Thermal expansion of polymers subjected to low-amplitude temperature cycling

The temperature dependence of the thermal expansion of polymers subjected to small harmonic temperature oscillations about certain base temperatures near the glass transition range is considered. The conformational component of the expansion as a function of temperature is calculated in terms of the conformational transition kinetics. The temperature dependences of the expansion and the expansion vs. oscillation phase shift are analyzed with allowance for the vibrationally anharmonic component. The thermal expansion of polyvinylacetate at base temperatures of 295–320 K, oscillation frequencies of 0.3 and 0.1 Hz, and an oscillation amplitude of 0.8 K are studied experimentally. The measured and calculated data for the expansion and expansion vs. temperature phase shift are shown to be in good agreement.