Non-equilibrium interfaces in colloidal fluids

TL;DR

This paper theoretically investigates the early-stage relaxation of non-equilibrium interfaces in colloidal fluids, revealing that interfacial properties approach equilibrium values faster than the bulk phases, with implications for experimental studies.

Contribution

It demonstrates that interfacial structure and tension relax towards equilibrium during early-stage non-equilibrium, regardless of bulk phase deviations, providing new insights into colloidal interface dynamics.

Findings

Interfacial tension approaches equilibrium values during early relaxation.

Relaxation behavior is qualitatively similar regardless of bulk phase non-equilibrium.

Scaling forms differ between equilibrium and non-equilibrium systems.

Abstract

The time-dependent structure, interfacial tension, and evaporation of an oversaturated colloid-rich (liquid) phase in contact with an undersaturated colloid-poor (vapor) phase of a colloidal dispersion is investigated theoretically during the early-stage relaxation, where the interface is relaxing towards a local equilibrium state while the bulk phases are still out of equilibrium. Since systems of this type exhibit a clear separation of colloidal and solvent relaxation time scales with typical times of interfacial tension measurements in between, they can be expected to be suitable for analogous experimental studies, too. The major finding is that, irrespective of how much the bulk phases differ from two-phase coexistence, the interfacial structure and the interfacial tension approach those at two-phase coexistence during the early-stage relaxation process. This is a surprising observation since it implies that the relaxation towards global equilibrium of the interface is not following but preceding that of the bulk phases. Scaling forms for the local chemical potential, the flux, and the dissipation rate exhibit qualitatively different leading order contributions depending on whether an equilibrium or a non-equilibrium system is considered. The degree of non-equilibrium between the bulk phases is found to not influence the qualitative relaxation behavior (i.e., the values of power-law exponents), but to determine the quantitative deviation of the observed quantities from their values at two-phase coexistence. Whereas the underlying dynamics differs between colloidal and molecular fluids, the behavior of quantities such as the interfacial tension approaching the equilibrium values during the early-stage relaxation process, during which non-equilibrium conditions of the bulk phases are not changed, can be expected to occur for both types of systems.