Microscopic mechanisms of the shape memory effect in crosslinked polymers

In this work we perform coarse-grained molecular dynamics (MD) simulations to study the molecular origins of the thermal shape memory effect in crosslinked polymer materials. Thermal shape memory polymers (SMPs) are materials able to hold a deformed shape when cooled below the glass transition temperature, and subsequently recover the initial shape when heated. To use SMPs in various applications requires materials which reliably hold and recover their shapes; this has sparked recent synthesis work to create new SMP materials with optimized properties. Here we use coarse-grained MD simulations with different polymer chain models to determine which parameters affect relevant SMP behavior and to investigate the molecular mechanisms at the level of individual chains during temperature cycling. The simulations show how temperature-dependent chain mobility leads to shape memory polymer behavior. In particular, we demonstrate the importance of attractive monomer interactions in leading to 'good' SMP behavior. The results suggest promising routes for material development. Additionally, the mechanisms identified with the simple simulation model can be used to inform multi-scale models of SMP material behavior.