Linear Stress Relaxation and Probe Reorientation: Comparison of the Segmental Dynamics of Two Glassy Polymers during Physical Aging

Abstract

Segmental dynamics of glassy poly(methyl methacrylate) (PMMA) and poly(lactic acid) (PLA) have been measured over 8 h of aging via both optical probe reorientation and mechanical stress relaxation experiments performed in the linear response regime, in a temperature range between 6 and 30 K below the glass transition temperature (Tg). A clear power law relationship between relaxation times and aging times is observed in all experiments. For both PLA and PMMA glasses, the probe reorientation times are strongly correlated with stress relaxation times over the observed range of aging times and aging temperatures, with the two relaxation times related by a power law with an exponent of ∼1. Comparisons of these data sets with previously published work indicate that the relationship between the two relaxation times is not influenced by secondary relaxation processes, low levels of crosslinking, or the presence of a plasticizer. These results support the view that the probe reorientation technique is a good reporter of segmental dynamics in the glassy state.