Pressure Scanning Volumetry of Physically Aged Polymer Glasses, Fictive Pressure, and Memory Effect

Physical aging of a glass decreases its volume, V, entropy, and enthalpy, H, toward the equilibrium state values. For glasses usually formed by cooling a melt, the effect is modeled in terms of non-exponential, nonlinear structural relaxation by using a plot of the heat capacity, Cp = (dH/dT)p, against T obtained from differential scanning calorimetry (DSC) cooling and heating scans. A melt becomes glass also on isothermal pressurizing and the glass formed becomes liquid on depressurizing, showing a hysteresis of the sigmoid-shape plot of −(dV/dp)T against p, which resembles the thermal hysteresis observed in the Cp against T plots. By analogy with DSC, it was named pressure scanning volumetry (PSV). Here, we use the known values of non-exponential and nonlinearity parameters β and x and volume of activation for structural relaxation time, ΔV*, of atactic poly(propylene) to investigate the effect of aging pressure, page, of aging time, tage, and of the pressurizing rate on aging features in PSV scans. The scans show a post- 𝑝g→l feature on depressurizing before the −(dV/dp)T overshoot peak appears. We provide quantitative plots (i) of the monotonic decrease of V and increase of fictive pressure, pf, with tage and (ii) of the memory (Kovacs) effect in V and pf of the polymer and (iii) provide generic plots of −(dV/dp)T against p for different combinations of β, x, and ΔV*. The study is of academic significance because PSV scans show a change in the density fluctuation response. It is of technological significance in polymer-extrusion processing and it may stimulate the commercial development of computer-controlled, high-pressure equipment.