Surface modification of thin polystyrene films

The sulfonation of polystyrene (PS) films with 50 and 96% sulfuric acid as a function of time is presented. In contrast to previous literature reports, we showed that the treatment of PS films even with dilute sulfuric acid yields sulfonated surfaces after reaction times of 30 s(-1) h. The hydrophilicity of the modified PS increased considerably in comparison to the unreacted PS films. X-ray photoelectron spectroscopy yielded evidence for the sulfonation of PS at the surface. Unreacted spin-coated PS films were very smooth, while modified PS showed some clumps dispersed on a flat surface, as analyzed by atomic force microscopy. The surface morphology was identified as a phase-separated system composed of domains of unreacted PS and a matrix of sulfonated PS by fluorescence microscopy using the positively charged dye rhodamine B. The adsorption of the polycation diallyldimethylammonium chloride on the sulfonated PS surface could be detected. The thickness of the adsorbed polycation was 2.2 nm.