We have discovered the existence of extremely polydisperse High Internal-Phase-Ratio Emulsions (HIPE) in which the internal-phase droplets, present at 95% volume fraction, remain spherical and organize themselves in the available space according to Apollonian packing rules. Such Apollonian emulsions are obtained from dispersing oil dropwise in water in the presence of very little surfactant, and allowing them to evolve at rest for a week. The packing structure of the droplets was confirmed through size distribution measurements that evolved spontaneously towards power laws with the known Apollonian exponents, as well as comparison of the structure factors of aged HIPEs measured by Small-Angle X-ray Scattering with that of a numerically simulated Random Apollonian Packing. Thanks to the perfect sphericity of the droplets, Apollonian emulsions were found to display Newtonian ow even at such extremely high volume fraction. We argue that these fascinating space-filling assemblies of spherical droplets are a result of coalescence and fragmentation processes obeying simple geometrical rules of conserving total volume and sphericity, minimizing the elastic energy associated with interactions of neighbouring droplets.
We have discovered the existence of polydisperse High Internal-Phase-Ratio Emulsions (HIPE) in which the internal-phase droplets, present at 95% volume fraction, remain spherical and organize themselves in the available space according to Apollonian packing rules. These polydisperse HIPE are formed during emulsification of surfactant-poor compositions of oil-surfactant-water two-phase systems. Their droplet size-distributions evolve spontaneously towards power laws with the Apollonian exponent. Small-Angle X-Ray Scattering performed on aged HIPEs demonstrated that the droplet packing structure…
Jammed matter is by definition impenetrable to light, rendering the characterization of the 3D geometry difficult. Confocal microscopy of a dyed, refractive index matched emulsion nevertheless allows one to image the jammed system. Here we explain the origin of the mechanism of enhanced fluorescence at the contacts of jammed emulsion droplets in terms of a blue-shifted fluorescence emission band due to the change in the polarity of the interfacial environment. We then use this information to determine the contact network in the emulsion, which models a frictionless jammed system. This enables …
We report a new mechanism for nucleation in a monolayer of hexagonally packed monodisperse droplet arrays. Upon cooling, we observe solidified droplets to nucleate their supercooled neighbors giving rise to an autocatalytic-like mechanism for accelerated crystallization. This collective mode of nucleation depends on the strength and nature of droplet contacts. Intriguingly, the statistical distribution of the solidified droplet clusters is found to be independent of emulsion characteristics except surfactant. In contrast to classical nucleation theory, our work highlights the need to consider …
We revisit the scaling properties of growing spheres randomly seeded in d=2,3 and 4 dimensions using a mean-field approach. We model the insertion probability without assuming a priori a functional form for the radius distribution. The functional form of the insertion probability shows an unprecedented agreement with numerical simulations in d=2, 3 and 4 dimensions. We infer from the insertion probability the scaling behavior of the Random Apollonian Packing and its fractal dimensions. The validity of our model is assessed with sets of 256 simulations each containing 20 million spheres in 2, 3…
Using confocal microscopy we investigate the effect of attraction on the packing of polydisperse emulsions under gravity. We find that the distributions of neighbors, coordination number, and local packing fraction as a function of attraction are captured by recently proposed geometrical modeling and statistical mechanics approaches to granular matter. This extends the range of applicability of these tools to polydisperse, attractive jammed packings. Furthermore, the dependence of packing density and average coordination number on the strength of attraction provides the first experimental test…
We have developed Norland Optical Adhesive (NOA) flow focusing devices, making use of the excellent solvent compatibility and surface properties of NOA to generate micron scale oil-in-water emulsions with polydispersities as low as 5%. While current work on microfluidic oil-in-water emulsification largely concerns the production of droplets with sizes on the order of 10s of micrometres, large enough that Brownian motion is negligible, our NOA devices can produce droplets with radii ranging from 2 μm to 12 μm. To demonstrate the utility of these emulsions as colloidal model systems we produce f…
We study long range density fluctuations (hyperuniformity) in two-dimensional jammed packings of bidisperse droplets. Taking advantage of microfluidics, we systematically span a large range of size and concentration ratios of the two droplet populations. We identify various defects increasing long range density fluctuations mainly due to organization of local particle environment. By choosing an appropriate bidispersity, we fabricate materials with a high level of hyperuniformity. Interesting transparency properties of these optimized materials are established based on numerical simulations.
