Soft electrostatic repulsion in particle monolayers at liquid interfaces: surface pressure and effect of aggregation.

Non-densely packed interfacial monolayers from charged micrometre-sized colloid particles find applications for producing micropatterned surfaces. The soft electrostatic repulsion between the particles in a monolayer on an air/water (or oil/water) interface is mediated by the non-polar fluid, where Debye screening is absent and the distances between the particles are considerably greater than their diameters. Surface pressure versus area isotherms were measured at the air/water interface. The experiments show that asymptotically the surface pressure is inversely proportional to the third power of the interparticle distance. A theoretical model is developed that predicts not only the aforementioned asymptotic law but also the whole surface pressure versus area dependence. An increase in the surface pressure upon aggregation of charged particles in the interfacial monolayers is experimentally established. This effect is explained by the developed theoretical model, which predicts that the surface pressure should linearly increase with the square root of the particle mean aggregation number. The effect of added electrolyte on the aggregation is also investigated. The data lead to the conclusion that 'limited aggregation' exists in the monolayers of charged particles. In brief, the stronger electrostatic repulsion between the bigger aggregates leads to a higher barrier to their coalescence that, in turn, prevents any further aggregation, i.e. negative feedback is present.This article is part of the themed issue 'Soft interfacial materials: from fundamentals to formulation'.

Surface pressure isotherm for a monolayer of charged colloidal particles at a water/nonpolar-fluid interface: experiment and theoretical model.

Monolayers from electrically charged micrometer-sized silica particles, spread on the air/water interface, are investigated. Because of the electrostatic repulsion, the distances between the particles are considerably greater than their diameters, i.e., we are dealing with nondensely packed interfacial layers. The electrostatic repulsion between the particles occurs through the air phase. Surface pressure vs area isotherms were measured by Langmuir trough, and the monolayers' morphology was monitored by microscope. The mean area per particle is determined by Delaunay triangulation and Voronoi diagrams. In terms of mean area, the surface pressure for monolayers from polydisperse and monodisperse particles obeys the same law. The experiments show that Π âˆ L(-3) at large L, where Π is the surface pressure and L is the mean interparticle distance. A theoretical cell model is developed, which predicts not only the aforementioned asymptotic law but also the whole Π(L) dependence. The model presumes a periodic distribution of the surface charge density, which induces a corresponding electric field in the air phase. Then, the Maxwell pressure tensor of the electric field in the air phase is calculated and integrated according to the Bakker's formula to determine the surface pressure. Thus, all collective effects from the electrostatic interparticle interactions are taken into account as well as the effects from the particle finite size. By evaporation of water, the particle monolayers are deposited on a solid substrate placed on the bottom of the trough. The electrostatic interparticle repulsion is strong enough to withstand the attractive lateral capillary immersion forces that are operative during the drying of the monolayer on the substrate. The obtained experimental results and the developed theoretical model can be useful for prediction and control of the properties of nondensely packed interfacial monolayers from charged particles that find applications for producing micropatterned surfaces.

Monolayers of charged particles in a Langmuir trough: Could particle aggregation increase the surface pressure?

The effect of aggregation on the surface pressure, Π, of monolayers from charged micrometer-sized colloidal particles on the air/water interface is investigated. Π is completely due to the long-range electrostatic repulsion between the particles mediated by their electrostatic field in the air. The most probable origin of particle aggregation is the attraction between capillary quadrupoles due to undulated contact lines on particle surfaces. Aggregates have higher charge and repel each other stronger than single particles. The data analysis by means of a theoretical model implies that Π linearly increases with n(1/2); n is the mean aggregation number, which can be determined from the experimental Π vs. area curves. The presence of electrolyte promotes aggregation, which tends to increase Π, but simultaneously reduces the surface charge that leads to lower Π. For our system, the first effect prevails and apparently paradoxical behavior is observed: the addition of salt in water enhances the electrostatic surface pressure. The data indicate limited aggregation: the rise of the electrostatic barrier prevents the further coalescence of aggregates if they have become sufficiently large. The results contribute for a better understanding of the factors that control the interactions in monolayers of charged particles at liquid interfaces.