Role of neighboring domains in determining the magnitude and direction of Tg-confinement effects in binary, immiscible polymer systems

Christopher M. Evans, Soyoung Kim, Connie B. Roth, Rodney D. Priestley, Linda J. Broadbelt, John M. Torkelson

Research output: Contribution to journalArticlepeer-review

32 Scopus citations


The glass transition temperature (Tg) of a polystyrene (PS) nanolayer is shown to be strongly tuned by the presence of neighboring immiscible polymer layers over a 100 °C range spanning temperatures above and below the bulk PS Tg. Fluorescence spectroscopy is used to measure the glass transition temperature (Tg) of the ultrathin dye-labeled PS layers at specific regions within multilayer films of immiscible polymers. The Tg of a 14-nm-thick PS layer is 45 °C atop poly(n-butyl methacrylate) and 144 °C atop poly(4-vinyl pyridine). Additionally, the Tg of an 11- to 14-nm thick PS layer is shown to be the same as that reported by a near-infinitely-dilute PS blend component [Evans and Torkelson Macromolecules 2012, 45, 8319] with the same neighboring polymer, which indicates a common physical origin of Tg perturbations in both systems. The magnitude of Tg-confinement effects depends not only on the Tg of the neighboring domain but is also strongly correlated with neighboring domain fragility, a fundamental property of glass formers which provides a link between medium-range structural order and dynamics.

Original languageEnglish (US)
Pages (from-to)180-187
Number of pages8
StatePublished - Dec 2 2015
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry


  • Glass transition
  • Nanoconfinement
  • Polymer blends


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