Soap-Film Membranes for CO2/Air Separation.

Thin liquid films are a potential game changer in the quest for efficient gas separation strategies. Such fluid membranes, which are complementary to their solid counterparts involving porous materials, can achieve complex separation by combining permeability and adsorption mechanisms in their liquid core and at their surface. In addition, unlike porous solid membranes that must be regenerated between separation steps to recover a gas-free porosity, thus preventing continuous operation, liquid membranes can be regenerated using continuous liquid flow through the fluid film. Here, building on the self-sustained mobile film technique, we propose a simple experimental setup allowing direct quantitative assessment of the gas permeability of soap films stabilized by different surfactant types. Using a simple prototypical example involving O2/N2 mixtures, the measurement principle is first presented to establish a proof of concept. As the gas solubilities and diffusivities are known, the results of such experiments can be compared with microscopic models to disentangle the liquid core and surface permeabilities from a direct macroscopic transport response of the film subjected to a gas concentration difference. The same dynamical experiments performed for air enriched in CO2 indicate that the permeability of the soap film varies with the molar fraction in the gas compartment, a feature not observed for O2/N2. These experimental findings pave the way for the design of novel separation technologies in fields and situations where porous solid membranes are of limited efficiency.

Relation between oxidation kinetics and reactant transport in an aqueous foam.

HYPOTHESIS: Aqueous foams are expected to constitute exquisite particularly suitable reactive medium for the oxidation of metals, since the reactant H+ can be supplied through the continuous liquid phase, while the reactant O2 can be transported through the gas bubbles. EXPERIMENTS: To test this hypothesis, we investigated the oxidation of a metallic copper cylinder immersed in an aqueous foam. To study the relation between the transport of these reactants and the kinetics of the chemical reaction we use a forced drainage setup which enables us to control both the advection velocity of the H+ ions through the foam and the foam liquid fraction. FINDINGS: We find experimentally that the mass of dissolved copper presents a maximum with the drainage flow rate, and thus with the foam liquid fraction. Modeling analytically the transfer of H+ and O2 through the foams enables us to show that this non-monotonic behavior results from a competition between the advective flux of H+ ions and the unsteady diffusion of O2 through the thin liquid films which tends to be slower as the area of the thin liquid films decreases with the drainage flow rate and the liquid fraction. This study shows for the first time how to optimize the foam structure and drainage flow in reactive foams in which the reactants are present both in the liquid and gaseous phases.

Impact of Fluorocarbon Gaseous Environments on the Permeability of Foam Films to Air.

A foam film, free to move and stabilized with tetradecyltrimethylammonium bromide or sodium dodecylsulfate surfactants, is deposited inside of a cylindrical tube. It separates the tube into two distinct gaseous compartments. The first compartment is filled with air, while the second one contains a mixture of air and perfluorohexane vapor (C6F14), which is a barely water-soluble fluorinated compound. This foam film thus acts as a liquid semipermeable membrane for gases equivalent to the solid semipermeable membranes conventionally used in fluid separation processes. To infer the rate of air transfer through the membrane, we measure the displacement of the mobile foam film. From this, we deduce the instantaneous permeability of the membrane. In contrast to the permeability of solid membranes, which inexorably decreases over time because they become clogged, an anticlogging effect is observed with a permeability that systematically increases over time. Because the thickness of the film is constant over time, we attribute this to the possibility of adsorbing or desorbing fluorinated gas molecules on the liquid membrane. Indeed, because the partial pressure of the fluorinated gas is high at the beginning of the experiment, the density of the adsorbed molecules is also high, which leads to a low permeability to air transfer. On the contrary, at the end of the experiment, the partial pressure in fluorinated gas and thus the density of the adsorbed molecules are low. This leads to a higher permeability and a less clogged membrane.

Transition from Exponentially Damped to Finite-Time Arrest Liquid Oscillations Induced by Contact Line Hysteresis.

To clarify the role of wetting properties on the damping of liquid oscillations, we studied the decay of oscillations of liquid columns in a U-shaped tube with controlled surface conditions. In the presence of sliding triple lines, oscillations are strongly and nonlinearly damped, with a finite-time arrest and a dependence on initial amplitude. We reveal that contact angle hysteresis explains and quantifies this solidlike friction.

Rupture of granular rafts: effects of particle mobility and polydispersity.

