Localization in liquid phase separation: Coarsening and stable structures.

Abstract

Dynamics of pattern formation in self-organizing systems subjected to spontaneous suppression of diffusion through a recently proposed source-sink-boundary templating technique is presented based on three-dimensional numerical simulations. This template disorder is introduced to divide the system into three different subregions, i.e., a source (outer subregion) at higher potential and a sink (inner subregion) region at a lower potential with the help of a boundary which is at the highest potential. The boundary allows only one-way diffusion from source to sink so diffusion stops completely whenever the sink is filled to its capacity. This technique was shown to be able to spontaneously form stable and complex patterns in the source and the sink parts. While the technique is applicable to any self-organizing or phase-separating system whenever certain conditions are met, a physically realizable system of liquid films supported on chemically heterogeneous substrates which self-organizes through morphological phase separation is chosen to study the dynamics. Free-energy functional of this system shows an asymmetric double-well potential and the Maxwell's double tangent construction on this free energy gives rise to two distinct and finite equilibrium phases. Disorder is introduced in the form of chemical heterogeneity to divide the whole system into different subregions each consisting of two equilibrium phases, thus enabling more finite equilibrium points in the same system. The dynamics uncovers two different pathways for stable localized structures, viz., the defect and the direct pathway. Thinner films are likely to favor the defect pathway whereby the equilibrium pattern forms after coarsening, whereas thicker films will predominantly choose the direct pathway of pattern formation by phase separation. The final localized structure is same irrespective of the chosen pathway. The dynamics also shows that the patterns formed in the inner subregion part can be seen as a result of "localization" and those formed in the outer subregion are due to arrested diffusion under geometric or curvature constraints. Simple measures of localization in terms of free energy and its constituents are also presented. The identification of localization in the above systems opens up the possibility of a systematic approach to create controlled structures at nano- and submicrometer scales with desired shape and size. These structures constitute new building blocks of advanced and tailored materials.