Foam coarsening under a steady shear: interplay between bubble rearrangement and film thinning dynamics.

Aqueous foams are unstable and age by drainage and coarsening. Today, these effects are well described, as also their impact on foam properties. In that respect, the foam viscoelastic properties evolve in time as a consequence of coarsening which tends to increase the mean bubble size. Here, we investigate the reverse coupling, and study if and how the continuous flow of a foam can impact its dynamics of coarsening. We introduce a new protocol where brief oscillatory measurements are inserted during a constant steady shear, allowing us to monitor the relative variation of the bubble size with time (obtained from the one of the elastic modulus G') as a function of the applied shear rate. It turns out that the coarsening rate is strongly impacted by the applied shear: this rate is continuously reduced above a critical shear rate, which itself decreases with the bubble size. This coarsening-rate reduction is interpreted as the result of out-of-equilibrium and shear-dependent film thicknesses, being higher than at rest. The critical shear rate, above which films are dynamically sustained at higher thickness than at equilibrium, emerges from the competition between the rate of rearrangements and the time required to drain the thick film created during the rearrangement. We thus report here a first experimental proof and measurements of out-of-equilibrium film thicknesses within a sheared foam, and of the impact this has on coarsening.

One step generation of single-core double emulsions from polymer-osmose-induced aqueous phase separation in polar oil droplets.

Water-in-oil-in-water emulsions (W/O/W) are aqueous droplet(s) embedded within oil droplets dispersed in a continuous water phase. They are attracting interest due to their possible applications from cosmetic to food science since both hydrosoluble and liposoluble cargos can be encapsulated within. They are generally prepared using a one-step or a two-step method, phase inversion and also via spontaneous emulsification. Here, we describe a general and simple one-step method based on hydrophilic polymers dispersed in polar oils to generate osmose-induced diffusion of water into oil droplets, forming polymer-rich aqueous droplets inside the oil droplets. Polyethylene glycol, but also other hydrophilic polymers (branched polyethylene imine or polyvinyl pyrrolidone) were successfully dispersed in 1-octanol or other polar oils (oleic acid or tributyrin) to produce an O/W emulsion that spontaneously transformed into a W1/O/W2 emulsion, with the inner aqueous droplet (W1) only containing the hydrophilic polymer initially dispersed in oil. By combining single drop experiments, with macroscopic viscosity measurements, we demonstrated that the double emulsion resulted of water diffusion, which amplitude could be adjusted by the polymer concentration. The production of high internal phase emulsions was also achieved, together with a pH-induced transition from multiple to single core double emulsion. We expect this new method for producing double emulsions to find applications in domains of microencapsulation and materials chemistry.

Ultrastable and Responsive Foams Based on 10-Hydroxystearic Acid Soap for Spore Decontamination.

Currently, there is renewed interest in using fatty acid soaps as surfactants. Hydroxylated fatty acids are specific fatty acids with a hydroxyl group in the alkyl chain, giving rise to chirality and specific surfactant properties. The most famous hydroxylated fatty acid is 12-hydroxystearic acid (12-HSA), which is widely used in industry and comes from castor oil. A very similar and new hydroxylated fatty acid, 10-hydroxystearic acid (10-HSA), can be easily obtained from oleic acid by using microorganisms. Here, we studied for the first time the self-assembly and foaming properties of R-10-HSA soap in an aqueous solution. A multiscale approach was used by combining microscopy techniques, small-angle neutron scattering, wide-angle X-ray scattering, rheology experiments, and surface tension measurements as a function of temperature. The behavior of R-10-HSA was systematically compared with that of 12-HSA soap. Although multilamellar micron-sized tubes were observed for both R-10-HSA and 12-HSA, the structure of the self-assemblies at the nanoscale was different, which is probably due to the fact that the 12-HSA solutions were racemic mixtures, while the 10-HSA solutions were obtained from a pure R enantiomer. We also demonstrated that stable foams based on R-10-HSA soap can be used for cleaning applications, by studying spore removal on model surfaces in static conditions via foam imbibition.

Non linear elasticity of foam films made of SDS/dodecanol mixtures.

