Formation and characterization of perfluorocyclobutyl polymer thin films

Perfluorocyclobutyl (PFCB) polymers are a new class of materials that show promise as selective layer materials in the development of composite membranes for gas separations, such as carbon dioxide/methane (α_{pure gas} = 38.6) and oxygen/nitrogen (α_{pure gas} = 4.8) separations. In many of the flat sheet applications, a thin film of the selective layer that is free of major defects must be coated onto a support membrane. A focus of this study was to elucidate the impacts of solvents, polymer concentration, and dip‐coating withdrawal speed on PFCB thin film thickness and uniformity. An extension was proposed to the Landau–Levich model to estimate the polymer film thickness. The results show that the extended model fits the thickness‐withdrawal speed data well above about 55 mm/min, but, at lower withdrawal speeds, the data deviated from the model. This deviation could be explained by the phenomenon of polymer surface excess. Static surface excesses of polymer solutions were estimated by applying the Gibbs adsorption equation using measured surface tension data. Prepared films were characterized by ellipsometry. Refractive index was found to increase with decreasing film thickness below about 50 nm, indicating densification of ultrathin films prepared from PFCB solutions below the overlap concentration. Atomic force microscopy was used to characterize surface morphologies. Films prepared from tetrahydrofuran and chloroform yielded uniform nanolayers. However, films prepared using acetone as solvent yielded a partial dewetting pattern, which could be explained by a surface depletion layer of pure solvent between the bulk PFCB/acetone solution and the substrate. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013