RESUMEN
Understanding the structure of polymer/surfactant mixtures at the air-water interface is of fundamental importance and also of relevance to a variety of practical applications. Here, the complexation between a neutral 'tardigrade' comb co-polymer (consisting of a hydrophilic polyethylene glycol backbone with hydrophobic polyvinyl acetate grafts, PEG-g-PVAc) with an anionic surfactant (sodium dodecyl sulfate, SDS) at the air-water interface has been studied. Contrast-matched neutron reflectivity (NR) complemented by surface tension measurements allowed elucidation of the interfacial composition and structure of these mixed systems, as well as providing physical insights into the polymer/surfactant interactions at the air-water interface. For both polymer concentrations studied, below and above its critical aggregation concentration, cac, (0.2 cac and 2 cac, corresponding to 0.0002 wt% or 0.013 mM and 0.002 wt% or 0.13 mM respectively), we observed a synergistic cooperative behaviour at low surfactant concentrations with a 1-2 nm mixed interfacial layer; a competitive adsorption behaviour at higher surfactant concentrations was observed where the polymer was depleted from the air-water interface, with an overall interfacial layer thickness ~1.6 nm independent of the polymer concentration. The weakly associated polymer layer "hanging" proximally to the interface, however, played a role in enhancing foam stability, thus was relevant to the detergency efficacy in such polymer/surfactant mixtures in industrial formulations.
RESUMEN
Impurities in crystalline materials introduce disorder into an otherwise ordered structure due to the formation of lattice defects and grain boundaries. The properties of the resulting polycrystal can differ remarkably from those of the ideal single crystal. Here we investigate a quasi-two-dimensional system of colloidal spheres containing a small fraction of aspherical impurities and characterise the resulting polycrystalline monolayer. We find that, in the vicinity of an impurity, the underlying hexagonal lattice is deformed due to a preference for five-fold co-ordinated particles adjacent to impurities. This results in a reduction in local hexagonal ordering around an impurity. Increasing the concentration of impurities leads to an increase in the number of these defects and consequently a reduction in system-wide hexagonal ordering and a corresponding increase in entropy as measured from the distribution of Voronoi cell areas. Furthermore, through both considering orientational correlations and directly identifying crystalline domains we observe a decrease in the average polycrystalline grain size on increasing the concentration of impurities. Our data show that, for the concentrations considered, local structural modifications due to the presence of impurities are independent of their concentration, while structure on longer lengthscales (i.e. the size of polycrystalline grains) is determined by the impurity concentration.
