Droplets abound in nature and technology. In general, they are multicomponent, and, when out of equilibrium, have gradients in concentration, implying flow and mass transport. Moreover, phase transitions can occur, in the form of evaporation, solidification, dissolution or nucleation of a new phase. The droplets and their surrounding liquid can be binary, ternary or contain even more components, with several in different phases. Since the early 2000s, rapid advances in experimental and numerical fluid dynamical techniques have enabled major progress in our understanding of the physicochemical hydrodynamics of such droplets, further narrowing the gap from fluid dynamics to chemical engineering and colloid and interfacial science, arriving at a quantitative understanding of multicomponent and multiphase droplet systems far from equilibrium, and aiming towards a one-to-one comparison between experiments and theory or numerics. This Perspective discusses examples of the physicochemical hydrodynamics of droplet systems far from equilibrium and the relevance of such systems for applications. Droplets in general are multicomponent and experience gradients in concentration, often leading to transport phenomena and phase transitions. This Perspective discusses recent progress on the physicochemical hydrodynamics of such droplet systems and their relevance for many important applications.

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Physicochemical hydrodynamics of droplets out of equilibrium

An asymptotic model is derived for the competitive diffusion-limited evaporation of multiple thin sessile droplets under the assumption that the droplets are well separated. Exact solutions of the model are obtained for a pair of and for a polygonal array of identical droplets, and the model is found to perform well even outside its formal range of validity, up to and including the limit of touching droplets. The shielding effect of droplets on each other is demonstrated, and the model is used to investigate the effect of this shielding on droplet evolutions and lifetimes, as well as on the coffee-ring effect. The theoretical predictions of the model are found to be in good agreement with recent experimental results for seven relatively closely spaced droplets, suggesting that the model could be a useful tool for studying a wide range of other droplet configurations.

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Competitive evaporation of multiple sessile droplets

Surface nanobubbles: Theory, simulation, and experiment. A review.

The existence of stable nanoscopic gaseous domains in liquids, or nanobubbles, has attracted both skepticism and intrigue since classical theory predicts that spherical gas bubbles cannot achieve stable equilibrium Can we prove these gaseous domains exist, and if they do, how do they survive? We critically review contemporary theoretical perspectives of the stability of surface and bulk nanobubbles and explain how experiments either vindicate or disprove them We conclude with a discussion of unanswered questions and propose future directions for the field at large

Stability of surface and bulk nanobubbles

We numerically investigate both single and multiple droplet dissolution with droplets consisting of less dense liquid dissolving in a denser host liquid. In this situation, buoyancy can lead to convection and thus plays an important role in the dissolution process. The significance of buoyancy is quantified by the Rayleigh number , which is the buoyancy force over the viscous damping force. In this study, spans almost four decades from 0.1 to 400. We focus on how the mass flux, characterized by the Sherwood number , and the flow morphologies depend on. For single droplet dissolution, we first show the transition of the scaling from a constant value to , which confirms the experimental results by Dietrich et al. (J. Fluid Mech., vol. 794, 2016, pp. 45-67). The two distinct regimes, namely the diffusively and the convectively dominated regimes, exhibit different flow morphologies: when , a buoyant plume is clearly visible, which contrasts sharply with the pure diffusion case at low. For multiple droplet dissolution, the well-known shielding effect comes into play at low , so that the dissolution rate is slower as compared to the single droplet case. However, at high , convection becomes more and more dominant so that a collective plume enhances the mass flux, and remarkably the multiple droplets dissolve faster than a single droplet. This has also been found in the experiments by Laghezza et al. (Soft Matt., vol. 12 (26), 2016, pp. 5787-5796). We explain this enhancement by the formation of a single, larger plume rather than several individual plumes. Moreover, there is an optimal at which the enhancement is maximized, because the single plume is narrower at larger , which thus hinders the enhancement. Our findings demonstrate a new mechanism in collective droplet dissolution, which is the merging of the plumes, which leads to non-trivial phenomena, contrasting the shielding effect.

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Convection-dominated dissolution for single and multiple immersed sessile droplets

Microscopic bubble dissolution is driven by the diffusion of gas within the surrounding liquid. Asymptotic analysis is used to characterize collective shielding effects in bubble lattices, the resulting bubble lifetime and dissolution dynamics.

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Collective dissolution of microbubbles

A microscopic bubble of soluble gas always dissolves in finite time in an under-saturated fluid. This diffusive process is driven by the difference between the gas concentration near the bubble, whose value is governed by the internal pressure through Henry's law, and the concentration in the far field. The presence of neighbouring bubbles can significantly slow down this process by increasing the effective background concentration and reducing the diffusing flux of dissolved gas experienced by each bubble. We develop theoretical modelling of such diffusive shielding process in the case of small microbubbles whose internal pressure is dominated by Laplace pressure. We first use an exact semi-analytical solution to capture the case of two bubbles, analyse in detail the shielding effect and show that hydrodynamic effects are mostly negligible except in the case of almost-touching bubbles. In order to tackle the case of multiple bubbles, we then derive and validate two analytical approximate yet generic frameworks, first using the method of reflections and then by proposing a self-consistent continuum description. Using both modelling frameworks, we examine the dissolution of regular 1D, 2D and 3D bubble lattices. Bubbles located at the edge of the lattices dissolve first, while innermost bubbles benefit from the diffusive shielding effect, leading to the inward propagation of a dissolution front within the lattice. We show that diffusive shielding leads to severalfold increases in the dissolution time which grows logarithmically with the number of bubbles in 1D-lattices and algebraically in two and three dimensions, scaling respectively as its square root and 2/3-power. We further illustrate the sensitivity of the dissolution patterns to initial fluctuations in bubble size or arrangement in the case of large and dense lattices, as well as non-intuitive oscillatory effects.

Etienne Guérin

Papers

Collective dissolution of microbubbles

Collective dissolution of microbubbles