The impact of plasticisers on crystal nucleation, growth and melting in linear polymers

Abstract

Plasticisers are often added to crystallising polymers to improve their processability. Despite many experimental studies, very few modelling studies have been performed to provide fundamental understanding of the impact of plasticisers on polymer cyrstallisation kinetics and thermodynamics. In this work, molecular dynamics simulations are used to study crystallisation in a model linear polymer with plasticiser. We first demonstrate that the plasticiser lowers the amorphous phase glass transition, with the extent of the effect increasing with plasticiser concentration, due to increased polymer mobility. Using a model filler surface to induce crystallisation, we find that the plasticiser also reduces crystallisation and melting temperatures. Furthermore, we find that the plasticiser is expelled from the crystals during growth so that its concentration in the amorphous matrix increases with degree of crystallisation. This has a pronounced consequence for crystal melting, and we find a broad temperature range where the crystal is in equilibrium with the amorphous phase, which we rationalise in terms of free energy changes. This has potentially important consequences for the processing of linear polymers such as polyhydroxybutyrate (PHB), poly(l-lactic acid) (PLLA) and polyvinyl alcohol (PVA), by providing the opportunity for processing the polymer in a semicrystalline rather than fully amorphous state.