Spinodal stratification in ultrathin micellar foam films

We report the discovery of a hitherto unreported mechanism of drainage and rupture of micellar foam films that presents unexplored opportunities for understanding and controlling the stability, lifetime and properties of ubiquitous foams. It is well-known that ultrathin micellar foam films exhibit stratification, manifested as stepwise thinning and coexistence of thin-thick flat regions that differ in thickness by a nanoscopic step size equal to the intermicellar distance. Stratification typically involves the spontaneous formation and growth of thinner, darker, circular domains or thicker, brighter mesas. Mechanistically, domain expansion appears similar to hole growth in polymer films undergoing dewetting by nucleation and growth mechanism that can be described by considering metastable states resulting from a thickness-dependent oscillatory free energy. Dewetting polymer films occasionally phase separate into thick and thin regions forming an interconnected, network-like morphology by undergoing spinodal dewetting. However, the formation of thick-thin spinodal patterns has never been reported for freestanding films. In this contribution, we show that the thickness-dependent oscillatory contribution to free energy that arises due to confinement-induced layering of micelles can drive the formation of such thick-thin regions by undergoing a process we term as spinodal stratification. We visualize and characterize the nanoscopic thickness variations and transitions by using IDIOM (interferometry digital imaging optical microscopy) protocols to obtain exquisite thickness maps of freestanding films. We find that evaporation and enhanced drainage in vertical films play a critical role in driving the process, and spinodal stratification can occur in both single foam films and in bulk foam.