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.
The surface oxygen content of selected wood-based phosphoric acid-activated carbons was quantified using X-ray photoelectron spectroscopy (XPS) and correlated with the residual bulk phosphate levels of the carbons and their adsorptivity in solution. The adsorption of Al 3+ , Cu 2+ , and parachlorophenol, respectively, from water decreased as a function of increasing surface oxygen content of the carbons. When the carbon of lowest surface oxygen content was oxidized with ozone to impart a surface oxygen content comparable to that of a carbon with a much higher phosphate level, adsorption of Al 3+ , Cu 2+ , and para-chlorophenol from water decreased proportionally. The increase in polarity of the carbon surface was accompanied by a decrease in pH and appeared to be the dominant factor with respect to the adsorption of the target species from water.
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