Foam film elasticity plays a significant role in film drainage and film stability and is thus expected to influence foam dynamical properties. It strongly depends on the foaming solution composition and differs from the interface elasticity measured in unconfined geometries. We use a deformable frame to deform an assembly of five films and we measure the tension and extension of each film. This provides a simple and accurate determination of the film elasticity, in the linear and non-linear regimes, for a set of SDS/dodecanol mixtures, at various concentrations. We show that the non-linear elastic behavior is well reproduced by Mysel's model coupled with a Langmuir coadsorption isotherm for a large range of chemical compositions.

Adjusting the water-sensitivity of sugar/boronate-based organogels.

During the investigation of the water-sensitivity of (arylboronate alkylglucoside)-based organogels, we evaluated a series of twelve potential organogelators. They were synthesised in a single step from the corresponding arylboronic acids and alkylglucosides. Eight of them showed organogelation abilities in three solvents (toluene, cyclohexane, and ethyl myristate). Conformational minimisations of the potential organogelators permitted a clear relationship between the arylboronate orientation and the gelation effectiveness to be established. These gels were characterised by rheometry and SEM which revealed a gel-state originating from the self-assembly of the organogelators into long entangled fibres. SAXS confirmed the mode of packing in a hexagonal phase. Gels in toluene were found to be water-sensitive both after addition of a small amount of water and immersion into water. This study demonstrated that the main parameter impacting the water-sensitivity was the length of the alkyl chain at the anomeric position of the glucoside unit, much more than the functionalisation of an arylboronate moiety.

Self-Propulsion of a Volatile Drop on the Surface of an Immiscible Liquid Bath.

We demonstrate the self-propulsion of a volatile drop on the surface of a bath of an immiscible liquid. Evaporative heat pumping is converted into directed motion through thermocapillary stresses, which arise from the coupling between surface-tension-driven flows and temperature advection. A propulsive force arises from convection-sustained temperature gradients along the drop interface, resulting in a warmer pool of liquid being advected by the hydrodynamic flow in the underlying bath toward the back of the drop. The dependence of the drop speed on the activity source, i.e., the evaporation flux, is derived with scaling arguments and captures the experimental data.

Boron Effect on Sugar-Based Organogelators.

The reaction of several alkylglucosides with phenyl boronic acid permitted easy access to a series of alkylglucoside phenyl boronate derivatives. This type of compound has structures similar to those of known benzylidene glucoside organogelators except for the presence of a boronate function in place of the acetal one. Low to very low concentrations of these amphiphilic molecules produced gelation of several organic solvents. The rheological properties of the corresponding soft materials characterized them as elastic solids. They were further characterized by SEM to obtain more information on their morphologies and by SAXS to determine the type of self-assembly involved within the gels. The sensitivity of the boronate function towards hydrolysis was also investigated. We demonstrated that a small amount of water (5 % v/v) was sufficient to disrupt the organogels leading to the original alkylglucoside and phenyl boronic acid; an important difference with the stable benzylidene-based organogelators. Such water-sensitive boronated organogelators could be suitable substances for the preparation of smart soft material for topical drug delivery.

Stability of a directional Marangoni flow.

Marangoni flows result from surface-tension gradients, and these flows occur over finite distances on the surface, but the subsequent secondary flows can be observed on much larger lengthscales. These flows play major roles in various phenomena, from foam dynamics to microswimmer propulsion. We show here that if a Marangoni flow of soluble surfactants is confined laterally, the flow forms an inertial surface jet. A full picture of the flows on the surface is exhibited, and the velocity profile of the jet is predicted analytically, and is successfully compared with the experimental measurements. Moreover, this straight jet eventually destabilizes into meanders. A quantitative comparison between the theory and our experimental observations yields a very good agreement in terms of critical wavelengths. The characterization and understanding of the 2D flows generated by confined Marangoni spreading is a first step to understand the role of inertial effects in the Marangoni flows with and without confinement.

Controlling Foam Stability with the Ratio of Myristic Acid to Choline Hydroxide.

