Recent advances in the evolution of interfaces: thermodynamics, upscaling, and universality

We consider the evolution of interfaces in binary mixtures permeating strongly heterogeneous systems such as porous media. To this end, we first review available thermodynamic formulations for binary mixtures based on \emph{general reversible-irreversible couplings} and the associated mathematical attempts to formulate a \emph{non-equilibrium variational principle} in which these non-equilibrium couplings can be identified as minimizers. Based on this, we investigate two microscopic binary mixture formulations fully resolving heterogeneous/perforated domains: (a) a flux-driven immiscible fluid formulation without fluid flow; (b) a momentum-driven formulation for quasi-static and incompressible velocity fields. In both cases we state two novel, reliably upscaled equations for binary mixtures/multiphase fluids in strongly heterogeneous systems by systematically taking thermodynamic features such as free energies into account as well as the system's heterogeneity defined on the microscale such as geometry and materials (e.g. wetting properties). In the context of (a), we unravel a \emph{universality} with respect to the coarsening rate due to its independence of the system's heterogeneity, i.e. the well-known ${\cal O}(t^{1/3})$-behaviour for homogeneous systems holds also for perforated domains. Finally, the versatility of phase field equations and their \emph{thermodynamic foundation} relying on free energies, make the collected recent developments here highly promising for scientific, engineering and industrial applications for which we provide an example for lithium batteries

Wetting of prototypical one- and two-dimensional systems: Thermodynamics and density functional theory.

Consider a two-dimensional capped capillary pore formed by capping two parallel planar walls with a third wall orthogonal to the two planar walls. This system reduces to a slit pore sufficiently far from the capping wall and to a single planar wall when the side walls are far apart. Not surprisingly, wetting of capped capillaries is related to wetting of slit pores and planar walls. For example, the wetting temperature of the capped capillary provides the boundary between first-order and continuous transitions to condensation. We present a numerical investigation of adsorption in capped capillaries of mesoscopic widths based on density functional theory. The fluid-fluid and fluid-substrate interactions are given by the pairwise Lennard-Jones potential. We also perform a parametric study of wetting in capped capillaries by a liquid phase by varying the applied chemical potential, temperature, and pore width. This allows us to construct surface phase diagrams and investigate the complicated interplay of wetting mechanisms specific to each system, in particular, the dependence of capillary wetting temperature on the pore width

Density functional study of condensation in capped capillaries.

We study liquid adsorption in narrow rectangular capped capillaries formed by capping two parallel planar walls (a slit pore) with a third wall orthogonal to the two planar walls. The most important transition in confined fluids is arguably condensation, where the pore becomes filled with the liquid phase which is metastable in the bulk. Depending on the temperature T, the condensation in capped capillaries can be first-order (at $T\leqslant {{T}_{\text{cw}}}$ ) or continuous (at $T\gt {{T}_{\text{cw}}}$ ), where ${{T}_{\text{cw}}}$ is the capillary wetting temperature. At $T \gt {{T}_{\text{cw}}}$ , the capping wall can adsorb mesoscopic amounts of metastable under-condensed liquid. The onset of condensation is then manifested by the continuous unbinding of the interface between the liquid adsorbed on the capping wall and the gas filling the rest of the capillary volume. In wide capped capillaries there may be a remnant of wedge filling transition, which is manifested by the adsorption of liquid drops in the corners. Our classical statistical mechanical treatment predicts a possibility of three-phase coexistence between gas, corner drops and liquid slabs adsorbed on the capping wall. In sufficiently wide capillaries we find that thick prewetting films of finite length may be nucleated at the capping wall below the boundary of the prewetting transition. Prewetting then proceeds in a continuous manner manifested by the unbinding interface between the thick and thin films adsorbed on the side walls. Our analysis is based on a detailed numerical investigation of the density functional theory for the fluid equilibria for a number of illustrative case studies

Self-similarity of solitary waves on inertia-dominated falling liquid films

We propose consistent scaling of solitary waves on inertia-dominated falling liquid films, which accurately accounts for the driving physical mechanisms and leads to a self-similar characterization of solitary waves. Direct numerical simulations of the entire two-phase system are conducted using a state-of-the-art finite volume framework for interfacial flows in an open domain that was previously validated against experimental film-flow data with excellent agreement. We present a detailed analysis of the wave shape and the dispersion of solitary waves on 34 different water films with Reynolds numbers Re=20–120 and surface tension coefficients σ=0.0512–0.072Nm−1 on substrates with inclination angles β=19◦ − 90◦. Following a detailed analysis of these cases we formulate a consistent characterization of the shape and dispersion of solitary waves, based on a newly proposed scaling derived from the Nusselt flat film solution, that unveils a self-similarity as well as the driving mechanism of solitary waves on gravity-driven liquid films. Our results demonstrate that the shape of solitary waves, i.e., height and asymmetry of the wave, is predominantly influenced by the balance of inertia and surface tension. Furthermore, we find that the dispersion of solitary waves on the inertia-dominated falling liquid films considered in this study is governed by nonlinear effects and only driven by inertia, with surface tension and gravity having a negligible influence

Wetting on a spherical wall: influence of liquid-gas interfacial properties

We study the equilibrium of a liquid film on an attractive spherical substrate for an intermolecular interaction model exhibiting both fluid-fluid and fluid-wall long-range forces. We first reexamine the wetting properties of the model in the zero-curvature limit, i.e., for a planar wall, using an effective interfacial Hamiltonian approach in the framework of the well known sharp-kink approximation (SKA). We obtain very good agreement with a mean-field density functional theory (DFT), fully justifying the use of SKA in this limit. We then turn our attention to substrates of finite curvature and appropriately modify the so-called soft-interface approximation (SIA) originally formulated by Napi\'orkowski and Dietrich [Phys. Rev. B 34, 6469 (1986)] for critical wetting on a planar wall. A detailed asymptotic analysis of SIA confirms the SKA functional form for the film growth. However, it turns out that the agreement between SKA and our DFT is only qualitative. We then show that the quantitative discrepancy between the two is due to the overestimation of the liquid-gas surface tension within SKA. On the other hand, by relaxing the assumption of a sharp interface, with, e.g., a simple smoothing of the density profile there, markedly improves the predictive capability of the theory, making it quantitative and showing that the liquid-gas surface tension plays a crucial role when describing wetting on a curved substrate. In addition, we show that in contrast to SKA, SIA predicts the expected mean-field critical exponent of the liquid-gas surface tension