Reversible encapsulation of liquid materials is a technical challenge in many applications such as for the transport and controlled delivery of active ingredients. In contrast to most state-of-the-art processes, capillary adsorbed solid particles can achieve chemical-reaction-free encapsulation by forming dense rafts which isolate the liquid from its surroundings. While the production conditions of such capsules have been characterized, the control of the armor robustness remains poorly described and understood. In this paper, we probe the armor robustness via impacts of droplets on encapsulated materials. Thereby, we establish the mechanisms and conditions of armor rupture and derive models that predict the rupturing thresholds or probabilities. Using monodisperse sized particles and gradually increasing the impacting drop velocity, a sharp transition from sustained to coalescing drops is observed. On mobile rafts made of particles at the water/air interface, the velocity threshold increases with increasing particle diameter while an opposite trend is observed on immobile rafts made of particles trapped at a gelified interface. Two models based on particle pair and triplet interactions, respectively, quantitatively match the experiments. Assembling rafts with particles of two different sizes significantly smoothens the coalescence transition, regardless of particle mobility. Beyond apparent similarities, rationalizing the rupturing probability of mobile and immobile armor evidences very different sensitivity to heterogeneities. On immobile armor, drop coalescence remains random and thus well described by the statistical particle distribution while on mobile armor the ruptures are preferably localized at the non-percolated parts of the granular network.

Low gas permeability of particulate films slows down the aging of gas marbles.

Introducing solid particles into liquid films drastically changes their properties: "gas marbles" can resist overpressure and underpressure ten times larger than their pure liquid counterparts - also known as soap bubbles - before deforming. Such gas marbles can therefore prove to be useful as gas containers able to support stresses. Yet, as their liquid counterparts, they can undergo gas transfer, which can reduce the scope of their applications. However, their permeability has never been characterized. In this paper, we measure the gas permeability of gas marbles through dedicated experiments. Our results show that particulate films are less permeable to gas than their pure liquid counterparts. We attribute this limited overall gas flux to the particles that reduce the surface area through which gas diffuses.

Stable oil-laden foams: Formation and evolution.

The interaction between oil and foam has been the subject of various studies. Indeed, oil can be an efficient defoaming agent, which can be highly valuable in various industrial applications where undesired foaming may occur, as seen in jet-dyeing processes or waste water treatment plant. However, oil and foam can also constructively interact as observed in detergency, fire-fighting, food and petroleum industries, where oil can be in the foam structure or put into contact with the foam without observing a catastrophic break-up of the foam. Under specific physico-chemistry conditions, the oil phase can even be trapped inside the aqueous network of the foam, thus providing interesting complex materials made of three different fluid phases that we name oil-laden foam (OLF). In this review, we focus on such systems, with a special emphasis on dry OLF, i.e. with a total liquid volume fraction, ε smaller than 5%. We first try to clarify the physical and chemical conditions for these systems to appear, we review the different techniques of the literature to obtain them. Then we discuss their structure and identify two different OLF morphologies, named foamed emulsion, in which small oil globules are comprised within the network of the aqueous foam and biliquid foams, where the oil also comprised in the aqueous foam network is continuous at the scale of several bubbles. Last, we review the state of the art of their evolution in particular concerning topological changes, coalescence, coarsening and drainage.

Surfactant- and Aqueous-Foam-Driven Oil Extraction from Micropatterned Surfaces.

Liquid-infused surfaces are rough or patterned surfaces in which a lubricating fluid, such as oil, is infused, which exhibits various original properties (omniphobicity, biofouling, drag reduction). An outer flow in a confined geometry can entrain the oil trapped between the pattern of the surfaces by shearing the oil-water interface and cause the loss of the omniphobic properties of the interface. Starting from the theoretical analysis of Wexler et al. (Shear-driven failure of liquid-infused surfaces. Phys. Rev. Lett. 2015, 114, 168301), where a pure aqueous solution is the outer phase, we extend the predictions by introducing an extraction efficiency parameter α and by accounting for new dynamical effects induced by surfactants and aqueous foams. For surfactant solutions, decreasing the oil-water interfacial tension (γow) not only enhances oil extraction as expected but also modifies the dynamics of the receding oil-water interface through the variations of the receding contact angle (θ) with the capillary number (Ca), which is the ratio between the viscous and the capillary forces at the oil-water interface. For aqueous foams, the extraction dynamics are also influenced by the foam flow: oil is sheared by the thin film between the bubbles and the lubricating layer, which imposes a stronger interfacial shear compared to pure aqueous solutions. In both surfactant and foam cases, the experimental observations show the existence of nonuniform extraction dynamics related to the surfactant-induced instability of a two-fluid shear flow.

