Vibrational and configurational heat capacity of poly(vinyl acetate) from dynamic measurements.

The complex heat capacity C(p) () of poly(vinyl acetate) has been measured at 20.95 mrads modulation frequency during the cooling as well as on heating at 24, 8, and 2 Kh and during cooling at 0.5 Kh. The study is complemented with (the rate-dependent) C(p,app) measured during cooling and heating at 60, 24, and 8 Kh. At low temperatures, the real component of C(p) () yields the unrelaxed C(p) or C(p,vib), the vibrational part of C(p). It is found to be indistinguishable from C(p,glass) and lies on a line extrapolated to its equilibrium melt's temperature. At T near T(g),DeltaC(p)(=C(p,melt)-C(p,glass)) shows no detectable contribution from C(p,vib). The finding conflicts with a modified entropy theory calculation [E. A. DiMarzio and F. Dowell, J. Appl. Phys. 50, 6061 (1979)], which had predicted that approximately 27% of DeltaC(p) of poly(vinyl acetate) at T near T(g) is vibrational in origin and the remainder configurational. At T<T(g), the real component of C(p) (*) varies more slowly with T than C(p,app).