Non-equilibrium interfacial tension during relaxation

TL;DR

This paper investigates the concept of non-equilibrium interfacial tension during relaxation in colloidal and polymer systems, revealing its potential negativity and impact on density perturbation morphology.

Contribution

It provides a theoretical framework for non-equilibrium interfacial tension, including its possible negative values and effects on system relaxation.

Findings

Non-equilibrium interfacial tension can be negative.

Negative non-equilibrium interfacial tension is compatible with positive equilibrium tension.

Sign of interfacial tension influences density perturbation morphology.

Abstract

The concept of a non-equilibrium interfacial tension, defined via the work required to deform the system such that the interfacial area is changed while the volume is conserved, is investigated theoretically in the context of the relaxation of an initial perturbation of a colloidal fluid towards the equilibrium state. The corresponding general formalism is derived for systems with planar symmetry and applied to fluid models of colloidal suspensions and polymer solutions. It is shown that the non-equilibrium interfacial tension is not necessarily positive, that negative non-equilibrium interfacial tensions are consistent with strictly positive equilibrium interfacial tensions, and that the sign of the interfacial tension can influence the morphology of density perturbations during relaxation.