The interfacial and foam properties of a model system based on the mixture between myristic acid and choline hydroxide have been investigated as a function of the molar ratio ( R) between these two components and temperature. The aim of this study was to obtain insight on the links between the self-assemblies in bulk and in the foam liquid channels, the surfactant packing at the interface, and the resulting foam properties and stability. A multiscale approach was used combining small angle neutron scattering, specular neutron reflectivity, surface tension measurements, and photography. We highlighted three regimes of foam stability in this system by modifying R: high foam stability for R < 1, intermediate at R ∼ 1, and low for R > 1. The different regimes come from the pH variations in bulk linked to R. The pH plays a crucial role at the molecular scale by setting the ionization state of the myristic acid molecules adsorbed at the gas-liquid interface, which in turn controls both the properties of the monolayer and the stability of the films separating the bubbles. The main requirement to obtain stable foams is to set the pH close to the p Ka in order to have a mixture of protonated and ionized molecules giving rise to intermolecular hydrogen bonds. As a result, a dense monolayer is formed at the interface with a low surface tension. R also modifies the structure of self-assembly in bulk and therefore within the foam, but such a morphological change has only a minor effect on the foam stability. This study confirms that foam stability in surfactant systems having a carboxylic acid as polar headgroup is mainly linked to the ionization state of the molecules at the interface.

Design of responsive foams with an adjustable temperature threshold of destabilization.

Thermoresponsive foams that refer to foams for which the stability can be switched between the stable and unstable state have recently attracted growing interest due to their possible industrial applications. Our approach to design such foams is based on the use of fatty acids, with various counterions and molar ratios. It is the first example of foams with a temperature threshold of destabilization which can be continuously set between 20 °C and 75 °C.

Morphological Transition in Fatty Acid Self-Assemblies: A Process Driven by the Interplay between the Chain-Melting and Surface-Melting Process of the Hydrogen Bonds.

In surfactant systems, the major role of the nature of the counterion in the surfactant behavior is well-known. However, the effect of the molar ratio between the surfactant and its counterion is less explored in the literature. We investigated the effect of the molar ratio (R) between 12-hydroxystearic acid (12-HSA) and various alkanolamines as a function of the temperature in aqueous solution from the molecular scale to the mesoscale. By coupling microscopy techniques and small-angle neutron scattering, we showed that 12-HSA self-assembled into multilamellar tubes and transitioned into micelles at a precise temperature. This temperature transition depended on both the molar ratio and the alkyl chain length of the counterion and could be precisely tuned from 20 to 75 °C. This thermal behavior was investigated by differential scanning calorimetry and wide-angle X-ray scattering. We highlighted that the transition at the supramolecular scale between tubes and micelles came from two different mechanisms at the molecular scale as a function of the molar ratio. At low R, with an excess of counterion, the transition came from the chain-melting phenomenon. At high R, with an excess of 12-HSA, the transition came from both the chain-melting process and the surface-melting process of the hydrogen bonds. At the mesoscale, this transition of supramolecular assemblies from tubes to micelles delimited a regime of high bulk viscosity, with a regime of low viscosity.

Blast wave attenuation in liquid foams: role of gas and evidence of an optimal bubble size.

Liquid foams are excellent systems to mitigate pressure waves such as acoustic or blast waves. The understanding of the underlying dissipation mechanisms however still remains an active matter of debate. In this paper, we investigate the attenuation of a weak blast wave by a liquid foam. The wave is produced with a shock tube and impacts a foam, with a cylindrical geometry. We measure the wave attenuation and velocity in the foam as a function of bubble size, liquid fraction, and the nature of the gas. We show that the attenuation depends on the nature of the gas and we experimentally evidence a maximum of dissipation for a given bubble size. All features are qualitatively captured by a model based on thermal dissipation in the gas.

Thermodynamics of binary gas adsorption in nanopores.

MCM-41 nanoporous silicas show a very high selectivity for monoalcohols over aprotic molecules during adsorption of a binary mixture in the gas phase. We present here an original use of gravimetric vapour sorption isotherms to characterize the role played by the alcohol hydrogen-bonding network in the adsorption process. Beyond simple selectivity, vapour sorption isotherms measured for various compositions help to completely unravel at the molecular level the step by step adsorption mechanism of the binary system in the nanoporous solid, from the first monolayers to the complete liquid condensation.

Responsive aqueous foams.

