Interfacial properties of native β-lactoglobulin monomers and their heat-induced fibers, of two different lengths, were investigated at pH 2, through surface tension measurements at water-air and water-oil interfaces and interfacial shear rheology at the water-oil interface. The applied heat treatment generates a mixed system of fibers with unconverted monomers and hydrolyzed peptides. The surface tension of this system at the water-air interface decreased more rapidly than the surface tension of native monomers, especially at short times (10(-3) to 10(2) s). This behavior was not observed when the unconverted monomers and peptides were removed by dialysis. At the water-oil interface, the adsorption kinetics was much faster than at the water-air interface, with a plateau interfacial pressure value reached after 1 h of adsorption. For all the systems, interfacial shear rheology showed the formation of a highly elastic interface, with solid-like behavior at 1-10(3) s time scales. The highest modulus was observed for the long fibers and the lowest for the native monomers. Creep-compliance curves in the linear regime could be reduced to a single master curve, showing similar spectra of relaxation times for all investigated systems. Upon large deformations, the interfaces formed with long fibers showed the most rigid and fragile behavior. This rigidity was even more pronounced in the presence of unconverted monomers.

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Interfacially stabilized nonaqueous lipid-based foams, which we name here oleofoams, are rarely encountered as opposed to the large number of aqueous foams stabilized by molecular or particulate emulsifiers. There is no case well described in the literature with a convincing characterization of the interfacial contribution to oleofoam stability. Methods for filling this gap are described here, which reach out to a large part of the lipid phase diagram. We bring here complete evidence that lipidic crystals made of a high fraction of fully soluble monoglyceride (MG) in oil do not only adsorb at the oil-air interface but also can easily form a jammed, closely packed layer of crystals around the bubbles of a foam produced by whipping (Pickering effect). Very fine bubbles, soft textures, or firmer ones such as for shaving foams could be obtained, with a high air fraction (up to 75%), which is unprecedented. A thin, jammed layer of crystals on bubbles can cause bubbles to retain nonspherical shapes in the absence of bulk effects for times much longer than the characteristic capillary relaxation time for bare bubbles, which is actual evidence for Pickering-type interfacial stabilization. By comparing to foams obtained by depressurization, we show that whipping is necessary for bubble wrapping with a layer of crystals. The origin of high stability against Ostwald ripening at long times is also discussed. Furthermore, we show that these Pickering whipped foams have rheological properties dominated by interfacial or film contributions, which is of high interest for food and cosmetics applications because of their high moduli. This system can be considered to be a model of the crystallization behavior of MG in oil, which is similar to that in many fats. Our methods are very general in the context of lipid-based foaming, in particular, from food materials, and were used in patent applications.

A strategy to halt dissolution of particle-coated air bubbles in water based on interfacial rheology design is presented. Whereas previously a dense monolayer was believed to be required for such an "armored bubble" to resist dissolution, in fact engineering a 2D yield stress interface suffices to achieve such performance at submonolayer particle coverages. We use a suite of interfacial rheology techniques to characterize spherical and ellipsoidal particles at an air-water interface as a function of surface coverage. Bubbles with varying particle coverages are made and their resistance to dissolution evaluated using a microfluidic technique. Whereas a bare bubble only has a single pressure at which a given radius is stable, we find a range of pressures over which bubble dissolution is arrested for armored bubbles. The link between interfacial rheology and macroscopic dissolution of ∼ 100 µm bubbles coated with ∼ 1 µm particles is presented and discussed. The generic design rationale is confirmed by using nonspherical particles, which develop significant yield stress at even lower surface coverages. Hence, it can be applied to successfully inhibit Ostwald ripening in a multitude of foam and emulsion applications.interfacial rheology | foams | yield stress | Ostwald ripening | emulsions T uning the interparticle interaction potential in bulk suspensions has long been a strategy to engineer the properties of colloidal suspensions. In this work, we apply this paradigm to interfacial materials, specifically particle-stabilized drops and bubbles. These systems with high interfacial area have broad applicability from food formulation and processing (1, 2), encapsulation (3, 4), ultrasound medical technologies (5), to lowweight/high-strength materials (6). One of the key challenges in using solid stabilized emulsions and foams in applications is curtailing Ostwald ripening, which causes the growth/shrinkage of large/small bubbles and increased size heterogeneity (7).Ripening occurs due to differences in the Laplace pressure in bubbles of different radii; large bubbles grow, while small bubbles shrink. This suggests that strategies to impart a resistance to dilation or compression of the interface would retard or entirely stop Ostwald ripening. Previously, fully covered, "jammed," particle coated bubbles were shown to fully resist dissolution of this nature (8)(9)(10)(11)(12). When the ratio of particle size to bubble size is large (a/R > 0.1), specific faceted shapes may moreover reduce the mean curvature to zero, thereby reducing the driving force to zero (10). However, stability is also observed at much smaller a/R ratios, suggesting other factors come into play. Previous work supposed the particles do not interact with each other, but since such interactions have a major role in interfacial rheology, they can potentially contribute to bulk bubble and emulsion stability as well.Here, we design and characterize model viscoplastic interfacial systems consisting of spherical and nonspherical particles at an air-water int...

