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Two methods have been developed for the controlled formation of carboxylic acid units at the surfaces of aryloxyphosphazene high polymers. The first involves a permanganateinduced oxidation of p-methylphenoxy side groups, with the surface density of carboxylic acid units being controlled by the ratio of p-methylphenoxy to phenoxy groups along the polymer chains. The second approach involves a base-induced hydrolysis of carboxylate ester functions at the para-positions of surface aryloxy side groups. In this method the surface density of carboxyl units is controlled by the reaction conditions, especially by the temperature and the solvent for the base. The same ester functions were converted to alcohol moieties by surface reductions using lithium aluminum hydride in diethyl ether. The surface structures before and after these reactions were studied by a combination of contact angle measurements, X-ray photoelectron spectroscopy, scanning electron microscopy with X-ray microanalysis, and ATR-IR spectroscopy.

X-ray photoelectron spectroscopy was used to analyze a thin film of polymethylmethacrylate (PMMA) which was spin cast from a 2% weight solution of PMMA in toluene onto a gold substrate. A Hewlett Packard 5950A ESCA spectrometer was used for this investigation.

X-ray photoelectron spectroscopy was used to analyze a thin film of polystyrene. Spin casting from a 2% by weight solution of polystyrene in toluene was utilized. Film thickness was determined to be 60 nm by ellipsometry. The thin film was examined with a Hewlett Packard 5950A ESCA spectrometer.

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