Vapor-induced swelling of supported methacrylic and siloxane polymer films: Determination of interaction parameters

White light reflectance spectroscopy is applied to monitor vapor-induced thickness changes of polymer films, supported on suitable silicon substrates. Assuming unidirectional swelling due to the constraining support, the equilibrium volume swelling of four methacrylic polymers and two siloxane-based copolymers upon exposure to various activities of water, methanol, ethanol, and ethyl acetate vapor, at 30°C is evaluated. The deduced sorption isotherms were fitted to the Flory-Huggins equation and interaction parameters, as well as solubility coefficients at infinite solute dilution, were deduced for each binary system. The relative sorption capacity of the different classes of polymers toward the four vapors are in line with the expected solubility interactions between solvent and solute. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010