Ultrathin foam films containing supramolecular structures like micelles in bulk and adsorbed surfactant at the liquid–air interface undergo drainage via stratification. At a fixed surfactant concentration, the stepwise decrease in the average film thickness of a stratifying micellar film yields a characteristic step size that also describes the quantized thickness difference between coexisting thick–thin flat regions. Even though many published studies claim that step size equals intermicellar distance obtained using scattering from bulk solutions, we found no reports of a direct comparison between the two length scales. It is well established that step size is inversely proportional to the cubic root of surfactant concentration but cannot be estimated by adding micelle size to Debye length, as the latter is inversely proportional to the square root of surfactant concentration. In this contribution, we contrast the step size obtained from analysis of nanoscopic thickness variations and transitions in stratifying foam films using Interferometry Digital Imaging Optical Microscopy (IDIOM) protocols, that we developed, with the intermicellar distance obtained using small-angle X-ray scattering. We find that stratification driven by the confinement-induced layering of micelles within the liquid–air interfaces of a foam film provides a sensitive probe of non-DLVO (Derjaguin–Landau–Verwey–Overbeek) supramolecular oscillatory structural forces and micellar interactions.

Drainage via stratification in micellar foam films formulated with ionic surfactants shows dramatic changes on salt addition: both the step size and the number of steps in their stepwise thinning diminish. As the stratification process is governed by supramolecular oscillatory structural forces that arise due to confinement-induced structuring of micelles, it is apparent that salt addition reduces the magnitude, periodicity, and decay length of the oscillatory forces. In this contribution, we characterize the changes in micellar size, shape, and interactions on salt addition in bulk solutions using small-angle X-ray scattering (SAXS) to understand and elucidate the influence of salt on stratification in micellar foam films and, more broadly, on the oscillatory structural forces. Adding salt leads to a significant reduction in long-range correlations between micelles and smaller intermicellar distances. These effects manifest as a weakening of the primary peak of the structure factor, ascertained from SAXS spectra, accompanied by its shift to higher wave vectors. Weakened long-range correlations diminish the magnitude and periodicity of the oscillatory disjoining pressure leading to smaller step sizes, fewer steps, and a rich nanoscopic topography, due to the influence of disjoining pressure on the deformable interfaces. The step sizes in stratifying thin films and intermicellar distances in bulk solutions present incongruous values, implying an imperfect analogy with studies on charged nanoparticles with matched and salt concentration-independent values of measured interparticle distances that equal the periodicity of force−distance curves. We anticipate that our findings are significant for multicomponent soft and biological matter containing self-assembled supramolecular structures wherein screened Coulomb interactions govern the self-assembly, interfacial adsorption, interactions, dynamics, and stability.

Sodium Naphthenates (NaNs), found in crude oils and oil sands process-affected water (OSPW), can act as surfactants and stabilize undesirable foams and emulsions. Despite the critical impact of soap-like NaNs...