Nanoridge Formation and Dynamics of Stratification in Micellar Freestanding Films.

Abstract

Controlling and predicting the stability and lifetime of freestanding films, including foam and emulsion films, is crucial for many industrial and biological applications. Freestanding films (thickness <100 nm), stabilized by surfactants above the critical micelle concentration, exhibit stratification or stepwise thinning. Stratification proceeds by formation of thinner domains that grow at the expense of surrounding films. In this Article, we address several longstanding challenges related to the experimental characterization and theoretical description of thickness variations, forces, fluxes and flows underlying stratification. We show that nanoridges form and grow at the moving front around expanding domains, and we visualize their shape evolution using Interferometry Digital Imaging Optical Microscopy (IDIOM) protocols with an unprecedented spatiotemporal resolution (thickness <10 nm, time <1 ms). We develop a theoretical model for drainage via stratification under the influence of supramolecular oscillatory surface forces arising from the confinement-induced layering of micelles, and we show that the nanoridge growth and domain expansion dynamics can be modeled quantitatively.