Remarkable properties have emerged recently for aqueous foams, including ultrastability and responsiveness. Responsive aqueous foams refer to foams for which the stability can be switched between stable and unstable states with a change in environment or with external stimuli. Responsive foams have been obtained from various foam stabilizers, such as surfactants, proteins, polymers, and particles, and with various stimuli. Different strategies have been developed to design this type of soft material. We briefly review the two main approaches used to obtain responsive foams. The first approach is based on the responsiveness of the interfacial layer surrounding the gas bubbles, which leads to responsive foams. The second approach is based on modifications that occur in the aqueous phase inside the foam liquid channels to tune the foam stability. We will highlight the most sophisticated approaches, which use light, temperature, and magnetic fields and lead to switchable foam stability.

Smart Nonaqueous Foams from Lipid-Based Oleogel.

Oil foams are composed of gas bubbles dispersed in an oil phase. These systems are scarcely studied despite their great potential in diverse fields such as the food and cosmetic industries. Contrary to aqueous foams, the production of oil foams is difficult to achieve due to the inefficiency of surfactant adsorption at oil-air interfaces. Herein, we report a simple way to produce oil foams from oleogels, whose liquid phase is a mixture of sunflower oil and fatty alcohols. The temperature at which the oleogel formed was found to depend on both fatty alcohol chain length and concentration. The air bubbles in the oleogel foam were stabilized by fatty alcohol crystals. Below the melting temperature of the crystals, oleogel foams were stable for months. Upon heating, these ultrastable foams collapsed within a few minutes due to the melting of the crystal particles. The transition between crystal formation and melting was reversible, leading to thermoresponsive nonaqueous foams. The reversible switching between ultrastable and unstable foam depended solely on the temperature of the system. We demonstrate that these oleogel foams can be made to be photoresponsive by using internal heat sources such as carbon black particles, which can absorb UV light and dissipate the absorbed energy as heat. This simple approach for the formulation of responsive oil foams could be easily extended to other oleogel systems and could find a broad range of applications due to the availability of the components in large quantities and at low cost.

Development of casein microgels from cross-linking of casein micelles by genipin.

Casein micelles are porous colloidal particles, constituted of casein molecules, water, and minerals. The vulnerability of the supramolecular structure of casein micelles face to changes in the environmental conditions restrains their applications in other domains besides food. Thus, redesigning casein micelles is a challenge to create new functionalities for these biosourced particles. The objective of this work was to create stable casein microgels from casein micelles using a natural cross-linker, named genipin. Suspensions of purified casein micelles (25 g L(-1)) were mixed with genipin solutions to have final concentrations of 5, 10, and 20 mM genipin. Covalently linked casein microgels were formed via cross-linking of lysyl and arginyl residues of casein molecules. The reacted products exhibited blue color. The cross-linking reaction induced gradual changes on the colloidal properties of the particles. The casein microgels were smaller and more negatively charged and presented smoother surfaces than casein micelles. These results were explained based on the cross-linking of free NH2 present in an external layer of κ-casein. Light scattering and rheological measurements showed that the reaction between genipin and casein molecules was intramicellar, as one single population of particles was observed and the values of viscosity (and, consequently, the volume fraction of the particles) were reduced. Contrary to the casein micelles, the casein microgels were resistant to the presence of dissociating agents, e.g., citrate (calcium chelating) and urea, but swelled as a consequence of internal electrostatic repulsion and the disruption of hydrophobic interactions between protein chains. The casein microgels did not dissociate at the air-solution interface and formed solid-like interfaces rather than a viscoelastic gel. The potential use of casein microgels as adaptable nanocarriers is proposed in the article.

Yielding and flow of solutions of thermoresponsive surfactant tubes: tuning macroscopic rheology by supramolecular assemblies.

In this article, we show that stimuli-induced microscopic transformations of self-assembled surfactant structures can be used to tune the macroscopic bulk and interfacial rheological properties. Previously, we had described the formation of micron-sized 12-hydroxystearic acid tubes having a temperature-tunable diameter in the bulk, and also adsorbing at the air-water interface. We report now a detailed study of the bulk and interfacial rheological properties of this solution of thermoresponsive tubes as a function of temperature. In the bulk, the structural modifications of tubes with temperature lead to sharp and non-monotonous changes of rheological behavior. As well, at the air-water interface, the interfacial layer is shifted several times from rigid-like to fluid-like as the temperature is increased, due to morphological changes of the adsorbed interfacial layer. The temperature-induced variations in the fatty acid supramolecular organization and the richness in structural transitions at this microscopic level lead to unique rheological responses in comparison with conventional surfactant systems. Also, this study provides new insights into the required packing conditions for the jamming of anisotropic soft objects and highlights the fact that this system becomes glassy under heating. Due to these unique macroscopic properties both in the bulk and at the interface, this simple system with stimuli-responsive viscoelasticity is of interest for their potential applications in pharmacology or cosmetic formulations.

