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Updated: Apr 8, 2026

Cooling Rate Dependent Ellipsometry Measurements to Determine the Dynamics of Thin Glassy Films
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Cooling Rate Dependent Ellipsometry Measurements to Determine the Dynamics of Thin Glassy Films

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Cooperative strings and glassy interfaces.

Thomas Salez1, Justin Salez2, Kari Dalnoki-Veress3

  • 1Perimeter Institute for Theoretical Physics, Waterloo, ON, Canada N2L 2Y5; Laboratoire de Physico-Chimie Théorique, UMR CNRS Gulliver 7083, ESPCI ParisTech, PSL Research University, 75005 Paris, France; thomas.salez@espci.fr jforrest@perimeterinstitute.ca.

Proceedings of the National Academy of Sciences of the United States of America
|June 24, 2015
PubMed
Summary
This summary is machine-generated.

This study presents a minimal theory of glass formation, explaining glassy dynamics through molecular crowding and cooperative rearrangements. It successfully predicts bulk relaxation and interfacial layer behavior in thin polymer films.

Keywords:
cooperative rearrangementglass transitionthin films

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Area of Science:

  • Condensed Matter Physics
  • Materials Science
  • Polymer Physics

Background:

  • Glass formation is a complex phenomenon involving molecular rearrangements.
  • Understanding the dynamics of glassy systems is crucial for materials design.
  • The role of molecular crowding and cooperative motion in glass transition remains an active area of research.

Purpose of the Study:

  • To develop a minimal theory for glass formation incorporating molecular crowding and cooperative rearrangement.
  • To investigate the influence of free interfaces on glassy dynamics.
  • To derive key relations in glass transition theory and predict temperature-dependent properties.

Main Methods:

  • Theoretical modeling based on molecular crowding and string-like cooperative rearrangement.
  • Derivation of scaling expressions for particle participation in cooperative strings.
  • Inclusion of thermal dilatation to derive the Vogel-Fulcher-Tammann relation.
  • Analysis of system size effects near free interfaces.

Main Results:

  • A scaling expression for the number of particles in cooperative strings was obtained.
  • The Adam-Gibbs description of glassy dynamics was recovered.
  • The Vogel-Fulcher-Tammann relation was derived by including thermal dilatation.
  • A temperature-dependent cooperative length (ξ) for bulk relaxation was predicted.
  • Agreement with experimental measurements of glass transition temperature in thin polymer films was achieved.
  • Quantification of the temperature-dependent thickness (hm) of the interfacial mobile layer was enabled.

Conclusions:

  • The minimal theory provides a unified framework for understanding bulk and interfacial glass formation.
  • Molecular crowding and cooperative rearrangement are key mechanisms governing glassy dynamics.
  • The theory accurately predicts the behavior of thin polymer films, including interfacial effects.