Dynamics of Droplet Pinch-Off at Emulsified Oil-Water Interfaces: Interplay between Interfacial Viscoelasticity and Capillary Forces.

The presence of submicrometer structures at liquid-fluid interfaces modifies the properties of many science and technological systems by lowering the interfacial tension, creating tangential Marangoni stresses, and/or inducing surface viscoelasticity. Here we experimentally study the break-up of a liquid filament of a silica nanoparticle dispersion in a background oil phase that contains surfactant assemblies. Although self-similar power-law pinch-off is well documented for threads of Newtonian fluids, we report that when a viscoelastic layer is formed in situ at the interface, the pinch-off dynamics follows an exponential decay. Recently, such exponential neck thinning was found theoretically when surface viscous effects were taken into account. We introduce a simple approach to calculate the effective relaxation time of viscoelastic interfaces and estimate the thickness of the interfacial layer and the viscoelastic properties of liquid-fluid interfaces, where the direct measurement of interfacial rheology is not possible.

Spongy all-in-liquid materials by in-situ formation of emulsions at oil-water interfaces.

Printing a structured network of functionalized droplets in a liquid medium enables engineering collectives of living cells for functional purposes and promises enormous applications in processes ranging from energy storage to tissue engineering. Current approaches are limited to drop-by-drop printing or face limitations in reproducing the sophisticated internal features of a structured material and its interactions with the surrounding media. Here, we report a simple approach for creating stable liquid filaments of silica nanoparticle dispersions and use them as inks to print all-in-liquid materials that consist of a network of droplets. Silica nanoparticles stabilize liquid filaments at Weber numbers two orders of magnitude smaller than previously reported in liquid-liquid systems by rapidly producing a concentrated emulsion zone at the oil-water interface. We experimentally demonstrate the printed aqueous phase is emulsified in-situ; consequently, a 3D structure is achieved with flexible walls consisting of layered emulsions. The tube-like printed features have a spongy texture resembling miniaturized versions of "tube sponges" found in the oceans. A scaling analysis based on the interplay between hydrodynamics and emulsification kinetics reveals that filaments are formed when emulsions are generated and remain at the interface during the printing period. Stabilized filaments are utilized for printing liquid-based fluidic channels.

Wetting Dynamics of Nanoparticle Dispersions: From Fully Spreading to Non-sticking and the Deposition of Nanoparticle-Laden Surface Droplets.

Controlled transport of liquid droplets on solid surfaces is critical in many practical applications, such as self-cleaning surfaces, coating, drug delivery, and agriculture. Non-adhesive liquid drops levitate on solid surfaces; therefore, they are highly mobile and directed toward desired locations by external stimuli. Although research on liquid-repellent surfaces has proliferated, the existing methods are still limited to creating surface roughness or coating the liquid droplets. Here, we create non-contact aqueous drops on hydrophilic surfaces in an oleic environment and use them to deposit submicrometer droplets encapsulating nanoparticles on solid surfaces. A glass surface is buried under an oil phase that contains a high concentration of Span 80 surfactants, and a drop of silica nanoparticle dispersion is released on the solid surface. We study the effect of surfactant concentration in oil and nanoparticle concentration in water on wetting dynamics and report a plethora of droplet spreading regimes from fully wetting to non-wetting. We find a threshold Span 80 concentration above which surfactant assemblies are formed on the solid and prevent the direct contact of the drop with the surface. At the same time, water-in-oil emulsions are generated at the drop-oil interface. The drop moves and leaves a trace of emulsions with encapsulated nanoparticles on the solid. We demonstrate the possibility of local surface coating with hydrophilic nanoparticles in a hydrophobic medium. The developed methodology in this study is a generic approach facilitating the droplet patterning in numerous applications, from pharmaceutical polymetric carriers to the formulation of cosmetics, insecticides, and biomedical diagnoses.

Spontaneous Formation of Double Emulsions at Particle-Laden Interfaces.

HYPOTHESIS: Traditionally, double emulsions are produced in the presence of both oil-soluble and water-soluble surfactants in sequential droplet formation settings or unique fluidic designs. Micelles, assemblies of surfactants in liquid mediums, can generate single emulsion droplets without requiring input energy. We hypothesize that the synergy between nanoparticles in one phase, and micelles in the other phase can spontaneously generate double emulsions. Nanoparticles can become surface-activated by adsorbing surfactants and form the second type of emulsions from the initially emulsified phase by micelles. EXPERIMENTS: We design a thermodynamically-driven emulsification platform where double emulsions are spontaneously formed as soon an aqueous nanoparticle dispersion is placed in contact with an oleic micellar solution. Confocal and cryogenic-scanning electron microscopies are utilized to characterize structure and intensity of emulsions at various concentrations of silica nanoparticle and Span micelles. The rate of particle surface activation and emulsification and the amount of water intake are quantified using dynamic light scattering, dynamic interfacial tension, and density measurements. FINDINGS: Nanoscale water droplets nucleate in the oil in form of swollen micelles. Over time, nanoparticles form a water-shell encapsulating the swollen-micelle rich oil phase. The gradual surfaceactivation of nanoparticles is key in self-double emulsification and controlling the emulsion intensity. We build on this new discovery and design a novel system for double emulsification. Incorporating nanoparticles into spontaneous emulsification systems opens novel routes for designing emulsion-based materials.

Polymeric-nanofluids stabilized emulsions: Interfacial versus bulk rheology.

HYPOTHESIS: The properties of oil-in-water emulsions are influenced by the rheology of the aqueous phase (continuous phase) and the rheology of the oil-water interfaces. The bulk and interfacial rheological parameters can be tuned by incorporating nanoparticles (NPs) featuring different surface chemistries and polymers with different chemical or physical structures. Therefore, NPs and polymers can be used to formulate emulsions with different properties. EXPERIMENTS: The viscoelasticity at the oil-(aqueous phase) interface and the bulk viscoelasticity of aqueous phase were investigated in the presence of different fumed silica NPs (i.e., hydrophilic, hydrophobic, and slightly hydrophobic) and polymers with two different molecular weights. Bulk and interfacial viscoelastic properties were investigated, employing oscillatory rheological techniques. Furthermore, morphology and stability of the oil-in-(aqueous nanofluid) emulsions were explored utilizing bulk emulsification and single drop coalescence experiments. FINDINGS: Introducing polymers into the aqueous nanofluids had opposite effects on bulk and interfacial viscoelasticity. Despite the significant increase in bulk viscoelasticity upon addition of polymers into the aqueous nanofluids, the interfacial viscoelasticity and emulsion stability considerably decreased. The slightly hydrophobic NP nanofluids without polymers showed no bulk viscoelasticity, but displayed the highest interfacial viscoelasticity and emulsion stability. This provided us a unique opportunity to unravel the importance of bulk and interfacial viscoelasticity on oil-in-water emulsification and proved the dominant role of interfacial viscoelasticity over bulk viscoelasticity on emulsion stability.