A direct comparison of surface and bulk chain-relaxation in polystyrene

Wen Li Wu, Sharadha Sambasivan, Chia Ying Wang, W. E. Wallace, J. Genzer, D. A. Fischer

Research output: Contribution to journalArticlepeer-review

30 Scopus citations


Near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy was used to measure simultaneously the relaxation rates of polystyrene (PS) molecules at the free surface and in the bulk. The samples were uniaxially stretched and annealed at temperatures below the bulk glass transition temperature of PS. The surface and bulk chain relaxation was monitored by measuring the partial-electron and the fluorescence NEXAFS yields, respectively, both parallel and perpendicular to the stretching direction. The decay of the optical birefringence was also measured to provide an independent measure of the bulk relaxation. Relaxation of PS chains was found to occur faster on the surface relative to the bulk. The magnitude of the surface glass transition temperature suppression over the bulk was estimated based on the information on the temperature dependence of the rates.

Original languageEnglish (US)
Pages (from-to)127-132
Number of pages6
JournalEuropean Physical Journal E
Issue number1
StatePublished - Sep 2003
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • General Materials Science
  • Biophysics
  • Biotechnology
  • Surfaces and Interfaces


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