Pressure and cooling rate-induced densification of atactic polystyrene

The exact knowledge of postprocessing polymer-specific volume is often a factor of enormous strategic importance from an industrial point of view. The subject is complicated by the fact that the specific volume of solid polymers at a constant temperature and pressure is not only a function of the current temperature and pressure, but is also a consequence of the whole formation history from the melt. In this work, specific volumes of samples solidified in different conditions are analyzed and related to their formation history. A wide range of cooling rates (from 5 X 10(-3) to 300 K/s) and solidification pressures (from 0.1 to 80 MPa) are examined. The results show a synergic effect of the cooling rate and solidification pressure: Lower cooling rates result in a much higher pressure-induced densification with respect to higher cooling rates. A simple phenomenological model which essentially links the densification effect to the dependence of the glass transition temperature upon the cooling rate and solidification pressure is adopted to describe the experimental data. Starting from the densification effect, the effect of the pressure and cooling rate on the glass transition temperature is evaluated. Furthermore, some conclusions about the dependence of the volume relaxation time on the temperature and pressure in the glass transition range are achieved. (C) 2003 Wiley Periodicals, Inc.