12-hydroxystearic acid-mediated in-situ surfactant generation: A novel approach for organohydrogel emulsions.

HYPOTHESIS: Organohydrogel emulsions display unique rheological properties and contain hydrophilic and lipophilic domains highly desirable for the loading of active compounds. They find utility in various applications from food to pharmaceuticals and cosmetic products. The current systems have limited applications due to complex expensive formulation and/or processing difficulties in scale-up. To solve these issues, a simple emulsification process coupled with unique compounds are required. EXPERIMENTS: Here, we report an organohydrogel emulsion based only on a low concentration of 12-hydroxystearic acid acting as a gelling agent for both oil and water phases but also as a surfactant. The emulsification process is based on in-situ surfactant transfer. We characterize the emulsification process occurring at the nanoscale by using tensiometry experiments. The emulsion structure was determined by coupling Small Angle X-ray and neutron scattering, and confocal Raman microscopy. FINDINGS: We demonstrate that the stability and unique rheological properties of these emulsions come from the presence of self-assembled crystalline structures of 12-hydroxystearic acid in both liquid phases. The emulsion properties can be tuned by varying the emulsion composition over a wide range. These gelled emulsions are prepared using a low energy method offering easy scale-up at an industrial level.

Strong improvement of interfacial properties can result from slight structural modifications of proteins: the case of native and dry-heated lysozyme.

Identification of the key physicochemical parameters of proteins that determine their interfacial properties is still incomplete and represents a real stake challenge, especially for food proteins. Many studies have thus consisted in comparing the interfacial behavior of different proteins, but it is difficult to draw clear conclusions when the molecules are completely different on several levels. Here the adsorption process of a model protein, the hen egg-white lysozyme, and the same protein that underwent a thermal treatment in the dry state, was characterized. The consequences of this treatment have been previously studied: net charge and hydrophobicity increase and lesser protein stability, but no secondary and tertiary structure modification (Desfougères, Y.; Jardin, J.; Lechevalier, V.; Pezennec, S.; Nau, F. Biomacromolecules 2011, 12, 156-166). The present study shows that these slight modifications dramatically increase the interfacial properties of the protein, since the adsorption to the air-water interface is much faster and more efficient (higher surface pressure). Moreover, a thick and strongly viscoelastic multilayer film is created, while native lysozyme adsorbs in a fragile monolayer film. Another striking result is that completely different behaviors were observed between two molecular species, i.e., native and native-like lysozyme, even though these species could not be distinguished by usual spectroscopic methods. This suggests that the air-water interface could be considered as a useful tool to reveal very subtle differences between protein molecules.

Two-mode dynamics in dispersed systems: the case of particle-stabilized foams studied by diffusing wave spectroscopy.

The stabilization of aqueous foams solely by solid particles is an active field of research. Thanks to controlled particle chemistry and production devices, we are able to generate large volumes of such foams. We previously investigated some of their unique properties, especially the strongly reduced coarsening. Here we report another type of study on these foams: performing diffusing wave spectroscopy (DWS), we investigate for the first time the internal dynamics on the scales of both the particles and the bubbles. When compared to surfactant foams, unusual features are observed; in particular, two well-separated modes are found in the dynamics, both evolving with foam aging. We propose an interpretation of these specificities, taking into account both the scattering by free particles in the foam fluid (fast mode), and by the foam structure (slow mode). To validate our interpretation, we show that independent measurements of the interstitial fluid scattering length, obtained indirectly on the foam and directly on the drained liquid, are in good agreement. We have also identified the experimental conditions required to observe such two-process dynamics. Counter-intuitively, the fraction of free particles within the foam interstitial fluid has to be very low to get an optimal signature of these particles on the DWS correlation curves. This study also sheds light on the partitioning of the particles inside the foams and at the interfaces, as the foam ages. Lastly, the results shown here (obtained by analyzing the fluctuations of the transmitted light) implement the previous ones (obtained by analyzing the mean transmitted intensity), and prove that the foam structure is actually not fully frozen.