Microscale mobile surface double layer in a glassy polymer.

Yuan, Hailin; Yan, Jinsong; Gao, Ping; Kumar, Sanat K; Tsui, Ophelia K C · Sci Adv · 2022

basic_science · Level V

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Abstract

This study examines the origin of the widely different length scales, <i>h</i><sub>t</sub>-nanometers to micrometers-that have been observed for the propagation of the near-surface enhanced mobility in glassy polymers. Mechanical relaxations of polystyrene films with thicknesses, <i>h</i>, from 5 nm to 186 μm have been studied. For <i>h</i> < ~1 μm, the films relaxed faster than the bulk and the relaxation time decreased with decreasing <i>h</i> below ~100 nm, consistent with the enhanced dynamics originating from a near-surface nanolayer. For <i>h</i> > ~1 μm, a bulk-like relaxation mode emerged, while the fast mode changed to one that extended over ~1 μm from the free surface. These findings evidence that the mobile surface region is inhomogeneous, comprising a nanoscale outer layer and a slower microscale sublayer that relax by different mechanisms. Consequently, measurements probing the enhanced mobility of different mechanisms may find vastly different <i>h</i><sub>t</sub>'s as shown by the literature.