No abstract

We have investigated a new class of food-grade particles, whey protein microgels, as stabilisers of triglyceride-water emulsions. The sub-micron particles stabilized oil-in-water emulsions at all pH with and without salt. All emulsions creamed but exhibited exceptional resistance to coalescence. Clear correlations exist between the properties of the microgels in aqueous dispersion and the resulting emulsion characteristics. For conditions in which the particles were uncharged, fluid emulsions with relatively large drops were stabilised, whereas emulsions stabilized by charged particles contained smaller flocculated drops. A combination of optical microscopy of the drops and spectrophotometry of the resolved aqueous phase allowed us to estimate the interfacial adsorption densities of the particles using the phenomenon of limited coalescence. We deduce two classes of particle arrangement. Complete adsorption of the particles was obtained when they were neutral or when their charges were screened by salt resulting in at least one particle monolayer at the interface. By contrast, only around 50% of the particles adsorbed when they were charged with emulsion drops being covered by less than half a monolayer. These findings were supported by direct visualization of drop interfaces using cryo-scanning electron microscopy. Uncharged particles were highly aggregated and formed a continuous 2-D network at the interface. Otherwise particles organized as individual aggregates separated by particle-free regions. In this case, we suggest that some particles spread at the interface leading to the formation of a continuous protein membrane. Charged particles displayed the ability to bridge opposing interfaces of neighbouring drops to form dense particle disks protecting drops against coalescence; this is the main reason for the flocculation and stability of emulsions containing sparsely covered drops.

We study oil-in-water emulsions stabilised by pH-sensitive colloidal silica or latex particles. Depending on the composition of the continuous phase, the same type of particles and the same emulsification process lead to emulsions characterised either by large drops densely covered by the particles, or to small droplets which are weakly covered. The two kinetically stable states can be tuned reversibly by using pH or salinity as compositional stimuli. We examine the emulsions' behaviour in these two limiting cases and we discuss the possible mechanisms allowing stabilisation, especially in the case of low surface coverage.

We used soft microgels made of poly(N-isopropylacrylamide) (pNIPAM) of variable cross-linking degrees and the same colloidal size to stabilize oil-in-water Pickering emulsions. The extent of droplet flocculation increased and the resistance of the emulsions to mechanical stresses decreased as the cross-linking density was augmented. Large flat films were separating the droplets, and we could measure the adhesion angle at the junction with the free interfaces through several microscopy methods. The size of the flat films and the values of the angles were reflecting strong adhesive interactions between the interfaces as a result of microgel bridging. In parallel, cryo-SEM imaging of the thin films allowed a precise determination of their structure. The evolution of the adhesion angle and of the film structure as a function of microgels cross-linking density provided interesting insights into the impact of particle softness on film adhesiveness and emulsion stability. We exploited our main findings to propose a novel route for controlling the emulsions end-use properties (flocculation and stability). Owing to particle softness and thermal sensitivity, the interfacial coverage was a path function (it depended on the sample "history"). As a consequence, by adapting the emulsification conditions, the interfacial monolayer could be trapped in a very dense and rigid configuration, providing improved resistance to bridging flocculation and to flow-induced coalescence.