Macromolecules, Vol.27, No.23, 6936-6941, 1994
Cooperative Chain Rotations as a Mechanism of the Alpha-Delta Phase-Transition in Poly(Vinylidene Fluoride)
Possible microscopic mechanisms of the electric-field-induced transition from the nonpolar alpha-phase to the polar delta-phase in poly(vinylidene fluoride) are analyzed theoretically. The energetics characterizing the mechanism connected with independent chain rotations is calculated. It is shown that this mechanism becomes energetically favorable only in the range of very high electric fields E > E(cr) within which the cu-phase transforms into the beta-phase, but not into the delta-phase. Owing to this result we propose another transition mechanism, which involves cooperative rotations of neighboring chains in polymer crystallites. It is emphasized that two-dimensional correlations of chain rotations should play the main role in the (alpha-delta-phase transition. The activation energy characterizing the formation of "two-dimensional" delta-phase nuclei is derived and evaluated. The kinetics of the alpha-delta-phase transition is calculated in the frame of the theory of absolute reaction rates. A characteristic time tau of this structural transformation is estimated and compared with available experimental data.