| Abstract: | Stoichiometric and nonstoichiometric polyion complex films were prepared from poly(sodium p-styrene sulfonate) and poly(diallyl dimethyl ammonium chloride). X-ray photoelectron spectroscopy revealed that the ionic groups in the complex are more ionized than in each component polymer. Fluorescence measurements showed that the complex had a main emission peak around 300 nm, whereas the peak for its original polyanion occurred at 324 nm. With the monomer and excimer peaks of the phenyl rings taken to be at 294 and 324 nm, respectively, the ratio of excimer to monomer emission intensities increased in proportion to the mole fraction of polyanion in the observed range 0.44–0.59. There was no discontinuity at the stoichiometric composition. Furthermore, the change in peak position shows that the local aggregation of phenyl groups in the polyanion was destroyed by complexation with the polycation through Coulombic forces. These results, together with the visual observation of the transparency of the films, mean that the mixing between polyanion and polycation chains in the polyion complex is on the molecular level and that this polymer alloy is miscible. |
