Communication: slow relaxation, spatial mobility gradients, and vitrification in confined films

Mirigian, Stephen; Schweizer, Kenneth S.

doi:10.1063/1.4900507

Title: Communication: slow relaxation, spatial mobility gradients, and vitrification in confined films

Journal Article · Fri Oct 31 00:00:00 EDT 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4900507· OSTI ID:1265311

Mirigian, Stephen ^[1]; Schweizer, Kenneth S. ^[1]

Univ. of Illinois, Urbana, IL (United States)

Two decades of experimental research indicate that spatial confinement of glass-forming molecular and polymeric liquids results in major changes of their slow dynamics beginning at large confinement distances. A fundamental understanding remains elusive given the generic complexity of activated relaxation in supercooled liquids and the major complications of geometric confinement, interfacial effects, and spatial inhomogeneity. For this research, we construct a predictive, quantitative, force-level theory of relaxation in free-standing films for the central question of the nature of the spatial mobility gradient. The key new idea is that vapor interfaces speed up barrier hopping in two distinct, but coupled, ways by reducing near surface local caging constraints and spatially long range collective elastic distortion. Effective vitrification temperatures, dynamic length scales, and mobile layer thicknesses naturally follow. In conclusion, our results provide a unified basis for central observations of dynamic and pseudo-thermodynamic measurements.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: AC05-00OR22725

OSTI ID:: 1265311

Journal Information:: Journal of Chemical Physics, Vol. 141, Issue 16; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

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