Adsorption of anionic polyelectrolytes to dioctadecyldimethylammonium bromide monolayers

Monolayers of dioctadecyldimethylammonium bromide (DODA) at the air/water i nterface were used as model for charged surfaces to study the adsorption of anionic polyelectrolytes. After spreading on a pure water surface the mono layers were compressed and subsequently transferred onto a polyelectrolyte solution employing the Fromherz technique. The polyelectrolyte adsorption w as monitored by recording the changes in surface pressure at constant area. For poly(styrene sulfonate) and carboxymethylcellulose the plot of the sur face pressure as function of time gave curves which indicate a direct corre lation between the adsorbed amount and surface pressure as well as a solely diffusion controlled process. In the case of rigid rod-like poly(p-phenyle ne sulfonate)s the situation is more complicated. Plotting the surface pres sure as function of time results in a curve with sigmoidal shape, character ized by an induction period. the induction period can be explained by a dom ain formation, which can be treated like a crystallization process. Employi ng the Avrami expression developed for polymer crystallization, the change in the surface pressure upon adsorption of rigid rod-like poly(p-phenylene sulfonate)s can be described.