Polymer-Ion Interaction Weakens the Strain-Rate Dependence of Extension-Induced Crystallization for Poly(ethylene oxide).

Abstract

The crystallization of poly(ethylene oxide) (PEO)-sodium iodine (NaI) composites is investigated by differential scanning calorimetry (DSC), extensional rheology, and in situ small-angle X-ray scattering (SAXS) with the aim of demonstrating versatile roles played by polymer-ion interactions. In the isothermal quiescent crystallization process, a decrease in the crystal growth rate is observed for PEO-NaI and is attributed to slow chain movement caused by the coordination between cations and polymer. In situ SAXS on extensional flow-induced crystallization (FIC) exhibits enhanced kinetics and orientation for both PEO and PEO-NaI with increasing strain rate. However, an overall weaker strain-rate dependence of FIC is observed for PEO-NaI, which can be interpreted as a synergistic consequence of promoted nucleation under flow and impeded crystal growth by polymer-ion interaction. A possible microscopic mechanism is proposed to account for the experimental observation based on the formation of transient cross-linking points in PEO-NaI and their influence on the entanglement network of polymer under various flow fields. The disclosed strain-rate dependence and various ion effects on the behavior of PEO-salt composites contribute to a comprehensive understanding of polymer-ion solid polyelectrolytes.