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Swelling of Poly(n-butyl methacrylate) Films Exposed to Supercritical Carbon Dioxide: A Comparative Study with Polystyrene
J K BAL, G VIGNAUD, I AHMED, Y GROHENS
Published in American Chemical Society
2016
Volume: 32
   
Issue: 7
Pages: 1716 - 1722
Abstract
We report here the swelling and relaxation properties of confined poly(n-butyl methacrylate) (PBMA) films having thicknesses of less than 70 nm under supercritical carbon dioxide (scCO2) using the X-ray reflectivity technique. Swellability is found to be dominant in thinner films compared to thicker ones as a consequence of the confinement-induced densification of the former. Swellability is proportionately increased with the density of the film. PBMA films exhibit a more significant swelling than do PS films, and their differences become more prominent with the increase in film thickness. A comparison between the results obtained for polystyrene (PS) and PBMA ultrathin films reveals that the swellability is dependent upon the specific intermolecular interaction between CO2 and the chemical groups available in the polymers. Owing to strong Lewis acid-base interactions with scCO2 and the lower glass-transition temperature (bulk Tg ≈ 29 °C), PBMA films exhibit a greater amount of swelling than do PS films (bulk Tg ≈ 100 °C). Though they reach to the different swollen state upon exposition, identical relaxation behavior as a function of aging time is evidenced. This unprecedented behavior can be ascribed to the strong bonding between trapped CO2 and PBMA that probably impedes the release of CO2 molecules from the swollen PBMA films manifested in suppressed relaxation. (Graph Presented). © 2016 American Chemical Society.
About the journal
JournalData powered by TypesetLangmuir
PublisherData powered by TypesetAmerican Chemical Society
ISSN0743-7463