Thermodynamic equilibrium of binary mixtures on curved surfaces.

Abstract

We study the global influence of curvature on the free energy landscape of two-dimensional binary mixtures confined on closed surfaces. Starting from a generic effective free energy, constructed on the basis of symmetry considerations and conservation laws, we identify several model-independent phenomena, such as a curvature-dependent line tension and local shifts in the binodal concentrations. To shed light on the origin of the phenomenological parameters appearing in the effective free energy, we further construct a lattice-gas model of binary mixtures on nontrivial substrates, based on the curved-space generalization of the two-dimensional Ising model. This allows us to decompose the interaction between the local concentration of the mixture and the substrate curvature into four distinct contributions, as a result of which the phase diagram splits into critical subdiagrams. The resulting free energy landscape can admit, as stable equilibria, strongly inhomogeneous mixed phases, which we refer to as "antimixed" states below the critical temperature. We corroborate our semianalytical findings with phase-field numerical simulations on realistic curved lattices. Despite this work being primarily motivated by recent experimental observations of multicomponent lipid vesicles supported by colloidal scaffolds, our results are applicable to any binary mixture confined on closed surfaces of arbitrary geometry.