Direct observation of long chain enrichment in flow-induced nuclei from molecular dynamics simulations of bimodal...

Modelling of flow-induced nucleation in polymers suggest that long chains are enriched in nuclei, relative to their melt concentration. This enrichment has important consequences for the nucleation rate and mechanism, but cannot be directly observed with current experimental techniques. Instead, we ran united atom molecular dynamics simulations of bimodal polyethylene blends, comprising linear chains at a 50 : 50 mix of long (1000 carbon) and short (500-125 carbon) chains, under shear flow. We developed a method to extract the nucleus composition during a transient start-up flow. Our simulations show significant and systematic enrichment of long-chains for all nucleus sizes up to and beyond the critical nucleus. This enrichment is quantitatively predicted by the recent polySTRAND model [Read et al. Phys. Rev. Lett. 2020, 124, 147802]. The same model parameters also correctly capture the nucleus induction time in our simulations. All parameters of the model were fitted to a small subset of our data in which long chain enhancement was absent. We conclude that long-chain enrichment is central to the mechanism of flow-induced nucleation and that this enrichment must be captured to correctly predict the nucleation rate.