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Films of polystyrene (PS) and poly(methyl methacrylate) (PMMA) blend have been annealed at a temperature above their glass transition temperatures for up to 48 h. Surface chemical compositions of the cast and annealed films were measured by X-ray photoelectron spectroscopy (XPS) while surface topographical changes were followed by atomic force microscopy (AFM). The blend films spin-cast from chloroform produce nonequilibrium surfaces with a significant excess of PMMA. The polymer component with a lower surface free energy, PS, is shown to segregate to the surface upon annealing. The PS surface concentration of the films, containing 50% PS:50% PMMA in the bulk, was evaluated using the ester peak in XPS C 1s spectra (sampling depth ∼ 9 nm) and found to increase from ∼5% (freshly spin-cast film) to a saturated level of ∼47% after 17 h of annealing. AFM imaging reveals evolution of blend morphology with annealing time. The spin-cast films prior to annealing exhibit pitted topography with typical pit size of ∼1.2 μm and depth of 30−40 nm. As the annealing process proceeds, these pits get continually shallower. Frictional force microscopy with hydroxylated tips recorded surface phase separations for the films of 2−4 h annealing. As the annealing continues to above 14 h, the pitted structure becomes distorted. The surface enrichment and morphology changes upon annealing are explained by dewetting of PMMA relative to PS.

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The surfaces of standard untreated polystyrene cell culture dishes have been oxidatively modified for up to 8 min exposure time using an ultraviolet ozone treater in order to promote cell adhesion. Surface oxygen chemisorption and topographical modification has been characterized using monochromatic X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), respectively. The oxidation process is shown to proceed at low exposure times (<60 s) via the formation of CsOR groups, although some R2CdO and RO-CdO groups are also formed. At longer treatments, RO-CdO groups become the dominant species, although the other groups are also present. The maximum level of oxygen reached is 36 atomic %. Some of the oxygen present at surfaces treated at times of >60 s is in the form of loosely bound low molecular weight oxidized material (LMWOM) which is produced by oxidative scission of the PS backbone. Water washing leads to a reduction in surface oxygen content mainly by the removal of ROsCdO and R2CdO functional groups. The residual stable oxygen levels, which can be introduced, are approximately 20-25 atomic %. Surface chemistry changes are accompanied by the formation of surface spikes which are about 30 nm high and 300-400 nm wide. A correlation between treatment time/oxygen level and overall roughness is observed. The effect of washing upon the topography is to slightly increase the surface roughness, although not to a significant degree. The attachment kinetics of adhesion for Chinese hamster ovary cells show that adhesion occurs much more rapidly for oxidized surfaces than for untreated control materials. A direct correlation between the levels of oxidation and the rate of cell adhesion is demonstrated.

Polystyrene (PS) and poly(methyl methacrylate) (PMMA) thin films (<100 nm thickness) have been spin-cast from chloroform solution onto cleaved mica surfaces (roughness within 0.2 nm). An algorithm for calculating the film thicknesses based on the relative intensities of the C 1s peak of the films and the Si 2s peak of the mica from angle-resolved X-ray photoelectron spectroscopy (XPS) is presented. The film thickness changes as a function of casting conditions. Data from this approach are comparable with thickness measured by an atomic force microscopy (AFM) tip-scratch method in the range 1.5-5.5 nm. Thicknesses of the films are shown to increase linearly with concentration of cast solutions.