Jumping In and Out of the Phase Diagram Using Electric Fields: Time Scale for Remixing of Polystyrene/Poly(vinyl...

We demonstrate it is possible to repeatedly jump polystyrene (PS)/poly(vinyl methyl ether) (PVME) blends from the one-phase to two-phase region by simply turning on and off an electric field at a fixed temperature near the phase boundary. This builds on our previous work that established electric fields enhance the miscibility of PS/PVME blends by shifting the phase separation temperature T_S(E) of 50/50 blends up by 13.5 ± 1.4 K when field strengths of E = 1.7 × 10⁷ V/m are applied (J. Chem. Phys. 2014, 141, 134908). Monitoring the early stages of phase separation and remixing by fluorescence, we measure the remixing time scale τ(T) with and without electric fields, finding τ(T) is unchanged by the presence of the field and well fit by a Vogel-Fulcher-Tammann expression. These observations are consistent with a mobility-limited process several degrees from the phase boundary where electric fields have shifted the miscibility transition.