Effect of Dilution on the Nonequilibrium Polyelectrolyte/Surfactant Association

Polyelectrolyte (PE)/surfactant (S) mixtures play a distinguished role in the efficacy of shampoos and toiletries primarily due to the deposition of PE/S precipitates on the hair surface upon dilution of the formulations. The classical interpretation of this phenomenon is a simple composition change during which the system enters the two-phase region. Recent studies, however, indicated that the phase properties of PE/S mixtures could be strongly affected by the applied solution preparation protocols. In the present work, we aimed at studying the impact of dilution on the nonequilibrium aggregate formation in the sodium poly(styrenesulfonate) (NaPSS)/dodecyltrimethylammonium bromide (DTAB)/NaCl system. Mixtures prepared with hundredfold dilution of concentrated NaPSS/DTAB/NaCl solutions in water were compared with those ones made by rapid mixing of dilute NaPSS/NaCl and DTAB/NaCl solutions. The study revealed that the phase-separation concentration range as well as the composition, morphology, and visual appearance of the precipitates were remarkably different in the two cases. These observations clearly demonstrate that the dilution/deposition process is also related to the nonequilibrium phase properties of PE/S systems, which can be used to modulate the efficiency of various commercial applications.