Segmental dynamics in polymers: From cold melts to ageing and stressed glasses

Recent progress in developing statistical mechanical theories of supercooled polymer melts and glasses is reviewed. The focus is on those approaches that are either explicitly formulated for polymers, or are applications of more generic theories to interpret polymeric phenomena. These include two configurational entropy theories, a percolated free volume distribution model, and the activated barrier hopping nonlinear Langevin theory. Both chemically-specific and universal aspects are discussed. After a brief summary of classic phenomenological approaches, a discussion of the relevant length scales and key experimental phenomena in both the supercooled liquid and glassy solid state is presented including ageing and nonlinear mechanical response. The central concepts that underlie the theories in the molten state are then summarized and key predictions discussed, including the glass transition in oriented polymer liquids and deformed rubber networks. Physical ageing occurs in the nonequilibrium glass, and theories for its consequences on the alpha relaxation are discussed. Very recent progress in developing a segment scale theory for the dramatic effects of external stress on polymer glasses, including acceleration of relaxation, yielding, plastic flow and strain hardening, is summarized. The article concludes with a discussion of outstanding theoretical challenges.