Physical Aging of Miscible Polymer Blends

Physical aging measurements were performed on various polymeric glasses with the overriding goal of developing a better molecular picture of the nonequilibrium glassy state. To this end, aging-induced changes in mechanical properties and in the thermodynamic state (volume and enthalpy) were assessed for two different miscible polymer blends as a function of both composition and aging temperature. This investigation considered the physical aging behavior of blends containing atactic polystyrene (a-PS) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) as well as mixtures of poly(methyl methacrylate) (PMMA) and poly(styrene-co-acrylonitrile) (SAN). Substantial attractive chemical interactions are characteristic of a-PS/PPO blends but are absent in PMMA/SAN blends. The distinct nature of interactions for these two blends resulted in differences in the compositional dependence of secondary relaxation intensity, segmental cooperativity which dictates glass formation kinetics, and density (prior to aging). The variation of volume relaxation rate with aging temperature and composition was interpreted based upon these characteristics for the two systems. In addition, a general relationship was uncovered which linked structural relaxation rates for amorphous polymers to their respective segmental relaxation characteristics (glass transition cooperativity or fragility), which in turn are well understood from a molecular standpoint. This work, therefore, established a basis for comprehending glassy state volume and enthalpy relaxation rates based upon molecular characteristics. Developing an understanding of the connection between the evolving thermodynamic state and mechanical property changes fared less well. The fact that the thermodynamic and mechanical properties can have very different relaxation time responses governing their changes in the nonequilibrium glassy state was clearly evident in an extensive study of the physical aging characteristics of an amorphous polyimide material. For some materials, interpretation of mechanical aging behavior was obscured by thermorheological complexity arising due to overlap of a secondary relaxation with the main chain softening dispersion.