Equilibrium behavior and dilational rheology of polyelectrolyte/insoluble surfactant adsorption films: didodecyldimethylammonium bromide and sodium poly(styrenesulfonate).

The surface pressure of monolayers of an insoluble surfactant, didodecyldimethylammonium bromide (DODAB), has been measured onto subphases with different concentrations of poly(styrenesulfonate) (PSS) and at different temperatures. The presence of PSS in the subphase shifts the surface-pressure (Pi) curves to larger areas per DODAB molecule, A, and shifts the surface phase transition to higher Pi's. The presence of PSS chains decreases the surface electric potential; the decrease is higher than expected from the formation of a double layer between the DODAB molecules and the PSS segments. Increasing the temperature shifts the surface-pressure curves to higher areas and also increases the values of Pi of the surface phase transition. The effect of the PSS chains on the Pi versus A curves is contrary to the one induced by the presence of inert electrolytes in the subphase. The behavior is consistent with the existence of a dense layer of PSS segments beneath the DODAB monolayer at low PSS concentrations, c. Two PSS layers exist at higher concentrations, a dense layer immediately below the DODAB and a less-dense layer, below the first one, that protrudes deep into the subphase. The surface-pressure relaxation curves have been found to be bimodal through the whole range of surface pressures and at all the values of polymer concentration studied. These results point out that the adsorption layers behave mainly as elastic bodies, with zero-frequency elasticity, epsilon(omega = 0), which agrees with the equilibrium compressibility modulus. The increase [epsilon(omega = 1) - epsilon(omega = 0)] has been found to be independent of both polymer concentration and molecular weight. The zero-frequency-dilational viscosity, kappa(omega = 0), strongly increases with Pi in the two-dimensional condensed-liquid region. The surface viscosity strongly decreases with increasing frequency; the decreasing rate is higher than the one found for the monolayers of nonionic insoluble polymers. kappa(omega = 0) has also been found to be independent of both polymer concentration and molecular weight. These results seem to indicate that it is the film formed by the DODAB molecules and the first dense polymer layer that determines the surface viscoelastic moduli of this system.