Kinetics of re‐embrittlement of (anti)plasticized glassy polymers after mechanical rejuvenation

Mechanical rejuvenation is known to dramatically alter the deformation behavior of amorphous polymers. Polystyrene (PS)—for example, typically known as a brittle polymer—can be rendered ductile by this treatment, while a ductile polymer like polycarbonate (PC) shows no necking anymore and deforms homogeneously in tensile deformation. The effects are only of temporary nature, as because of physical aging the increasing yield stress, accompanied by intrinsic strain softening, renders PS brittle after a few hours, while for PC necking in tensile testing returns in a few months after the mechanical rejuvenation treatment. In this study, it is found that physical aging upon rejuvenation in both PS and PC can be delayed in two different ways: (1) by reducing the molecular mobility through antiplasticization and (2) by applying toughening agents (rubbery core–shell particles). For the first route, even though progressive aging is found to decrease with increasing amounts of antiplasticizer added, dilution of the entanglement network results in enhanced brittleness. Besides antiplasticization effects, also some typical plasticization effects are observed, like a reduction in matrix T_g. For the second route, traditional rubber toughening using acrylate core–shell modifiers also results in a reduced yield stress recovery, and ductile tensile deformation behavior is observed even 42 months after mechanical rejuvenation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 134–147, 2008