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Polyelectrolyte-surfactant mixtures and their interactions with fluid interfaces are an important research field due to their use in technological applications. Most of the existing knowledge on these systems is based on models in which the polyelectrolyte concentration is around 50 times lower than that used in commercial formulations. The present work marks a step to close the gap on the understanding of their behavior under more practically-relevant conditions. The adsorption of concentrated mixtures of poly(diallyldimethyl-ammonium) chloride and sodium N-lauroyl-N-methyltaurate at the water/vapor interface with a crude mixing protocol has been studied by different surface tension techniques, Brewster angle microscopy, neutron reflectometry, and several bulk characterization techniques. Kinetically-trapped aggregates formed during mixing influence the interfacial morphology of mixtures produced in the equilibrium one-phase region, yet fluctuations in the surface tension isotherm result depending on the tensiometric technique applied. At low bulk surfactant concentrations, the free surfactant concentration is very low, and the interfacial composition matches the trend of the bulk complexes, which is a behavior that has not been observed in studies on more dilute mixtures. Nevertheless, a transition to synergistic co-adsorption of complexes and free surfactant is observed at the higher bulk surfactant concentrations studied. This transition appears to be a special feature of these more concentrated mixtures, which deserves attention in future studies of systems with additional components.

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The adsorption of concentrated poly(diallyldimethylammonium chloride) (PDADMAC)-sodium lauryl ether sulfate (SLES) mixtures at the water/vapor interface has been studied by different surface tension techniques and dilational viscoelasticity measurements. This work tries to shed light on the way in which the formation of polyelectrolyte-surfactant complexes in the bulk affects the interfacial properties of mixtures formed by a polycation and an oppositely charged surfactant. The results are discussed in terms of a two-step adsorption-equilibration of PDADMAC-SLES complexes at the interface, with the initial stages involving the diffusion of kinetically trapped aggregates formed in the bulk to the interface followed by the dissociation and spreading of such aggregates at the interface. This latter process becomes the main contribution to the surface tension decrease. This work aids our understanding of the most fundamental basis of the physicochemical behavior of concentrated polyelectrolyte-surfactant mixtures which present complex bulk and interfacial interactions with interest in both basic and applied sciences.

The adsorption of mixtures of poly­(diallyldimethylammonium chloride) and sodium N-lauroyl-N-methyltaurate at the water/vapor interface has been studied using drop profile tensiometry and neutron reflectometry. This study sheds light on the mechanisms involved in the adsorption of polyelectrolyte–oppositely charged surfactants by the characterization of both equilibrium and dynamic features associated with the layer formation at the fluid interface. The results are discussed in terms of an adsorption−equilibration of the interfacial layers as a two-step process, with the initial stages involving the adsorption of polyelectrolyte−surfactant complexes formed in the bulk followed by the reorganization of the material at the interface. This work contributes to the understanding of the physicochemical features of systems that undergo complex bulk and interfacial interactions with importance in science and technology.

The deposition of layers of different polycations (synthetic or derived from natural, renewable resources) onto oppositely charged surfaces has been studied using ellipsometry and quartz crystal microbalance with dissipation monitoring (QCM-D). Information about the thickness of the deposited layers and their water content was ascertained. The adsorption of the different polycations onto negatively charged surfaces was found to be a complex process, which is influenced by the chemical nature of the polymer chains, ionic strength, polymer concentration and the addition of additives such as surfactants. The experimental picture shows a good agreement with theoretical calculations performed using the Self-Consistent Mean Field (SCF) approach. The results show that the electrostatically-driven deposition can be tuned by modifying the physico-chemical properties of the solutions and the chemical nature of the adsorbed polymer. This versatile approach is a big step forward in aiding the design of new polymers for many industrial applications and, in particular, the design of sustainable washing formulations for cosmetic applications.