Slow, nondiffusive dynamics in concentrated nanoemulsions.

Using multispeckle x-ray photon correlation spectroscopy, we have measured the slow, wave-vector-dependent dynamics of concentrated, disordered nanoemulsions composed of silicone oil droplets in water. The intermediate scattering function possesses a compressed exponential line shape and a relaxation time that varies inversely with wave vector. We interpret this dynamics as strain in response to local stress relaxation. The motion includes a transient component whose characteristic velocity decays exponentially with time following a mechanical perturbation of the nanoemulsions and a second component whose characteristic velocity is essentially independent of time. The steady-state characteristic velocity is surprisingly insensitive to the droplet volume fraction in the concentrated regime, indicating that the strain motion is only weakly dependent on the droplet-droplet interactions.

Effective structure factor of osmotically deformed nanoemulsions.

Extreme osmotic compression of nanoemulsion droplets, achieved by ultracentrifugation, can create solidlike biliquid foams without causing significant droplet coalescence. Using small-angle neutron scattering (SANS), we probe the structure of a uniform silicone oil-in-water nanoemulsion stabilized by sodium dodecyl sulfate over a wide range of volume fractions, phi, up to and beyond the limit associated with maximal random jamming of spheres, phiMRJ = 0.64. Although some features in the structure can be understood at lower phi using simple predictions for hard spheres, the anionic repulsion and deformability of the droplet interfaces creates departures from these predictions at higher phi. For phi near and beyond phiMRJ, the effective structure factor, Seff, as a function of wavenumber, q, exhibits a primary peak that is subunity. We speculate that this striking feature is due to the deformation of the droplets into nonspherical shapes as the system begins to approach the limit of a random array of nanoscopic thin films, Plateau borders, and vertexes characteristic of a polyhedral foam.

Dense cluster formation during aggregation and gelation of attractive slippery nanoemulsion droplets.

Using time-resolved small angle neutron scattering, we have measured the wave-number-dependent structure factor S(q) of monodisperse nanoemulsions that aggregate and gel after we suddenly turn on a strong, short-range, slippery attraction between the droplets. At high q, peaks in S(q) appear as dense clusters of droplets form, and S(q) increases strongly toward low q, as these dense clusters become locked into a rigid gel network, despite the fluidity of the films between the droplets. The long-time high-q structure of nanoemulsion gels formed by slippery diffusion-limited cluster aggregation is universal in shape and remarkably independent of the droplet volume fraction, phi.