International audienceBubbles are dynamic objects that grow and rise or shrink and disappear, often on the scale of seconds. This conflicts with their uses in foams where they serve to modify the properties of the material in which they are embedded. Coating the bubble surface with solid particles has been demonstrated to strongly enhance the foam stability, although the mechanisms for such stabilization remain mysterious. In this paper, we reduce the problem of foam stability to the study of the behavior of a single spherical bubble coated with a monolayer of solid particles. The behavior of this armored bubble is monitored while the ambient pressure around it is varied, in order to simulate the dissolution stress resulting from the surrounding foam. We find that above a critical stress, localized dislocations appear on the armor and lead to a global loss of the mechanical stability. Once these dislocations appear, the armor is unable to prevent the dissolution of the gas into the surrounding liquid, which translates into a continued reduction of the bubble volume, even for a fixed overpressure. The observed route to the armor failure therefore begins from localized dislocations that lead to large-scale deformations of the shell until the bubble completely dissolves. The critical value of the ambient pressure that leads to the failure depends on the bubble radius, with a scaling of ΔPcollapse∝R−1, but does not depend on the particle diameter. These results disagree with the generally used elastic models to describe particle-covered interfaces. Instead, the experimental measurements are accounted for by an original theoretical description that equilibrates the energy gained from the gas dissolution with the capillary energy cost of displacing the individual particles. The model recovers the short-wavelength instability, the scaling of the collapse pressure with bubble radius, and the insensitivity to particle diameter. Finally, we use this new microscopic understanding to predict the aging of particle-stabilized foams, by applying classical Ostwald ripening models. We find that the smallest armored bubbles should fail, as the dissolution stress on these bubbles increases more rapidly than the armor strength. Both the experimental and theoretical results can readily be generalized to more complex particle interactions and shell structures

An osmotic imbalance between the two water phases of multiple water-in-oil-in-water (W1/O/W2) emulsions results in either emulsion swelling or shrinking due to water migration across the oil layer. Controlled mass transport is not only of importance for emulsion stability but also allows transient emulsion thickening or the controlled release of encapsulated substances, such as nutriments or simply salt. Our prior work has shown that mass transport follows two sequential stages. In the first stage, the oil-phase structure is changed in a way that allows rapid, osmotically driven water transport in the second, osmotically dominated stage. These structural changes in the oil layer are strongly facilitated by the spontaneous formation of tiny water droplets in the oil phase, induced by the oil-soluble surfactant, i.e., polyglycerol polyricinoleate (PGPR). This study provides a simple method based on microscopy image analysis, allowing a detailed investigation of spontaneous W/O emulsification. It quantitatively describes the volume of droplets generated and the rate of droplet creation. Moreover, it describes the effect of spontaneous W/O emulsification on the swelling kinetics of microfluidic processed W1/O/W2 emulsions. Two different concentration regimes of the oil-soluble surfactant are identified: below a critical concentration the overall water transport rate increases, and above a critical concentration water transport stagnates because of maximized structure formation.

This contribution reports on the mass transport kinetics of osmotically imbalanced water-in-oil-in-water (W1/O/W2) emulsions. Although frequently studied, the control of mass transport in W1/O/W2 emulsions is still challenging. We describe a microfluidics-based method to systematically investigate the impact of various parameters, such as osmotic pressure gradient, oil phase viscosity, and temperature, on the mass transport. Combined with optical microscopy analyses, we are able to identify and decouple the various mechanisms, which control the dynamic droplet size of osmotically imbalanced W1/O/W2 emulsions. So, swelling kinetics curves with a very high accuracy are generated, giving a basis for quantifying the kinetic aspects of transport. Two sequential swelling stages, i.e., a lag stage and an osmotically dominated stage, with different mass transport mechanisms are identified. The determination and interpretation of the different stages are the prerequisite to control and trigger the swelling process. We show evidence that both mass transport mechanisms can be decoupled from each other. Rapid osmotically driven mass transport only takes place in a second stage induced by structural changes of the oil phase in a lag stage, which allow an osmotic exchange between both water phases. Such structural changes are strongly facilitated by spontaneous water-in-oil emulsification. The duration of the lag stage is pressure-independent but significantly influenced by the oil phase viscosity and temperature.

Oil-in-water and water-in-oil capsules, and flat membranes of tuneable thickness and composition were prepared in one single facile step, based on the interfacial complexation between chitosan and anionic phosphatidic fatty acids. The phosphatidic acid molecules were introduced via the oil phase. The thickness of the capsule shell or the membrane grows by a diffusion-controlled mechanism, hence can be tuned using e.g. concentration and formation time parameters. A mechanism is proposed to explain the observed behavior. The capsule size is set by the emulsification conditions applied. Microfluidic methods proved useful for the generation of hollow capsules of uniform size and thickness in one step. The capsules and membranes display remarkable integrity over several years in a pH window 2-14. The thickness can easily reach several micrometres within an hour for the wet capsule shell or membrane, which explains the high interfacial rheological properties measured. Hence various processes can be envisaged after their formation. The simple preparation opens the way to tailored, environmentresponsive composite systems for fabricating biopolymer-based materials for various applications. The capsules could be washed from the surrounding continuous phase and placed into one of arbitrary choice. Furthermore, the surface of the w/o capsules and of the membranes could be decorated by particles that attach to the water/oil interface with a high energy. The choice of the particle functionality is left open.