Evolution of particle size and morphology in plasma synthesis of few-layer graphene and soot

This paper examines the evolution of particle size and morphology of plasma-synthesized carbonaceous nanoparticles for various reactants, reactant concentrations, reactor temperatures, and positions within the reactor. Aerosol particles were characterized at various positions downstream from the plasma zone by spatially-resolved thermophoretic sampling and transmission electron microscopy, Raman spectroscopy, and by in situ time-resolved laser-induced incandescence. Depending on the carbon-bearing reactant (ethanol or toluene) and its concentration, either pure few-layer graphene (FLG) or soot-like particles, or a mixture of both, were generated. The initial carbon nucleation has been found to commence less than 12.4 cm downstream from the plasma nozzle. In the case of FLG formation, particles show an increasing level of crumpling with increasing distance downstream from the plasma zone. The process was numerically simulated with a 1D plug-flow reactor model employing a joint population balance model for graphitic and amorphous-like particles (FLG and soot-like, respectively). The simulation includes modified versions of inception, hydrogen-abstraction-carbon-addition (HACA), and polycyclic-aromatic hydrocarbon (PAH) adsorption models adapted from a pre-existing soot model. The simulations showed that the ratio of HACA/PAH adsorption determined by post-plasma C₂H₂ is the main factor that affects the soot-to-FLG ratio. This is also consistent with experimental observations as reducing the rate at which carbon precursor is supplied to the reactor leads to less C₂H₂ in the post-plasma zone, which results in less PAH adsorption, and consequently suppressed soot formation in favor of FLG synthesis.