Abstract
Positron annihilation lifetime and conductivity measurements have been performed for the poly(ether urethane) PEU-${\mathrm{LiClO}}_{4}$ complex as a function of temperature in the temperature range from 120 to 360 K and from 280 to 360 K, respectively. According to the variations of free volume and fractional free volume, the structural transition of PEU-${\mathrm{LiClO}}_{4}$ has been determined. Based on a polymer lattice model, the formation energy of a free-volume hole has been calculated in terms of fractional free volume derived from positron annihilation parameters. The temperature dependence of ionic conductivity obeys the Vogel-Tammann-Fulcher and Williams-Landel-Ferry equations, implying a free-volume transport mechanism. A direct relationship between the ionic conductivity and the fractional free volume has been established based on the experimental measurements. A linear least-squares procedure was used to evaluate the apparent activation energy in the Vogel-Tammann-Fulcher equation and several important parameters in the Williams-Landel-Ferry and Vogel-Tammann-Fulcher equations. The correlation between the segmental motion and the conductivity could be explained by means of the free-volume theory.
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