Abstract
Effects of a strong‐interacting amorphous polymer, poly(4‐vinyl phenol) (PVPh), and an alkali metal salt, lithium perchlorate (LiClO~4~), on the amorphous and crystalline domains in poly(ethylene oxide) (PEO) were probed by differential scanning calorimetry (DSC), optical microscopy (OM), and Fourier transform infrared spectroscopy (FTIR). Addition of lithium perchlorate (LiClO~4~, up to 10% of the total mass) led to enhanced T~g~'s, but did not disturb the miscibility state in the amorphous phase of PEO/PVPh blends, where the salt in the form of lithium cation and ClO anion was well dispersed in the matrix. Competitive interactions between PEO, PVPh, and Li^+^ and ClO ions were evidenced by the elevation of glass transition temperatures and shifting of IR peaks observed for LiClO~4~‐doped PEO/PVPh blend system. However, the doping distinctly influenced the crystalline domains of LiClO~4~‐doped PEO or LiClO~4~‐doped PEO/PVPh blend system. LiClO~4~ doping in PEO exerted significant retardation on PEO crystal growth. The growth rates for LiClO~4~‐doped PEO were order‐of‐magnitude slower than those for the salt‐free neat PEO. Dramatic changes in spherulitic patterns were also seen, in that feather‐like dendritic spherulites are resulted, indicating strong interactions. Introduction of both miscible amorphous PVPh polymer and LiClO~4~ salt in PEO can potentially be a new approach of designing PEO as matrix materials for electrolytes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3357–3368, 2006