The Influence of the Surface Chemistry of Cellulose Nanocrystals on Ethyl Lauroyl Arginate Foam Stability.

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.

From Individual Liquid Films to Macroscopic Foam Dynamics: A Comparison between Polymers and a Nonionic Surfactant.

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.

Dynamic stabilisation during the drainage of thin film polymer solutions.

The drainage and rupture of polymer solutions was investigated using a dynamic thin film balance. The polymeric nature of the dissolved molecules leads to significant resistance to the deformation of the thin liquid films. The influence of concentration, molecular weight, and molecular weight distribution of the dissolved polymer on the lifetime of the films was systematically examined for varying hydrodynamic conditions. Depending on the value of the capillary number and the degree of confinement, different stabilisation mechanisms were observed. For low capillary numbers, the lifetime of the films was the highest for the highly concentrated, narrowly-distributed, low molecular weight polymers. In contrast, at high capillary numbers, the flow-induced concentration differences in the film resulted in lateral osmotic stresses, which caused a dynamic stabilisation of the films and the dependency on molecular weight distribution in particular becomes important. Phenomena such as cyclic dimple formation, vortices, and dimple recoil were observed, the occurrence of which depended on the relative magnitude of the lateral osmotic and the hydrodynamic stresses. The factors which lead to enhanced lifetime of the films as a consequence of these flow instabilities can be used to either stabilise foams or, conversely, prevent foam formation.

Breakup of Thin Liquid Films: From Stochastic to Deterministic.

The thinning and rupture of thin liquid films is a ubiquitous process, controlling the lifetime of bubbles, antibubbles, and droplets. A better understanding of rupture is important for controlling and modeling the stability of multiphase products. Yet literature reports that film breakup can be either stochastic or deterministic. Here, we employ a modified thin film balance to vary the ratio of hydrodynamic to capillary stresses and its role on the dynamics of thin liquid films of polymer solutions with adequate viscosities. Varying the pressure drop across planar films allows us to control the ratio of the two competing timescales, i.e., a controlled hydrodynamic drainage time and a timescale related to fluctuations. The thickness fluctuations are visualized and quantified, and their characteristics are for the first time directly measured experimentally for varying strengths of the flow inside the film. We show how the criteria for rupture depend on the hydrodynamic conditions, changing from stochastic to deterministic as the hydrodynamic forces inside the film damp the fluctuations.

Mimicking coalescence using a pressure-controlled dynamic thin film balance.

The dynamics of thin films containing polymer solutions are studied with a pressure-controlled thin film balance. The setup allows the control of both the magnitude and the sign as well as the duration of the pressure drop across the film. The process of coalescence can be thus studied by mimicking the evolution of pressure during the approach and separation of two bubbles. The drainage dynamics, shape evolution and stability of the films were found to depend non-trivially on the magnitude and the duration of the applied pressure. Film dynamics during the application of the negative pressure step are controlled by an interplay between capillarity and hydrodynamics. A negative hydrodynamic pressure gradient promoted the thickening of the film, while the time-dependent deformation of the Plateau border surrounding it caused its local thinning. Distinct regimes in film break-up were thus observed depending on which of these two effects prevailed. Our study provides new insight into the behaviour of films during bubble separation, allows the determination of the optimum conditions for the occurrence of coalescence, and facilitates the improvement of population balance models.