Emulsions Stabilized by Gum Arabic: How Diversity and Interfacial Networking Lead to Metastability.

Gum arabic is a natural hydrocolloid composed of a diversity of amphiphilic species consisting of protein chains covalently linked to multiscale porous polysaccharides. Gum arabic is notably used as a food additive (E414) to provide metastability to oil-in-water emulsions, even after extensive dilution. Here, we investigate the mechanism underlying the emulsion stabilizing properties of gum arabic, using a combination of scattering and chromatographic analyses and the design of a harvesting method to collect adsorbed species. Increasing the interfacial packing of amphiphilic species leads to their irreversible interfacial aggregation, which is driven by hydrophobic interactions between protein chains. This aggregation is promoted by the size diversity of amphiphilic species, with smaller species first aggregating at intermediate interfacial packings, followed by larger species at higher packings. The resulting adsorbed layer can be considered as a shell composed of a two-dimensional protein network, irreversibly cross-linked through hydrophobic interactions, which is covalently linked to hyperbranched polysaccharide chains displaying severe conformational changes compared to their bulk structure. This shell is strongly anchored at the oil-water interface by the protein network and provides steric repulsions through the hydrated polysaccharides. Consequently, if such a shell is adequately formed during emulsification, emulsions stabilized by gum arabic may resist extensive mechanical stresses and display a long-term metastability even after drastic environmental changes. This paves the way toward more rational uses of gum arabic as an emulsion stabilizer in formulations and processes.

Emulsions Stabilized by Gum Arabic: Composition and Packing within Interfacial Films.

Gum arabic is a heterogeneous natural hydrocolloid commonly used in the agro-food industry to provide metastability to oil-in-water emulsions. Since aqueous solutions of gum arabic contain a complex mixture of protein/polysaccharide conjugates, the composition of interfacial films is expected to differ from the bulk composition. Here, we investigate the composition of interfacial films in oil/water emulsions stabilized by gum arabic at various concentrations, pH and salinity. Using both size exclusion and hydrophobic interaction chromatography separations, we show that the interface is enriched in protein-rich species displaying a broad range of sizes. These species are irreversibly adsorbed as monolayers at the oil/water interface. We observe that the surface coverage density, or packing, of the adsorbed species at oil/water interfaces drastically increases with both the increasing gum concentration and decreasing ionic repulsions, through increasing the ionic strength or decreasing the pH. Strikingly, these packing changes correspond to only minor composition changes in the adsorbed layer. We thus conclude that the key parameter modified in different formulations is the conformation of the adsorbed species rather than their composition distribution. These findings can be readily used to adjust the amount of gum arabic necessary to produce metastable emulsions.

Effect of mass transfer on the film drainage between colliding drops.

The influence of mass transfer on the drainage behaviour of the thin liquid film between two drops immersed in another liquid colliding at constant approach velocity has been studied experimentally. The liquid-liquid system used is glycerol in silicone oil. The transferred solute is acetone and the volume concentration difference across the interface ranges from 1 to 5%. The film thickness evolution has been measured using a laser interferometry technique. The direction of mass transfer (from the drops towards the film phase and inversely) has been investigated and the results compared to the case with no mass transfer. When the solute transfers from the drops towards the continuous phase, the drainage rate is significantly higher than in the case with no mass transfer. This result is interpreted as a consequence of the mass transfer induced surface mobility in the film region (the so-called Marangoni effect) due to localized surface tension differences. This effect has been demonstrated by the visualization of the flow patterns in the drops and in the film phase (using a particle tracer technique). In this case, the slope of the film height as a function of time seems to be independent of the approach velocity condition imposed on the drop and appears to be controlled by the interfacial tension gradient. In the opposite case, when the solute transfers from the continuous phase towards the drops, the film drainage rate is lowered with respect to the case of no mass transfer, goes to zero or even changes its sign depending on the mass transfer intensity. The results also show that in the range of solute concentration studied, the effect of mass transfer on the film drainage process takes place at large distances compared to the scales at which lubrication theory is valid.

Film Drainage between Colliding Drops at Constant Approach Velocity: Experiments and Modeling.

Experiments and modeling of the drainage of the thin liquid film between two deformable spherical drops approaching each other at constant velocity in another liquid are being presented. Two numerical models based on the lubrication theory have been developed considering the cases of immobile or mobile drop interfaces. The absolute film thickness and the thinning rate have been measured using laser interferometry for a wide range of capillary numbers. In all studied cases, the model with immobile interfaces was found to give the best predictions of the experimental time evolution of the film thickness and radial expansion. These results made it possible to derive a typical time scale of the drainage process. Copyright 2000 Academic Press.

Predictive Model for the Calculation of Interfacial Tension in Nonideal Electrolytic Systems

A new model is proposed for the calculation of the interfacial tension between an organic solvent and concentrated aqueous solutions of electrolytes. The interfacial tension is derived from the isothermal Gibbs equation. The increase or decrease of interfacial tension with concentrations are modeled using a Langmuir-type adsorption equation and the strong non-ideality of the mixtures is taken into account through the Mikulin equation. The model parameters are first determined with binary water-electrolyte solutions and are kept constant in the case of mixtures. The model has been applied to chloride solutions-chloride salts of various metals and hydrochloric acid-and compared with experimental data obtained by using the pendant drop technique and a Wilhelmy tensiometer. In all cases investigated, good agreement is observed, even in the case of stiff variations of interfacial tension with the electrolyte concentration and also at high concentrations of electrolytes.