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Foams can resist destabilizaton in ways that appear similar on a macroscopic scale, but the microscopic origins of the stability and the loss thereof can be quite diverse. Here, we compare both the macroscopic drainage and ultimate collapse of aqueous foams stabilized by either a partially hydrolyzed poly(vinyl alcohol) (PVA) or a nonionic low-molecular-weight surfactant (BrijO10) with the dynamics of individual thin films at the microscale. From this comparison, we gain significant insight regarding the effect of both surface stresses and intermolecular forces on macroscopic foam stability. Distinct regimes in the lifetime of the foams were observed. Drainage at early stages is controlled by the different stress-boundary conditions at the surfaces of the bubbles between the polymer and the surfactant. The stress-carrying capacity of PVA-stabilized interfaces is a result of the mutual contribution of Marangoni stresses and surface shear viscosity. In contrast, surface shear inviscidity and much weaker Marangoni stresses were observed for the nonionic surfactant surfaces, resulting in faster drainage times, both at the level of the single film and the macroscopic foam. At longer times, the PVA foams present a regime of homogeneous coalescence where isolated coalescence events are observed. This regime, which is observed only for PVA foams, occurs when the capillary pressure reaches the maximum disjoining pressure. A final regime is then observed for both systems where a fast coalescence front propagates from the top to the bottom of the foams. The critical liquid fractions and capillary pressures at which this regime is obtained are similar for both PVA and BrijO10 foams, which most likely indicates that collapse is related to a universal mechanism that seems unrelated to the stabilizer interfacial dynamics.

Guanidine-based surfactant ethyl lauroyl arginate (LAE) and cellulose nanocrystals (CNCs) form complexes of enhanced surface activity when compared to pure surfactants. The LAE-CNC mixtures show enhanced foaming properties. The dynamic thin-film balance technique (DTFB) was used to study the morphology, drainage and rupture of LAE-CNC thin liquid films under constant driving pressure. A total of three concentrations of surfactant and the corresponding mixtures of LAE with sulfated (sCNC) and carboxylated (cCNC) cellulose nanocrystals were studied. The sCNC and cCNC suspension with LAE formed thin films, with stability increasing with surfactant concentration and with complex rheological properties. In the presence of LAE, the aggregation of CNC was observed. While the sCNC aggregates were preferentially present in the film volume with a small fraction at the surface, the cCNC aggregates, due to their higher hydrophobicity, were preferentially located at film interfaces, forming compact layers. The presence of both types of aggregates decreased the stability of the thin liquid film compared to the one for the LAE solution with the same concentration. The addition of CNC to LAE was critical for foam formation, and foam stability was in qualitative agreement with the thin films’ lifetimes. The foam volume increased with the LAE concentration. However, there was an optimum surfactant concentration to achieve stable foam. In particular, the very resistant foam was obtained with cCNC suspensions that formed the interfaces with a complex structure and rheology. On the other hand, at high LAE concentrations, the aggregates of CNC may exhibit antifoaming properties.

We investigate the flow of viscous interfaces carrying an insoluble surface active material, using numerical methods to shed light on the complex interplay between Marangoni stresses, compressibility, and surface shear and dilatational viscosities. We find quantitative relations between the drag on a particle and interfacial properties as they are required in microrheology, i.e., going beyond the asymptotic limits. To this end, we move a spherical particle probe at constant tangential velocity, symmetrically immersed at either the incompressible or compressible interface, in the presence and absence of surfactants, for a wide range of system parameters. A full three-dimensional finite element calculation is used to reveal the intimate coupling between the bulk and interfacial flows and the subtle effects of the different physical effects on the mixed-type velocity field that affects the drag coefficient, both in the bulk and at the interface. For an inviscid interface, the directed motion of the particle leads to a gradient in the concentration of the surface active species, which in turn drives a Marangoni flow in the opposite direction, giving rise to a force exerted on the particle. We show that the drag coefficient at incompressible interfaces is independent of the origin of the incompressibility (dilatational viscosity, Marangoni effects or a combination of both) and that its higher value can not only be related to the Marangoni effects, as suggested earlier. In confined flows, we show how the interface shear viscosity suppresses the vortex at the interface, generates a uniform flow, and consequently increases the interface compressibility and the Marangoni force on the particle. We mention available experimental data and provide analytical approximations for the drag coefficient that can be used to extract surface viscosities.