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4704039 
Journal Article 
Investigation of Polymer-Solvent Interactions in Poly(styrene sulfonate) Thin Films 
Ferrell, WH; Kushner, DI; Hickner, MA 
2017 
Yes 
Journal of Polymer Science. Part B, Polymer Physics
ISSN: 0887-6266 
WILEY 
HOBOKEN 
55 
18 
1365-1372 
WOS:000406936100002 
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 (chi), 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 chi for the solvent-PSS-H system. The calculated solubility parameter of 40-44 MPa1/2 for PSS-H was determined through measured chi 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 chi between the water and polymer with decreasing film thickness. As the volume fraction of water approached similar to 0.3, the measured chi value was similar to 0.65, indicating the water interacted with the polymer in a similar manner, regardless of thicknesses. (C) 2017 Wiley Periodicals, Inc. 
confinement; Flory-Huggins theory; hydrophilic polymers; solubility parameter; swelling; spectroscopic ellipsometry; theory; water uptake