Oil-in-water emulsions were formed and stabilized at low amphiphile concentrations by combining hydrophilic nanoparticles (NPs) (i.e., bare colloidal silica) with a weakly interacting zwitterionic surfactant, caprylamidopropyl betaine, to generate a high hydrophilic-lipophilic balance. The weak interaction of the NPs with surfactant was quantified with contact angle measurements. Emulsions were characterized by static light scattering to determine the droplet size distributions, optical photography to quantify phase separation due to creaming, and both optical and electron microscopy to determine emulsion microstructure. The NPs and surfactant acted synergistically to produce finer emulsions with a greater stability to coalescence relative to the behavior with either NPs or surfactant alone. As a consequence of the weak adsorption of the highly hydrophilic surfactant on the anionic NPs along with the high critical micelle concentration, an unusually large surfactant concentration was available to adsorb at the oil-water interface and lower the interfacial tension. The synergy for emulsion formation and stabilization for the two amphiphiles was even greater in the case of a high-salinity synthetic seawater aqueous phase. Here, higher NP adsorption at the oil-water interface was caused by electrostatic screening of interactions between (1) NPs and the anionic oil-water interface and (2) between the NPs. This greater adsorption as well as partial flocculation of the NPs provided a more efficient barrier to droplet coalescence.

Environmentally benign clay particles are of great interest for the stabilization of Pickering emulsions. Dodecane-in-synthetic seawater (SSW) emulsions formed with montmorillonite (MMT) clay microparticles modified with bis(2-hydroxyethyl)oleylamine were stable against coalescence, even at clay concentrations down to 0.1% w/v. Remarkably, as little as 0.001% w/v surfactant lowered the hydrophilicity of the clay to a sufficient level for stabilization of oil-in-SSW emulsions. The favorable effect of SSW on droplet size reduction and emulsion stability enhancement is hypothesized to be due to reduced electrostatic repulsion between adsorbed clay particles and a consequent increase in the continuous phase (an aqueous clay suspension) viscosity. Water/oil (W/O) emulsions were inverted to O/W either by decreasing the mass ratio of surfactant-to-clay (transitional inversion) or by increasing the water volume fraction (catastrophic inversion). For both types of emulsions, coalescence was minimal and the sedimentation or creaming was highly correlated with the droplet size. For catastrophic inversions, the droplet size of the emulsions was smaller in the case of the preferred curvature. Suspensions of concentrated clay in oil dispersions in the presence of surfactant were stable against settling. The mass transfer pathways during emulsification of oil containing the clay particles were analyzed on the droplet size/stability phase diagrams to provide insight for the design of dispersant systems for remediating surface and subsurface oceanic oil spills.

The mechanism by which polymers, when grafted to inorganic nanoparticles, lower the interfacial tension at the oil-water interface is not well understood, despite the great interest in particle stabilized emulsions and foams. A simple and highly versatile free radical "grafting through" technique was used to bond high organic fractions (by weight) of poly(oligo(ethylene oxide) monomethyl ether methacrylate) onto iron oxide clusters, without the need for catalysts. In the resulting ∼1 μm hybrid particles, the inorganic cores and grafting architecture contribute to the high local concentration of grafted polymer chains to the dodecane/water interface to produce low interfacial tensions of only 0.003 w/v % (polymer and particle core). This "critical particle concentration" (CPC) for these hybrid inorganic/polymer amphiphilic particles to lower the interfacial tension by 36 mN/m was over 30-fold lower than the critical micelle concentration of the free polymer (without inorganic cores) to produce nearly the same interfacial tension. The low CPC is favored by the high adsorption energy (∼10(6) kBT) for the large ∼1 μm hybrid particles, the high local polymer concentration on the particles surfaces, and the ability of the deformable hybrid nanocluster cores as well as the polymer chains to conform to the interface. The nanocluster cores also increased the entanglement of the polymer chains in bulk DI water or synthetic seawater, producing a viscosity up to 35,000 cP at 0.01 s(-1), in contrast with only 600 cP for the free polymer. As a consequence of these interfacial and rheological properties, the hybrid particles stabilized oil-in-water emulsions at concentrations as low as 0.01 w/v %, with average drop sizes down to 30 μm. In contrast, the bulk viscosity was low for the free polymer, and it did not stabilize the emulsions. The ability to influence the interfacial activity and rheology of polymers upon grafting them to inorganic particles, including clusters, may be expected to be broadly applicable to stabilization of emulsions and foams.

During deep-sea oil leaks, dispersants may be used to break up the oil into droplets smaller than about 70 μm, which may then be bioremediated by bacteria before they reach the ocean surface. To investigate the mechanism of droplet formation as a function of dispersant type, concentration, and jet velocity, a flowing oleophilic stream containing amphiphiles was mixed with flowing dodecane and then atomized through a 0.25 mm circular nozzle. The minimum droplet diameters were 2.2, 4.5, and 24 μm for only 5 w:v % amphiphile in the oil phase for Corexit 9500A, Tergitol 15-S-7 (C 12 H 25 CH(OCH 2 CH 2 ) 7 OH), and a silica nanoparticle/Span 20 mixture, respectively. For Tergitol 15-S-7, the droplet size exhibited the expected scaling with Weber number (We) at low viscosity numbers (Vi < 50), where inertial forces overcome interfacial forces, and Reynolds number (Re) at high Vi numbers (Vi > 50), where inertial forces overcome viscous forces. However, in the case of the silica nanoparticle/ Span 20 mixture, the magnitude of the exponent of We scaling was found to be smaller than −3/5. A better understanding of how low concentrations of dispersants (with relatively high oil−water interfacial tensions) may be used to provide a sufficient We with high inertial forces (high Re) in jets to form small oil droplets, which is of interest for advancing environmental protection in the undesired event of a deep-sea oil leak.