Perylene Dye as a Measure of Dynamic Free Volume, Fragility, and Dynamic Glass Transition in Thin Polystyrene Films
Sarita Yadav, Connie B Roth
TL;DR
This paper shows how perylene dye can measure dynamic properties of thin polystyrene films, revealing faster relaxation dynamics in thinner films.
Contribution
The study introduces perylene dye as a novel dynamic probe for measuring glass transition and fragility in thin polymer films.
Findings
Perylene dye captures GHz vibrational fluctuations in thin polystyrene films.
Dynamic glass transition temperature Tgperyl is independent of film thickness down to 15 nm.
Relaxation dynamics in thin films are significantly faster than in bulk.
Abstract
We demonstrate the ability of perylene dye to capture the high frequency GHz vibrational density fluctuations of polymer matrices in thin polystyrene (PS) films with decreasing film thickness. From perylene’s temperature dependent fluorescence characteristics that are observed to be proportional to the polymer’s relaxation time τ(T), a perylene determined glass transition temperature Tgperyl is defined by the change in temperature dependence on cooling from a non-Arrhenius to Arrhenius behavior at the polymer’s T g. We find Tgperyl behaves like a dynamic measure of T g that is independent of film thickness h down to 15 nm. Fits to a Williams–Landel–Ferry (WLF) functional form above T g quantify a decrease in fragility with decreasing film thickness and demonstrate that the relaxation dynamics are significantly faster in thin films, with the average relaxation time at T g decreasing…
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Taxonomy
TopicsMaterial Dynamics and Properties · Advanced Physical and Chemical Molecular Interactions · Muon and positron interactions and applications