Direct Observation of the Dynamics of Latex Particles Confined inside Thinning Water-Air Films

The dynamics of micrometer-size polystyrene latex particles confined in thinning foam films was investigated by microscopic interferometric observation. The behavior of the entrapped particles depends on the mobility of the film surfaces, the particle concentration, hydrophobicity, and rate of film formation. When the films were stabilized by sodium dodecyl sulfate, no entrapment of particles between the surfaces was possible. When protein was used as a stabilizer, a limited number of particles were caught inside the film area due to the decreased mobility of the interfaces. In this case, extraordinary long-ranged (>100 Ìm) capillary attraction leads to two-dimensional (2D) particle aggregation. A major change occurs when the microspheres are partially hydrophobized by the presence of cationic surfactant. After the foam films are opened and closed a few times, a layer of particles simultaneously adsorbed to the two interfaces is formed, which sterically inhibits any further film opening and thinning. The particles within this layer show an excellent 2D hexagonal ordering. The experimental data are relevant to the dynamics of defects in coating films, Pickering emulsions, and particle assembly into 2D arrays

Theory of Shape-Shifting Droplets

Recent studies of cooled oil emulsion droplets uncovered transformations into a host of flattened shapes with straight edges and sharp corners, driven by a partial phase transition of the bulk liquid phase. Here, we explore theoretically the simplest geometric competition between this phase transition and surface tension in planar polygons and recover the observed sequence of shapes and their statistics in qualitative agreement with experiments. Extending the model to capture some of the three-dimensional structure of the droplets, we analyze the evolution of protrusions sprouting from the vertices of the platelets and the topological transition of a puncturing planar polygon.This work was supported in part by the Engineering and Physical Sciences Research Council (P. A. H.), an Established Career Fellowship from the EPSRC (R. E. G.), and the European Research Council (Grant EMATTER No. 280078 to S. K. S.)

Mechanisms and Control of Self-Emulsification upon Freezing and Melting of Dispersed Alkane Drops

Emulsification requires drop breakage and creation of a large interfacial area between immiscible liquid phases. Usually, high-shear or high-pressure emulsification devices that generate heat and increase the emulsion temperature are used to obtain emulsions with micrometer and submicrometer droplets. Recently, we reported a new, efficient procedure of self-emulsification (Tcholakova et al. Nat. Commun. 2017, 8, 15012), which consists of one to several cycles of freezing and melting of predispersed alkane drops in a coarse oil-in-water emulsion. Within these freeze-thaw cycles of the dispersed drops, the latter burst spontaneously into hundreds and thousands of smaller droplets without using any mechanical agitation. Here, we clarify the main factors and mechanisms, which drive this self-emulsification process, by exploring systematically the effects of the oil and surfactant types, the cooling rate, and the initial drop size. We show that the typical size of the droplets, generated by this method, is controlled by the size of the structural domains formed in the cooling-freezing stage of the procedure. Depending on the leading mechanism, these could be the diameter of the fibers formed upon drop self-shaping or the size of the crystal domains formed at the moment of drop-freezing. Generally, surfactant tails that are 0-2 carbon atoms longer than the oil molecules are most appropriate to observe efficient self-emulsification. The specific requirements for the realization of different mechanisms are clarified and discussed. The relative efficiencies of the three different mechanisms, as a function of the droplet size and cooling procedure, are compared in controlled experiments to provide guidance for understanding and further optimization and scale-up of this self-emulsification process