Gas-Phase Dynamics of Bundle Formation from High-Aspect-Ratio Carbon Nanotubes

In floating catalyst chemical vapor deposition (FCCVD), high-aspect-ratio carbon nanotubes (CNTs) are produced in the gas phase at high number concentrations and undergo collision and agglomeration, eventually giving rise to a macroscale aerogel, enabling functional material forms such as fibers or mats to be obtained directly from the synthesis process. The self-assembly behavior between high-aspect-ratio CNTs dictates the resulting morphology at the nanoscale and subsequently the bulk properties of the CNT product. Reorientation between CNTs after collision is a critical step that results in bundle formation and precedes aerogel formation. However, it has been challenging to study the phenomenon with existing methods as it spans multiple time and length scales. In this study, a physics-based semi-analytical model was developed to study the gas-phase reorientation dynamics of high-aspect-ratio CNTs and their bundles, with ±10% accuracy compared with mesoscale molecular dynamics simulations, but at <0.1% the computational cost. It was revealed that the reorientation time scale is dictated by the interplay among the van der Waals potential, drag, and the geometric configuration of CNTs upon collision. This then allows the time scale of reorientation (i.e., bundle formation) to be compared with other gas-phase dynamics in a typical FCCVD reactor and offers new insights into the self-assembly behavior of 1D nanoparticles in the gas phase.