Nanomechanics of Multi-Walled Carbon Nanotubes Growth Coupled with Morphological Dynamics of Catalyst Particles

Low-dimensional carbon nanostructures such as nanotubes, nanocones, and nanofibers can be grown in chemical vapor deposition (CVD) synthesis using catalyst nanoparticles. It is commonly observed that the morphology of solid catalyst nanoparticles continuously fluctuates during multi-walled carbon nanotube (MWCNT) growth. Interestingly, when the diameter of the inner tube of the growing MWCNT reduces below a threshold value, the catalyst nanoparticle snaps out of the MWCNT and recovers its spherical shape. If the MWCNT is tapered, the catalyst nanoparticle may also break. In this study, large-scale molecular dynamics simulations and nanomechanical modeling are employed to elucidate the complete process of MWCNT growth coupled with morphological change in the catalytic nanoparticles. It is shown that the tendency to decrease the surface energy of the catalyst nanoparticle is the major underlying driving force for the variation in morphology under the mechanical constraint of the growing MWCNT. Importantly, the predicted critical inner CNT radius at the onset of the shape recovery is in excellent agreement with experimental observations. The combination of molecular dynamics simulations and theoretical modeling offer an alternative perspective on co-evolution of catalyst nanoparticles and the growth of low-dimensional carbon nanostructures.