Investigation of polymer–solvent interactions in poly(styrene sulfonate) thin films

William H. Ferrell, Douglas I. Kushner, Michael A. Hickner

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25 Scopus citations


The swelling behavior of acid form poly(styrene sulfonate) (PSS-H) thin films were investigated using in situ spectroscopic ellipsometry (SE) to probe the polymer–solvent interactions of ion-containing polymers under interfacial confinement. The interaction parameter (χ), related to the polymer and solvent solubility parameters in the Flory–Huggins theory, describes the polymer-solvent compatibility. In situ SE was used to measure the degree of polymer swelling in various solvent vapor environments, to determine χ for the solvent-PSS-H system. The calculated solubility parameter of 40–44 MPa1/2 for PSS-H was determined through measured χ values in water, methanol, and formamide environments at a solvent vapor activity of 0.95. Flory–Huggins theory was applied to describe the thickness-dependent swelling of PSS-H and to quantify the water-PSS-H interactions. Confinement had a significant influence on polymer swelling at low water vapor activities expressed as an increased χ between the water and polymer with decreasing film thickness. As the volume fraction of water approached ∼0.3, the measured χ value was ∼0.65, indicating the water interacted with the polymer in a similar manner, regardless of thicknesses.

Original languageEnglish (US)
Pages (from-to)1365-1372
Number of pages8
JournalJournal of Polymer Science, Part B: Polymer Physics
Issue number18
StatePublished - Sep 15 2017

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Polymers and Plastics
  • Materials Chemistry


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