Response of adsorbed polyelectrolyte monolayers to changes in solution composition.

Reflectometry and quartz crystal microbalance are used to study the response of adsorbed polyelectrolyte monolayers to solutions of variable composition. These techniques respectively yield the dry and wet masses of the adsorbed layer, and by combing these results, one obtains the water content and the thickness of the polyelectrolyte films. The systems investigated are films of adsorbed poly(allyl amine) (PAH) and poly-L-lysine (PLL) on silica and films of poly(styrene sulfonate) (PSS) on amino-functionalized silica. When such films are adsorbed from concentrated polyelectrolyte solutions containing high levels of salt, they are found to swell reversibly up to a factor of 2 when incubated in solutions of low salt. This swelling is attributed to the strengthening of repulsive electrostatic interactions between the adsorbed polyelectrolyte chains. PAH films may also swell upon decrease of pH, and collapse upon a pH increase. This transition shows a marked hysteresis and can be rationalized by the competition of electrostatic repulsions between the chains and their attraction to the surface. The presently observed swelling phenomena are caused by a collective process driven by the electrostatic repulsion between the densely adsorbed polyelectrolyte chains. Such responsive layers are only obtained by adsorption from high polyelectrolyte and salt concentrations. Layers absorbed at low polyelectrolyte and salt concentrations show only minor swelling effects, since the adsorbed polyelectrolytes layers are dilute and the adsorbed polyelectrolyte chains interact only weakly.