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Andrei Dukhin

Publications and source records attributed to Andrei Dukhin.

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Nanobubbles, pristine emulsions, high ionic strength electrokinetics -- paradoxes of Colloid and Interface Science

There are three paradoxes in the modern Colloid and Interface Science supported by large bulk of experimental evidence and contradicting classical theoretical models: - Electrokinetics at high ionic strength; - Nanobubbles having life span on scale of days and weeks without any surface stabilization; - Pristine emulsions having life span on scale of days and weeks without any surface stabilization. We overview many dozens of experimental papers by broad spectrum of scientific groups from many countries. We consider this vast experimental data as unambiguous evidence that these phenomena exist. On other hand, classical theoretical models deny such possibility. This contradiction between experiment and theory justifies introduction of new theoretical models. We overview these models. It turns out that there is one common feature between most promising of them -- assumption regarding structured water layer at hydrophobic interface. That is why we combine these three phenomena in this review. There is extensive literature on century old idea of the structured water layer, experimental and theoretical. We overview this literature, which provides convincing support to this hypothesis. We discuss existing theoretical models that incorporate the structured interfacial water layer for the successful explanation of these phenomena in more detail. Theoretical model of electrokinetics at high ionic strength was developed several decades ago. Theoretical model explaining paradoxical longevity of nanobubbles and pristine emulsions by interaction between structured water layer and electric double layer is more recent.

cond-mat.soft

Evolution of surfactant-free 'pristine' emulsions

The term pristine interface was introduced by Beattie and Djerdjev 20 years ago for emulsions that consist of only water and oil with no surfactant. They are different from Pickering emulsions, which are also surfactant-free but stabilized with colloidal particles. In contrast to previous studies, we monitor the kinetics of the initial stages of emulsion formation. We conducted such tests in an open setup when samples are open to air and CO2 content in the water varies, and in closed setup when samples are isolated with fixed CO2 content. For the open setup, sonication and initial pH > 9 leads to emulsions with high zeta potential and sub-micron droplet size. There are two evolution patterns: short- and long-terms. The short term lasts about 1 day and has changing pH and zeta potential, but almost constant droplet size. The long term is is over several days or even weeks, with droplet size increase toward saturation value (rate dependent on mixing conditions), with pH and zeta potential remaining constant. Emulsification at the closed setup is much less pronounced and pH remains constant. This difference points to the importance of adsorbed CO2 and related carbonate ions in the formation of pristine emulsions and charging droplets interfaces. We hypothesize the existence of structured water molecule layer at the interface, following Eastoe and Ellis. The Electric Double Layer exerts a (dielectrostatic) force on the water dipole moments in this layer that compensates the Kelvins pressure. The droplet size from this model is close to our measurements. Also, there is a repulsion of the water dipole moments, which compensates for the surface tension parallel to the interface. After ruling out alternative hypotheses with our data, we conclude that the model suggested for explaining the stability of nano-bubbles is also consistent with our results for these pristine emulsions.

physics.chem-ph