Dissemin is shutting down on January 1st, 2025

Published in

American Institute of Physics, The Journal of Chemical Physics, 8(156), p. 084903, 2022

DOI: 10.1063/5.0081185

Links

Tools

Export citation

Search in Google Scholar

A β-NMR study of the depth, temperature, and molecular-weight dependence of secondary dynamics in polystyrene: Entropy–enthalpy compensation and dynamic gradients near the free surface

This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

Full text: Unavailable

Green circle
Preprint: archiving allowed
Green circle
Postprint: archiving allowed
Orange circle
Published version: archiving restricted
Data provided by SHERPA/RoMEO

Abstract

We investigated the depth, temperature, and molecular-weight (MW) dependence of the γ-relaxation in polystyrene glasses using implanted 8Li+ and β-detected nuclear magnetic resonance. Measurements were performed on thin films with MW ranging from 1.1 to 641 kg/mol. The temperature dependence of the average 8Li spin–lattice relaxation time [Formula: see text] was measured near the free surface and in the bulk. Spin–lattice relaxation is caused by phenyl ring flips, which involve transitions between local minima over free-energy barriers with enthalpic and entropic contributions. We used transition state theory to model the temperature dependence of the γ-relaxation, and hence [Formula: see text]. There is no clear correlation of the average entropy of activation [Formula: see text] and enthalpy of activation [Formula: see text] with MW, but there is a clear correlation between [Formula: see text] and [Formula: see text], i.e., entropy–enthalpy compensation. This results in the average Gibbs energy of activation, [Formula: see text], being approximately independent of MW. Measurements of the temperature dependence of [Formula: see text] as a function of depth below the free surface indicate the inherent entropic barrier, i.e., the entropy of activation corresponding to [Formula: see text] = 0, has an exponential dependence on the distance from the free surface before reaching the bulk value. This results in [Formula: see text] near the free surface being lower than the bulk. Combining these observations results in a model where the average fluctuation rate of the γ-relaxation has a “double-exponential” depth dependence. This model can explain the depth dependence of [Formula: see text] in polystyrene films. The characteristic length of enhanced dynamics is ∼6 nm and approximately independent of MW near room temperature.