Hofmeister Salts Affect Buildup of Thin Multilayer Films Surrounding Oil Droplets

The layer-by-layer electrostatic deposition method is a novel technique to precisely control the interfacial properties of multilayered films such as charge, thickness, permeability, and composition. The formation and stability of multilayered emulsions is however often plagued by extensive droplet flocculation and aggregation even at ideal polyelectrolyte concentrations where saturation should occur. Addition of salts may reduce the degree of attractive interactions ions and thus improve deposition. To test this hypothesis, the influence of different Hofmeister salts (KCl, NaCl, LiCl, and NH₄Cl) at various salt concentrations (0–2500 mM) on the aggregation behavior of multilayered emulsions was investigated. A simple coating process of fish gelatin interfacial membranes with sugar beet pectin was used. Our results show that mean particle diameter and particle size distribution of emulsions initially decreased from 600 nm to 328 nm with increasing salt concentrations up to 250 mM. Above a critical level (>500 mM), heavy aggregation of emulsions at the presence of chaotropic salts occurred whereas kosmotropes reduced flocculation and creaming. Microscopic images and isothermal titration calorimetry confirmed particle size measurements. Results thus suggest that addition of salts may be an extremely useful tool to modulate and improve depositioning of alternatingly charged polymers on surfaces.