of ionized particles in carbon plume is small, the effect of ionization on plume temperature can be considerable. Shielding effect is calculated for laser pulses with different time intervals between pulses. The effects of high temperature and low density of plume are conflicting and cause shielding behavior to be nonmonotonic. It is shown that the nonmonotonic dependence of the delivered laser energy, the pulse number, and the difference in shielding characteristics between planar and axisymmetric formulations increase with the time duration between two consecutive pulses.
The scattering and absorption of laser radiation by previously ablated plumes in laser ablation (known as the shielding effect) dramatically affect the efficiency of laser ablation process. The ablated plumes consisting of water vapor, droplets, and particles are modeled as a gas-particle equilibrium mixture by solution of the Euler equations combined with the transport equation for the ratio of heat capacities. Shielding effect on the overall ablated mass by multiple plumes is studied for a wide range of concentration of particles in vaporized plumes, various laser repetition rates, scattering, and absorption of laser energy. The shielding phenomenon is studied for short sequences of discrete plumes to focus on the shielding effect of individual plumes. The results of numerical modeling were compared to experimental results of laser-induced water explosive vaporization. Ablation rate was calculated for a single ablated plume and for the sequence of six laser pulses at the repetition rates of 0.33 and 1MHz at which gas dynamics interactions between plumes are strong but plumes have not yet form a continuous jet. A single ablated plume has an initial semispherical shape which transforms into mushroomlike cloud with a thin stem and a ring vortex as it was observed in experiments with water and cornea ablation. For the plume with a given ablated mass, the longer ejection of plume with smaller density produces the plume with smaller shielding capacity. For multiple laser pulses, the velocity of ejected mixture increases from the center of the target to its periphery because of the shielding effect. The ablated mass of the current plume depends on the attenuation of the incident laser beam energy caused by the propagation of laser beam through previously ablated plumes. In the case of laser energy absorption, the ablation rate per pulse exceeds 2–2.5 times the rate obtained for the laser energy scattering.
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