Volume recovery/relaxation, physical aging

The decrease in volume that accompanies physical aging is known as volume recovery or volume relaxation. Dilatometry (Dil) can be used to follow the volume relaxation in glasses by monitoring the time-dependence of the volume change on aging. The material is either cooled from above Tg to the aging temperature 7], (down-jump) and the isothermal volume contraction is measured or the sample is heated in the glassy state (up-jump), in which case an expansion follows. 

Cowie, J. M. G., Elliott, S., Ferguson, R Simha, R Physical aging smdies on poly(vinyl acetate) - enthalpy relaxation and its relation to volume recovery. Polymer Communications, 28(11), pp. 298-300 (1987). 

Below Tg (4,5) co-operative molecular processes are usually assumed to be inactive. However, physical ageing implies that conformational changes may be still able to occur if rather infrequently. Structural relaxation processes are observed to be non-exponential and are represented by a continuous distribution or stretched exponential form (d). Thermorheologically simplicity (TRS) implies that the molecular relaxation process has the same form at different temperatures (7) and the validity of this assumption is addressed in this paper. Isobaric volume recovery (8,9) has been described by a single parameter mc el, however all fi ee volume models (10,11) have limitations and a distribution of hole sizes and relaxation times leading to a pseudo-linear theory is a more realistic model(72). Comparison of data fi om various techniques should throw light on the molecular nature of physical agdng. 

The decrease in volume during physical aging is specifically known as volume recovery or volume relaxation. Volume recovery experiments include down-jump, up-jump, and memory experiments. The results of these experiments, which are shown and discussed later, demonstrate that structural recovery is both nonlinear, nonexponential and path-dependent. 

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