Identification of relaxation processes in pure polyethylene oxide (PEO) films by the dielectric permittivity and electric modulus formalisms

Abstract

The ac‐impedance of bulk‐like films of pure polyethylene oxide (PEO) polymer was measured as a function of frequency f in the range 0.1 to 107 Hz at various constant temperatures T (155 − 330 K). The as‐measured data were analyzed by electric permittivity and modulus formalisms to unveil which dielectric and conductive relaxation processes were responsible for their relaxation behavior below/above glass transition temperature Tg of pure PEO polymer. At T > Tg, none of the α‐, β‐, or γ‐relaxations could be inferred for studied pure PEO films from frequency variation of measured imaginary part ε′′(f, T) of complex dielectric permittivity , as low‐frequency losses masked real dielectric contribution to the measured ε′′(f, T) at low frequencies and high temperatures. However, at T < Tg, a broad, relaxation process has been observed in the high‐frequency part of their isothermal ε′′(f, T) − f spectra, which can be related to the β‐ or γ‐dielectric relaxation process. Nonlinear regressions of the measured ε′′(f, T) − f data for T < Tg yielded moral fits to a simple addition of a Havriliak‐Negami function, and a Bergman‐loss Kohlrausch‐Williams‐Watts‐type function, with the relaxation time τmax(T) obtained from Havriliak‐Negami‐fitting parameters, was found to follow a thermally activated Arrhenius‐like relaxation behavior. Conversely, representation of the imaginary part M′′(f, T > Tg) − f spectra of complex electric modulus was found to depict 2 overlapped relaxation processes, which were detached well by a nonlinear regression of a simple superposition of 2 different M′′(f) expressions having the form of the universal Bergman loss function, where it was found that the relaxation time is also thermally activated.