Adsorption properties of polyelectrolyte-surfactant complexes on hydrophobic surfaces studied by QCM-D.

Adsorption and deposition from turbid solutions are common in many industrial processes but notoriously difficult to investigate using standard optical techniques such as ellipsometry and reflectometry. In this report, we have addressed this problem by employing a quartz crystal microbalance with dissipation monitoring ability, QCM-D. The system under investigation consisted of a cationic polyelectrolyte, poly(vinylamine), PVAm, and an anionic surfactant, sodium dodecyl sulfate, SDS, which were mixed together in 10 mM NaCl solution. The polyelectrolyte and the surfactant readily associate in bulk solution, resulting in increased solution turbidity once large aggregates are formed. The solutions were placed in contact with a polystyrene surface, and the adsorption process was monitored by following the changes in the resonance frequency and dissipation factor. The results obtained can in most cases be evaluated using the Sauerbrey relation, but in some cases a more elaborate analysis is necessary. It is found that PVAm adsorbs to polystyrene in the absence of SDS. In the turbid region, deposition is observed, and the sensed mass exceeds the sum of that obtained for each of the components alone. On the other hand, at high SDS concentrations, the surfactant dominates in the adsorbed layer. Adsorption equilibrium is in most cases established within 1-2 h, the exception being found around the solution composition that results in the formation of charge-neutralized aggregates. In this case, a slow deposition of aggregates persists over prolonged times.