We investigate the jamming transition in packings of emulsions and granular materials via molecular dynamics simulations. The emulsion model is composed of frictionless droplets interacting via nonlinear normal forces obtained using experimental data acquired by confocal microscopy of compressed emulsions systems. Granular materials are modeled by Hertz-Mindlin deformable spherical grains with Coulomb friction. In both cases, we find power-law scaling for the vanishing of pressure and excess number of contacts as the system approaches the jamming transition from high volume fractions. We find …
We study the elasto-plastic behavior of dense attractive emulsions under mechanical perturbation. The attraction is introduced through non-specific depletion interactions between the droplets and is controlled by changing the concentration of surfactant micelles in the continuous phase. We find that such attractive forces are not sufficient to induce any measurable modification on the scalings between the local packing fraction and the deformation of the droplets. However, when the emulsions are flown through 2D microfluidic constrictions, we uncover a measurable effect of attraction on their …
An important strategy to stabilize emulsions is to arrest coalescence of the constituent droplets with an opposing rheological force. Colloidal particles adsorbed on the surface of emulsion droplets in a Pickering emulsion become increasingly crowded during successive coalescence events because the combined surface area of coalescing droplets is less than that of the constituent droplets. Beyond a critical density, the particles form a rigid shell around the droplet and inhibit both relaxation of the droplet shape and further coalescence. The resulting droplets have a nonuniform distribution o…
We propose an improved viscosity model accounting for experiments of emulsions of two immiscible liquids at arbitrary volume fractions and low shear rates. The model is based on a recursive-differential method formulated in terms of the appropriate scaling variable which emerges from an analysis of excluded volume effects in the system. This variable, called the effective filling fraction, incorporates the geometrical information of the system which determines the maximum packing and reduces to the bare filling fraction for infinitely diluted emulsions. The agreement of our model for the visco…
We perform computational studies of jammed particle packings in two dimensions undergoing isotropic compression using the well-characterized soft particle (SP) model and the deformable particle (DP) model that we developed for compressed bubbles and emulsions. In the SP model, circular particles are allowed to overlap, generating purely repulsive forces. In the DP model, particles minimize their perimeter, while deforming at fixed area to avoid overlap during compression. We directly compare the structural and mechanical properties of jammed particle packings generated using the SP and DP mode…
Using confocal microscopy, we measure the packing geometry and interdroplet forces as a function of the osmotic pressure in a 3D emulsion system. We find that the nonlinear elastic response of the pressure with density is not a result of the anharmonicity in the interaction potential, but of the corrections to the scaling laws of the microstructure away from the critical point. The bulk modulus depends on the excess contacts created under compression, which leads to the correction exponent α=1.5. Microscopically, the nonlinearities manifest themselves as a narrowing of the distribution of the …
Non-spherical emulsion droplets can be stabilized by densely packed colloidal particles adsorbed at their surface. In order to understand the microstructure of these surface packings, the ordering of hard spheres on ellipsoidal surfaces is determined through large scale computer simulations. Defects in the packing are shown generically to occur most often in regions of strong curvature; however, the relationship between defects and curvature is nontrivial, and the distribution of defects shows secondary maxima for ellipsoids of sufficiently high aspect ratio. As with packings on spherical surf…
Droplet microfluidics, in which micro-droplets serve as individual reactors, has enabled a wide range of high-throughput biochemical processes. Unlike solid wells typically used in current biochemical assays, droplets are subject to instability and can undergo breakup, especially under fast flow conditions. Although the physics of single drops has been studied extensively, the flow of crowded drops or concentrated emulsions, where droplet volume fraction exceeds 80 percent, is relatively unexplored in microfluidics. In this article and the related invited lecture from the 74th Annual Meeting o…
Jamming occurs in granular materials, as well as in emulsions, dense suspensions, and other amorphous, particulate systems. When the packing fraction $ϕ$, defined as the ratio of particle volume to system volume, is increased past a critical value $ϕ_c$, a liquid-solid phase transition occurs, and grains are no longer able to rearrange. Previous studies have shown evidence of spatial correlations that diverge near $ϕ= ϕ_c$, but there has been no explicit spatial renormalization group (RG) scheme that has captured this transition. Here, I present a candidate for such a scheme, using a block-spi…
High strength-to-weight ratio materials can be constructed by either maximizing strength or minimizing weight. Tensegrity structures and aerogels take very different paths to achieving high strength-to-weight ratios but both rely on internal tensile forces. In the absence of tensile forces, removing material eventually destabilizes a structure. Attempts to maximize the strength-to-weight ratio with purely repulsive spheres have proceeded by removing spheres from already stable crystalline structures. This results in a modestly low density and a strength-to-weight ratio much worse than can be a…
We consider a theoretical model for a binary mixture of colloidal particles and spherical emulsion droplets. The hard sphere colloids interact via additional short-ranged attraction and long-ranged repulsion. The droplet-colloid interaction is an attractive well at the droplet surface, which induces the Pickering effect. The droplet-droplet interaction is a hard-core interaction. The droplets shrink in time, which models the evaporation of the dispersed (oil) phase, and we use Monte Carlo simulations for the dynamics. In the experiments, polystyrene particles were assembled using toluene dropl…
Paradigmatic model systems, which are used to study the mechanical response of matter, are random networks of point-atoms, random sphere packings, or simple crystal lattices, all of these models assume central-force interactions between particles/atoms. Each of these models differs in the spatial arrangement and the correlations among particles. In turn, this is reflected in the widely different behaviours of the shear (G) and compression (K) elastic moduli. The relation between the macroscopic elasticity as encoded in G, K and their ratio, and the microscopic lattice structure/order, is not u…
