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The behavior of four oil-in-water (O/W) ioinic nanoemulsions composed of dodecane, and mixtures of dodecane with squalene and tetra-chloro-ethylene is studied. These nanoemulsions were stabilized with sodium dodecyl sulfate (SDS). The behavior of the turbidity and the average radius of the emulsions were followed as a function of time. The results illustrate the shortcomings of characterizing the stability of emulsions by their creaming rate.
We investigate the displacements of a probe particle inside a glass, when a strong external force is applied to the probe (active nonlinear microrheology). Calculations within mode coupling theory are presented for glasses of hard spheres and compared to Langevin and Brownian dynamics simulations. Under not too strong forces where the probe remains trapped, the probe density distribution becomes anisotropic. It is shifted towards the direction of the force, develops an enhanced tail in that direction (signalled by a positive skewness), and exhibits different variances along and perpendicular to the force direction. A simple model of an harmonically trapped probe rationalizes the low force limit, with strong strain softening setting in at forces of the order of a few thermal energies per particle radius.
The coalescence of liquid drops induces a higher level of complexity compared to the classical studies about the aggregation of solid spheres. Yet, it is commonly believed that most findings on solid dispersions are directly applicable to liquid mixtures. Here, the state of the art in the evaluation of the flocculation rate of these two systems is reviewed. Special emphasis is made on the differences between suspensions and emulsions. In the case of suspensions, the stability ratio is commonly evaluated from the initial slope of the absorbance as a function of time under diffusive and reactive conditions. Puertas and de las Nieves (1997) developed a theoretical approach that allows the determination of the flocculation rate from the variation of the turbidity of a sample as a function of time. Here, suitable modifications of the experimental procedure and the referred theoretical approach are implemented in order to calculate the values of the stability ratio and the flocculation rate corresponding to a dodecane-in-water nanoemulsion stabilized with sodium dodecyl sulfate. Four analytical expressions of the turbidity are tested, basically differing in the optical cross section of the aggregates formed. The first two models consider the processes of: a) aggregation (as described by Smoluchowski) and b) the instantaneous coalescence upon flocculation. The other two models account for the simultaneous occurrence of flocculation and coalescence. The latter reproduce the temporal variation of the turbidity in all cases studied (380 leq [NaCl] leq 600 mM), providing a method of appraisal of the flocculation rate in nanoemulsions.
We analyze the nonlinear active microrheology of dense colloidal suspensions using a schematic model of mode-coupling theory. The model describes the strongly nonlinear behavior of the microscopic friction coefficient as a function of applied external force in terms of a delocalization transition. To probe this regime, we have performed Brownian dynamics simulations of a system of quasi-hard spheres. We also analyze experimental data on hard-sphere-like colloidal suspensions [Habdas et al., Europhys. Lett., 2004, 67, 477]. The behavior at very large forces is addressed specifically.
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