Dynamic Compressibility of Poly (Vinyl Acetate) and Its Relation to Free Volume

The complex bulk compliance (dynamic compressibility) of a commercial sample of poly (vinyl acetate), AYAT, was measured at frequencies from 50 to 1,000 cycles per second, temperatures from 0 to 100 °C, and static hydrostatic stresses from 0 to 981 bars (gage pressure) using an alternating hydrostatic stress generated and detected by piezoelectric transducers mounted in an essentially noncompliant cavity with dimensions small in comparison to a wavelength. The above temperature range was more than sufficient to cover the dispersion region in which an inflection in the storage compliance and a maximum in the loss compliance were observed. The data were reduced to functions of reduced variables using the WLF Equations extended to include static pressure with the "universal" WLF Constants and dT/dP = 0.020 °C/bar. The difference in limiting compliances at zero and infinite frequencies was larger than that predicted from the dT/dP shift using the free volume concept. A discussion is presented on possible processes that might contribute to an excessive value between limiting compliances.