Cavity size, sorption and transport characteristics of thermally rearranged (TR) polymers

Yingying Jiang, Frank T. Willmore, David Sanders, Zachary P. Smith, Claudio P. Ribeiro, Cara M. Doherty, Aaron Thornton, Anita J. Hill, Benny D. Freeman, Isaac C. Sanchez

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90 Citations (Scopus)


Within a polymer thin film, free volume elements have a wide range of size and topology. This broad range of free volume element sizes determines the ability for a polymer to perform molecular separations. Herein, six permeable thermally rearranged (TR) polymers and their precursors were studied. Using atomistic models, cavity size (free volume) distributions determined by a combination of molecular dynamics and Monte Carlo methods were consistent with experimental observation that TR polymers are more permeable than their precursors. The cavity size distributions determined by simulation were also consistent with free volume distributions determined by positron annihilation lifetime spectroscopy. The diffusion, solubility and permeation of gases in TR polymers and their precursors were also simulated at 308 K, with results that agree qualitatively with experimental data.

Original languageEnglish
Pages (from-to)2244-2254
Number of pages11
Issue number10
Publication statusPublished - 4 May 2011
Externally publishedYes


  • Cavity size
  • Molecular simulation
  • TR polymer

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