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In quenched disordered out-of-equilibrium many-body colloidal systems, there are important distinctions between the glass transition, which is related to the onset of nonergodicity and loss of low-frequency relaxations caused by crowding, and the jamming transition, which is related to the dramatic increase in elasticity of the system caused by the deformation of constituent objects. For softer repulsive interaction potentials, these two transitions become increasingly smeared together, so measuring a clear distinction between where the glass ends and where jamming begins becomes very difficult or even impossible. Here, we investigate droplet dynamics in concentrated silicone oil-in-water nanoemulsions using light scattering. For zero or low NaCl electrolyte concentrations, interfacial repulsions are soft and longer in range, this transition sets in at lower concentrations, and the glass and the jamming regimes are smeared. However, at higher electrolyte concentrations the interactions are stiffer, and the characteristics of the glass-jamming transition resemble more closely the situation of disordered elastic spheres having sharp interfaces, so the glass and jamming regimes can be distinguished more clearly.

Motivated by improvements in diffusing wave spectroscopy (DWS) for nonergodic, highly optically scattering soft matter and by cursory treatment of collective scattering effects in prior DWS microrheology experiments, we investigate the low-frequency plateau elastic shear moduli G′p of concentrated, monodisperse, disordered oil-in- water emulsions as droplets jam. In such experiments, the droplets play dual roles both as optical probes and as the jammed objects that impart shear elasticity. Here, we demonstrate that collective scattering significantly affects DWS mean-square displacements (MSDs) in dense colloidal emulsions. By measuring and analyzing the scattering mean free path as a function of droplet volume fraction φ, we obtain a φ- dependent average structure factor. We use this to correct DWS MSDs by up to a factor of 4 and then calculate G′p predicted by the generalized Stokes–Einstein relation. We show that DWS-microrheological G′p(φ) agrees well with mechanically measured G′p(φ) over about three orders of magnitude when droplets are jammed but only weakly deformed. Moreover, both of these measurements are consistent with predictions of an entropic–electrostatic–interfacial (EEI) model, based on quasi- equilibrium free-energy minimization of disordered, screened-charge–stabilized, deformable droplets, which accurately describes prior mechanical measurements of G′p(φ) made on similar disordered monodisperse emulsions over a wide range of droplet radii and φ. This very good quantitative agreement between DWS microrheology, mechanical rheometry, and the EEI model provides a comprehensive and self-consistent view of weakly jammed emulsions. Extensions of this approach may improve DWS microrheology on other systems of dense, jammed colloids that are highly scattering.

We develop a free energy model that describes two key thermodynamic properties, the osmotic pressure Π and the linear elastic shear modulus G′p (i.e. plateau storage modulus), of concentrated monodisperse emulsions which have isotropic, disordered, droplet structures, and are stabilized using ionic surfactants. This model effectively incorporates the concept of random close packing or jamming of repulsive spheres into a free energy F that depends on droplet volume fraction ϕ and shear strain γ both below and above the a critical jamming point ϕc ≈ 0.646. This free energy has three terms: entropic, electrostatic, and interfacial (EEI). By minimizing F with respect to an average droplet deformation parameter that links all three terms, we show that the entropic term is dominant for ϕ well below ϕc, the electrostatic term is dominant for ϕ near but below ϕc, and the interfacial term dominates for larger ϕ. This EEI model describes measurements of G′p(ϕ) for charge-stabilized uniform emulsions having a wide range of droplet sizes, ranging from nanoscale to microscale, and it also is consistent with measurements of Π(ϕ). Moreover, it describes G′p(ϕ) for similar nanoemulsions after adding non-amphiphilic salt, when changes in the interfacial tension and the Debye screening length are properly taken into account. By unifying existing approaches, the EEI model predicts constitutive properties of concentrated ionic emulsions that have disordered, out-of-equilibrium structures through near- equilibrium free energy minimization, consistent with random driving Brownian excitations.

In quenched disordered out-of-equilibrium many-body colloidal systems, there are important distinctions between the glass transition, which is related to the onset of nonergodicity and loss of low-frequency relaxations caused by crowding, and the jamming transition, which is related to the dramatic increase in elasticity of the system caused by the deformation of constituent objects. For softer repulsive interaction potentials, these two transitions become increasingly smeared together, so measuring a clear distinction between where the glass ends and where jamming begins becomes very difficult or even impossible. Here, we investigate droplet dynamics in concentrated silicone oil-in-water nanoemulsions using light scattering. For zero or low NaCl electrolyte concentrations, interfacial repulsions are soft and longer in range, this transition sets in at lower concentrations, and the glass and the jamming regimes are smeared. However, at higher electrolyte concentrations the interactions are stiffer, and the characteristics of the glass-jamming transition resemble more closely the situation of disordered elastic spheres having sharp interfaces, so the glass and jamming regimes can be distinguished more clearly.