Antiplasticization of Polymer Materials: Structural Aspects and Effects on Mechanical and Diffusion-Controlled Properties.

Antiplasticization of glassy polymers, arising from the addition of small amounts of plasticizer, was examined to highlight the developments that have taken place over the last few decades, aiming to fill gaps of knowledge in the large number of disjointed publications. The analysis includes the role of polymer/plasticizer molecular interactions and the conditions leading to the cross-over from antiplasticization to plasticization. This was based on molecular dynamics considerations of thermal transitions and related relaxation spectra, alongside the deviation of free volumes from the additivity rule.