On the equivalence between the thermodynamic and dynamic measurements of the glass transition in confined polymers

Open Access

Abstract

7th IDMRCS: Relaxation in Complex Systems ; Understanding why the glass transition temperature (Tg) of polymers deviates substantially from the bulk with nanoscale confinement has been a 20-year mystery. Ever since the observation in the mid-1990s that the Tg values of amorphous polymer thin films are different from their bulk values, efforts to understand this behavior have intensified, and the topic remains the subject of intense research and debate. This is due to the combined scientific and technological implications of size-dependent glassy properties. Here, we discuss an intriguing aspect of the glassy behavior of confined amorphous polymers. As experimentally assessed, the glass transition is a dynamic event mediated by segmental dynamics. Thus, it seems intuitive to expect that a change in Tg due to confinement necessitates a corresponding change in molecular dynamics, and that such change in dynamics may be predicted based on our understanding of the glass transition. The aim of this perspectives article is to examine whether or not segmental dynamics change in accordance with the value of Tg for confined polymers based on bulk rules. We highlight past and recent findings that have examined the relationship between Tg and segmental dynamics of confined polymers. Within this context, the decoupling between these two aspects of the glass transition in confinement is emphasized. We discuss these results within the framework of our current understanding of the glass transition as well as efforts to resolve this decoupling. Finally, the anomalous decoupling between translational (diffusion) and rotational (segmental) motion taking place in the proximity of attractive interfaces in polymer thin films is discussed. ; RDP acknowledge support from the National Science Foundation (NSF) Materials Research Science and Engineering Center program through the Princeton Center for Complex Materials (DMR-0819860), the NSF through a CAREER Award (DMR-1053144) and the AFOSR through a YIP Award (FA9550-12-1-0223). SN acknowledges financial support from the Defay Foundation and the funds FER of the Université Libre de Bruxelles. DC acknowledges the University of the Basque Country and Basque Country Government (Ref. No. IT-654-13 (GV)), Depto Educacion, Universidades e investigacion and Spanish Government (Grant No. MAT2012-31088) for their financial support. ; Peer Reviewed