How emulsified droplets induce the bursting of suspended films of liquid mixtures.

Emulsion droplets of silicone oil (PDMS) are widely used as antifoaming agents but, in the case of non-aqueous foams, the mechanisms responsible for the bursting of the films separating the bubbles remain unclear. We consider a ternary non-aqueous liquid mixture in which PDMS-rich microdroplets are formed by spontaneous emulsification. In order to quantitatively assess the effect of the emulsified microdroplets, we measure the lifetime of sub-micrometer-thick suspended films of these emulsions as well as the time variations of their thickness profiles. We observe that a droplet entering the film reduces its lifetime by inducing a local and fast thinning. In most cases, we ascribe it to the spreading of the drop at one of the film interfaces with air, which drags the underlying liquid and eventually causes the film to burst rapidly. We explain why, despite slower spreading, more viscous droplets cause films to burst more efficiently. More rarely, microdroplets may bridge the two interfaces of the film, resulting in an even more efficient bursting of the film, which we explain.

Effect of a Surfactant Mixture on Coalescence Occurring in Concentrated Emulsions: The Hole Nucleation Theory Revisited.

By conducting both a bottle test and isolate drop-drop experiments, we determine the coalescence rates of water droplets within water-in-oil emulsions stabilized by a large amount of Span 80 in the presence of Tween 20, a surfactant that acts as a demulsifier. Using a microscopic model based on a theory of hole nucleation, we establish an analytical formula that quantitatively predicts the coalescence frequency per unit area of droplets whose interfaces are fully covered by surfactant molecules. Despite its simplicity and the strong assumptions made for its derivation, this formula captures our experimental findings on Span 80-stabilized emulsions as well as other results, found in the literature, remarkably well on a wide range of water-in-crude oil systems.

Coalescence in concentrated emulsions: theoretical predictions and comparison with experimental bottle test behaviour.

Fusion between emulsion drops, also called coalescence, may be undesirable for storage or sought after depending on the desired application. In this latter case, a complete separation of the two liquids composing the emulsion is required. The same objective may be applicable to foams. We have performed bottle test experiments on a model system of water in oil (w/o) emulsion stabilized by high amounts of hydrophobic surfactant Span 80. We observe two regimes for emulsion separation: the first regime, which is fast and includes sedimentation of the water droplets, and the second regime, which exhibits a very dense and stable emulsion zone. We predict the initial thickness of the dense zone as a simple function of surfactant concentration and mean droplet size. From the assumption that the coalescence rate depends only on the area of the thin film between two contacted droplets, we quantitatively model the separation kinetics of the dense emulsion zone. Our results give rise to a simple method that allows measuring the coalescence frequency per unit area, only by monitoring bottle test experiments.

Forced Imbibition in Porous Media: A Fourfold Scenario.

We establish a comprehensive description of the patterns formed when a wetting liquid displaces a viscous fluid confined in a porous medium. Building on model microfluidic experiments, we evidence four imbibition scenarios all yielding different large-scale morphologies. Combining high-resolution imaging and confocal microscopy, we show that they originate from two liquid-entrainment transitions and a Rayleigh-Plateau instability at the pore scale. Finally, we demonstrate and explain the long-time coarsening of the resulting patterns.

Physicochemical properties of aqueous core hydrogel capsules.

Capsules having a thin alginate hydrogel membrane and an aqueous core can be obtained by a process that involves a co-extrusion step in air followed by a sol-gel transition of the shell after immersion into a gelling bath. The possibility to encapsulate cells that further grow in these biocompatible compartments, and thus offer a versatile tool for cell culture, led us to investigate the physicochemical properties of the capsules. A cut-off pore size of the semi-permeable membrane is extrapolated from the release of polymers out of the capsule. When polymers cannot diffuse through the membrane, the osmotic pressure mismatch between the core and the surrounding medium triggers an inflation of the capsule. The swelling may reach a steady state that allows the determination of the elastic features of the hydrogel shell. On the other hand, the capsule membrane may rupture and then contract. From this stress-relaxation process, a critical deformation of the hydrogel shell above which plasticity occurs can be deduced. Finally, thanks to the physical nature of the hydrogel, the core content can be released by dissolving the membrane with the help of small electrolytes. The shell life is shown to vary inversely with the ionic strength of the solution.