Yield-stress fluids foams: flow patterns and controlled production in T-junction and flow-focusing devices.

We study the formation of yield-stress fluid foams in millifluidic flow-focusing and T-junction devices. First, we provide a phase diagram for the unsteady operating regimes of bubble production when the gas pressure and the yield-stress fluid flow rate are imposed. Three regimes are identified: a co-flow of gas and yield-stress fluid, a transient production of bubble and a flow of yield-stress fluid only. Taking wall slip into account, we provide a model for the pressure at the onset of bubble formation. Then, we detail and compare two simple methods to ensure steady bubble production: regulation of the gas pressure or flow-rate. These techniques, which are easy to implement, thus open pathways for controlled production of dry yield-stress fluid foams as shown at the end of this article.

Bending modulus of bidisperse particle rafts: Local and collective contributions.

The bending modulus of air-water interfaces covered by a monolayer of bidisperse particles is probed experimentally under quasistatic conditions via the compression of the monolayer, and under dynamical conditions studying capillary-wave propagation. Simple averaging of the modulus obtained solely with small or large particles fails to describe our data. Indeed, as observed in other configurations for monodisperse systems, bidisperse rafts have both a granular and an elastic character: chain forces and collective effects must be taken into account to fully understand our results.

Capillary imbibition of aqueous foams by miscible and nonmiscible liquids.

When put in contact with a large liquid drop, dry foams wick owing to surface-tension-driven flows until reaching equilibrium. This work is devoted to the dynamics of this imbibition process. We consider imbibition of both wetting or nonwetting liquid, by putting the dry foam into contact either with the foaming solution that constitutes the foam or with organic oils. Indeed, with the appropriate choice of surfactants, oil spontaneously invades the liquid network of the foam without damaging it. Our experiments show an early-time dynamics in t(1/2) followed by a late-time dynamics in t(1/4). These features, which differ from theoretical works predicting a t(1/3) dynamics, are rationalized considering the influence of the initial liquid fraction of the foam in the driving capillary force and the impact of gravity through the capillary-gravity equilibrium.

Bubble Formation in Yield Stress Fluids Using Flow-Focusing and T-Junction Devices.

We study the production of bubbles inside yield stress fluids (YSFs) in axisymmetric T-junction and flow-focusing devices. Taking advantage of yield stress over capillary stress, we exhibit a robust break-up mechanism reminiscent of the geometrical operating regime in 2D flow-focusing devices for Newtonian fluids. We report that when the gas is pressure driven, the dynamics is unsteady due to hydrodynamic feedback and YSF deposition on the walls of the channels. However, the present study also identifies pathways for potential steady-state production of bubbly YSFs at large scale.

Coalescence of dry foam under water injection.

When a small volume of pure water - typically a drop - is injected within an aqueous foam, it locally triggers the rupture of foam films, thus opening an empty cavity in the foam's bulk. We consider the final shape of this cavity and we quantify its volume as a function of the volume of injected water, the diameter of the bubbles and the liquid fraction of the foam. We provide quantitative understanding to explain how and when this cavity appears. We epitomize the dilution of surfactants at the water-air interfaces as the main cause lying behind the coalescence process. We identify a new coalescence regime for which a critical surfactant concentration rules the stability of the foam.

Oil repartition in a foam film architecture.

The propagation and distribution of oil inside the aqueous network of a foam is investigated in the case where oil can invade the foam without breaking it. The oil is injected into an elementary foam architecture of nine foam films and four vertices obtained by plunging a cubic frame in a foaming solution. The frame is then deformed to trigger a film switching (topological rearrangement named T1) and oil redistribution through this process is reported. Depending on the relative ratio of injected oil and water, different behaviours are observed. For small amounts of oil, a globule is trapped in one single node whereas for large oil volumes, it invades the four nodes of the foam film assembly. In both these cases, a T1 process does not change the oil distribution. However, for intermediate volumes, oil initially trapped in one node is able to propagate to the neighbouring nodes after the T1 process. This important observation shows that topological rearrangements, which naturally occur in foams when they evolve with time or when they flow, do affect the distribution of the third phase that they carry. These different regimes are captured by simple modeling based on the capillary pressure balance inside the foam network. Moreover, in the large-oil-volume limit, a transient situation is evidenced where an oil film is trapped within the freshly formed water film. This oil film modifies the dynamics of the T1 process and can be stable for up to a few minutes. We expect this mechanism to have consequences on the rheological properties of oil-laden foams. Film rupture dynamics is also experimentally captured.

