Abstract
Miscible liquids can phase separate in response to a composition change. In bulk fluids, the demixing begins on molecular-length scales, which coarsen into macroscopic phases. By contrast, confining a mixture in microfluidic droplets causes sequential phase separation bursts, which self-organize into rings of oil and water to make multilayered emulsions. The spacing in these nonequilibrium patterns is self-similar and scale-free over a range of droplet sizes. We develop a modified Cahn-Hilliard model, in which an immiscibility front with stretched exponential dynamics quantitatively predicts the spacing of the layers. In addition, a scaling law predicts the lifetime of each layer, giving rise to a stepwise release of inner droplets. Analogously, in long rectangular capillaries, a diffusive front yields large-scale oil and water stripes on the time scale of hours. The same theory relates their characteristic length scale to the speed of the front and the rate of mass transport. Control over liquid-liquid phase separation into large-scale patterns finds potential material applications in living cells, encapsulation, particulate design, and surface patterning.