Lab on a chip for a low-carbon future.

Transitioning our society to a sustainable future, with low or net-zero carbon emissions to the atmosphere, will require a wide-spread transformation of energy and environmental technologies. In this perspective article, we describe how lab-on-a-chip (LoC) systems can help address this challenge by providing insight into the fundamental physical and geochemical processes underlying new technologies critical to this transition, and developing the new processes and materials required. We focus on six areas: (I) subsurface carbon sequestration, (II) subsurface hydrogen storage, (III) geothermal energy extraction, (IV) bioenergy, (V) recovering critical materials, and (VI) water filtration and remediation. We hope to engage the LoC community in the many opportunities within the transition ahead, and highlight the potential of LoC approaches to the broader community of researchers, industry experts, and policy makers working toward a low-carbon future.

Dewetting-induced membrane formation by adhesion of amphiphile-laden interfaces.

We introduce an approach for forming bilayer polymer membranes by adhesion of amphiphile-laden interfaces. This adhesion is induced by a reduction of solvent quality for the amphiphilic diblock copolymers through selective evaporation of good solvent in the solvent mixture. By combining this membrane formation mechanism with a double-emulsion-templated approach for vesicle formation, we fabricate monodisperse polymersomes that exhibit excellent membrane uniformity, and structural stability, using a method that has high encapsulation efficiency. Moreover, we also show that the technique is versatile and can be applied to different block copolymers. The ability to direct the assembly of amphiphiles into a membrane creates new opportunities to engineer the structures of vesicles on the level of the individual bilayer leaflets.

Breaking of Emulsions with Chemical Additives: Using Surrogate Fluids to Develop a Novel Theoretical Framework and Its Application to Water-in-Crude Oil Emulsions.

We investigate the role of adding a water-soluble surfactant (Tween 20) that acts as a demulsifier on the stability of water-in-dodecane emulsions stabilized with Span 80. Performing bottle test experiments, we monitor the emulsion separation process. Initially, water droplets sediment fast (∼10 min) until they become closely packed and form the so-called dense packed layer (DPL). The presence of the DPL, a long-lived metastable high-water-fraction (70-90%) emulsion separating bulk oil and water layers, slows down significantly the kinetics (∼105 min) of water separation. Once the DPL is formed, the ratio of the volume of separated water to the total water amount is called as water separation efficiency. We assume that the emulsion stability is reached when the coverage of the emulsifier surfactant exceeds 80% and use the ideal solution approximation. From that, we rationalize the water separation efficiency and the minimum demulsifier concentration required to maximize it, in terms of the mean droplet size, the surfactant concentrations, the total water volume fraction, and the adsorption strength of the water-soluble surfactant. Model predictions and experimental findings are in excellent agreement. We further test the validity and robustness of our theoretical model, by applying it successfully to data found in the literature on water-in-crude oil emulsion systems. Ultimately, our results prove that the efficiency of a demulsifier agent to break a W/O emulsion strongly correlates to its adsorption strength at the W/O interface, providing a novel contribution to the selection guidelines of chemical demulsifiers.

Design of vesicles using capillary microfluidic devices: from magnetic to multifunctional vesicles.

In the core, in the shell, or both: a microfluidic device is used to design magnetic vesicles (liposomes and polymersomes) through chemical modification of the nanoparticle surface. Hydrophilic, hydrophobic and fluorescent quantum dot nanoparticles are used for elaborating the vesicles. Hybrid vesicles are easily obtained with a very high yield and excellent monodispersity.