Thomas G. Mason

New fundamental concepts in emulsion rheology

Abstract The field of emulsion rheology is developing rapidly due to investigations involving monodisperse emulsions having narrow droplet size distributions. The droplet uniformity facilitates meaningful comparisons between experiments, theories, and simulations.

Nanoscale double emulsions stabilized by single-component block copolypeptides

Water-in-oil-in-water emulsions are examples of double emulsions, in which dispersions of small water droplets within larger oil droplets are themselves dispersed in a continuous aqueous phase. Emulsions occur in many forms of processing and are used extensively by the foods, cosmetics and coatings industries. Because of their compartmentalized internal structure, double emulsions can provide advantages over simple oil-in-water emulsions for encapsulation, such as the ability to carry both polar and non-polar cargos, and improved control over release of therapeutic molecules. The preparation of double emulsions typically requires mixtures of surfactants for stability; the formation of double nanoemulsions, where both inner and outer droplets are under 100 nm, has not yet been achieved. Here we show that water-in-oil-in-water double emulsions can be prepared in a simple process and stabilized over many months using single-component, synthetic amphiphilic diblock copolypeptide surfactants. These surfactants even stabilize droplets subjected to extreme flow, leading to direct, mass production of robust double nanoemulsions that are amenable to nanostructured encapsulation applications in foods, cosmetics and drug delivery.

Shape-Controlled Colloidal Interactions in Nematic Liquid Crystals

Hairy Polygon Solution The packing of rods on the surface of a sphere leads to packing defects at the opposite poles. It is, however, possible to flat-pack rods onto a torus. This topological problem is well known as the hairy ball theorem, and arises when you place spherical particles inside a nematic liquid crystal. Lapointe et al. (p. 1083) considered the packing of liquid crystal molecules onto lithographically fabricated polygons and found that the number of dipoles that formed depended upon whether the polygon had an odd or even number of sides. The defect structures were attracted to each other, such that the liquid crystal could pull together the particles in a form of controlled self-assembly. Polygons dispersed in a liquid crystal solvent form either dipolar or quadrupolar interactions, thus driving self-assembly. Robust control over the positions, orientations, and assembly of nonspherical colloids may aid in the creation of new types of structured composite materials that are important from both technological and fundamental standpoints. With the use of lithographically fabricated equilateral polygonal platelets, we demonstrate that colloidal interactions and self-assembly in anisotropic nematic fluids can be effectively tailored via control over the particles’ shapes. The particles disturb the uniform alignment of the surrounding nematic host, resulting in both a distinct equilibrium alignment and highly directional pair interactions. Interparticle forces between polygonal platelets exhibit either dipolar or quadrupolar symmetries, depending on whether their number of sides is odd or even, and drive the assembly of a number of ensuing self-assembled colloidal structures.

DIFFUSING-WAVE-SPECTROSCOPY MEASUREMENTS OF VISCOELASTICITY OF COMPLEX FLUIDS

We present a new use of dynamic light scattering that permits the determination of the viscoelastic behavior of a complex fluid. By describing the motion of a scattering particle in a viscoelastic medium in terms of a generalized Langevin equation with a memory function, we relate the time evolution of its mean-square displacement to the frequency-dependent storage and loss moduli of the medium. The utility of this technique is illustrated through the application of diffusing-wave spectroscopy to probe the viscoelastic behavior of two complex fluids. The properties of a concentrated suspension of colloidal particles interacting as hard spheres are shown to be strongly influenced by the incipient colloidal glass transition, which leads to an extended range of frequencies over which they behave like an elastic solid. Similar elasticity is observed in a compressed emulsion, resulting in this case from the additional interfacial energy of the deformed droplets. In both cases diffusing-wave spectroscopy is used to measure the frequency dependence of the storage and loss moduli, and these results are compared with those from mechanical measurements. Besides providing a purely optical method for measuring mechanical properties, this technique provides new insight into the origin of the viscoelastic behavior.

MODEL FOR THE ELASTICITY OF COMPRESSED EMULSIONS

We present a new model to describe the unusual elastic properties of compressed emulsions. The response of a single droplet under compression is investigated numerically for different Wigner-Seitz cells. The response is softer than harmonic, and depends on the coordination number of the droplet. Using these results, we propose a new effective inter-droplet potential which is used to determine the elastic response of a monodisperse collection of disordered droplets as a function of volume fraction. Our results are in excellent agreement with recent experiments. This suggests that anharmonicity, together with disorder, are responsible for the quasi-linear increase of

Formation of Concentrated Nanoemulsions by Extreme Shear

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Structure of concentrated nanoemulsions

and

Shear-Induced Configurations of Confined Colloidal Suspensions

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Extreme emulsification: formation and structure of nanoemulsions

observed at

Entropic crystal–crystal transitions of Brownian squares

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