Mössbauer studies of polymers in the glassy state and near their glass transition

Mössbauer absorption spectra of glassy block and copolymers with lowT _G containing ferrocene have been recorded in a wide temperature range (4–330 K) to investigate the dynamical processes of the system, in the glassy state and around the glass transition. An inhomogeneous broadening due to conformational substates with different hyperfine parameters found at lower temperatures becomes motionally narrowed above 40 K. Whereas in the glassy state both the block and the copolymers reveal the same vibrational behaviour, we found differences in the vicinity of their respective glass transitions. For the block polymer an anomalous decrease of the recoilfree fractionf _A was found above the static glass transition. In agreement with neutron data on other polymers we attribute this behaviour to an onset of motions of the ferrocene units of higher than 10¹⁰ Hz. For the copolymers, however, a departure of lnf _A from linearity was detected already far below the staticT _G. We propose that this is caused by residual solvents which allow an easier cooperative rearrangement of the segments even belowT _G. First attempts to interpret the Mössbauer data by means of the predictions of the mode coupling theory are reported.