Capillary flow of oil in a single foam microchannel.

When using appropriate surfactants, oil and aqueous foam can be intimately mixed without the foam being destroyed. In this Letter, we show that a foam, initially free of oil, can draw an oil drop under the action of capillary forces and stretch it through the aqueous network. We focus on the suction of oil by a single horizontal foam channel, known as a Plateau border. In such confined channels, imbibition dynamics are governed by a balance between capillarity and viscosity. Yet, the scaling law for our system differs from that of classical imbibition in porous media such as aqueous foam. This is due to the particular geometry of the liquid channels: Plateau borders filled with foaming solution are always concave whereas they can be convex or flat when filled with oil. Finally, the oil slug, confined in the Plateau border, fragments into droplets following a film breakup.

Forced impregnation of a capillary tube with drop impact.

We experimentally investigate how the impregnation of porous media can be forced using the initial kinetic energy of an impacting drop. We focus on the scale of a single pore--either hydrophilic or hydrophobic--and thus study the impact of a single drop falling on vertical cylindrical capillary tubes. This experimental configuration therefore differs from the impregnation of a porous media because of the finite volume of the drop and its initial kinetic energy. We observe different limit regimes: at low impact velocity, we recover the classical results for impregnation. The liquid does not impregnate the hydrophobic pore while it is totally sucked into the hydrophilic one. At high impact velocities, the drop is broken in two parts: one part spreads at the top of the surface while an isolated slug is trapped within the pore. We determine the critical speeds for these regimes and obtain a full phase-diagram for our observations. We also stress the characteristics of impregnating slugs namely their volume and their motion within the pores.

Drops impacting inclined fibers.

Mats of fibers are often used to capture liquid drops, such as in filters or in fog's nets. It is desired to optimize the efficiency of capture, in particular in the limit of drops larger than the fibers, for which filters remain highly permeable. Here we show that the efficiency of capture is dramatically increased by tilting the fibers: then, the velocity V* below which a drop is fully captured is made much larger; moreover, the tilt maximizes the liquid volume left on the fiber when the impact velocity exceeds V*.

Osmotic pressure and structures of monodisperse ordered foam.

We present an experimental and numerical study of the osmotic pressure in monodisperse ordered foams as a function of the liquid fraction. The data are compared to previous results obtained for disordered monodisperse and polydisperse concentrated emulsions. Moreover, we report a quantitative investigation of the transition from a bubble close packing to a bcc structure as a function of the liquid volume fraction. These findings are discussed in the context of theoretical models that have been proposed in the literature.

Generation of polymerosomes from double-emulsions.

Diblock copolymers are known to spontaneously organize into polymer vesicles. Typically, this is achieved through the techniques of film rehydration or electroformation. We present a new method for generating polymer vesicles from double emulsions. We generate precision water-in-oil-in-water double emulsions from the breakup of concentric fluid streams; the hydrophobic fluid is a volatile mixture of organic solvent that contains dissolved diblock copolymers. We collect the double emulsions and slowly evaporate the organic solvent, which ultimately directs the self-assembly of the dissolved diblock copolymers into vesicular structures. Independent control over all three fluid streams enables precision assembly of polymer vesicles and provides for highly efficient encapsulation of active ingredients within the polymerosomes. We also use double emulsions with several internal drops to form new polymerosome structures.

Capturing drops with a thin fiber.

We study experimentally the dynamics of drops impacting horizontal fibers and characterize the ability of these objects to capture the drops. We first show that a drop larger than a critical radius cannot be trapped by a fiber whatever its velocity. We determine this critical size as a function of the fiber radius. Then we show that for smaller drops, different situations can occur: at a low impact velocity, the drop is entirely captured by the fiber, whereas some liquid is ejected when arriving faster. We quantify the threshold velocity of capture.