Antonio M. Puertas

Comparative Simulation Study of Colloidal Gels And Glasses

Using computer simulations, we identify the mechanisms causing aggregation and structural arrest of colloidal suspensions interacting with a short-ranged attraction at moderate and high densities. Two different nonergodicity transitions are observed. As the density is increased, a glass transition takes place, driven by excluded volume effects. In contrast, at moderate densities, gelation is approached as the strength of the attraction increases. At high density and interaction strength, both transitions merge, and a logarithmic decay in the correlation function is observed. All of these features are correctly predicted by mode coupling theory.

Simulation study of nonergodicity transitions : gelation in colloidal systems with short-range attractions

Computer simulations were used to study the gel transition occurring in colloidal systems with short-range attractions. A colloid-polymer mixture was modeled and the results were compared with mode coupling theory (MCT) expectations and with the results for other systems (hard-spheres system and Lennard-Jones system). The self-intermediate scattering function and the mean squared displacement were used as the main dynamical quantities. Two different colloid packing fractions have been studied. For the lower packing fraction, alpha-scaling holds and the wave-vector analysis of the correlation function shows that gelation is a regular nonergodicity transition within MCT. The leading mechanism for the novel nonergodicity transition is identified as the bond formation caused by the short-range attraction. The time scale and diffusion coefficient also show qualitatively the expected behavior, although different exponents are found for the power-law divergences of these two quantities. The non-Gaussian parameter was also studied and a very large correction to Gaussian behavior was found. The system with higher colloid packing fraction shows indications of a nearby high-order singularity, causing alpha scaling to fail, but the general expectations for nonergodicity transitions still hold.

Dynamical heterogeneities close to a colloidal gel

Dynamical heterogeneities in a colloidal fluid close to gelation are studied by means of computer simulations. A clear distinction between some fast particles and the rest, slow ones, is observed yielding a picture of the gel composed of two populations with different mobilities. Analyzing the statics and dynamics of both sets of particles, it is shown that the slow particles form a network of stuck particles, whereas the fast ones are able to move over long distances. Correlation functions show that the environment of the fast particles relaxes much faster than that of the slow ones, but at short times the bonds between fast particles are longer lived due to the flexibility of their structure. No stringlike motion is observed for the fast particles, but they occupy preferential sites in the surface of the structure formed by the slow ones.

Microrheology of colloidal systems

Microrheology was proposed almost twenty years ago as a technique to obtain rheological properties in soft matter from the microscopic motion of colloidal tracers used as probes, either freely diffusing in the host medium, or subjected to external forces. The former case is known as passive microrheology, and is based on generalizations of the Stokes-Einstein relation between the friction experienced by the probe and the host-fluid viscosity. The latter is termed active microrheology, and extends the measurement of the friction coefficient to the nonlinear-response regime of strongly driven probes. In this review article, we discuss theoretical models available in the literature for both passive and active microrheology, focusing on the case of single-probe motion in model colloidal host media. A brief overview of the theory of passive microrheology is given, starting from the work of Mason and Weitz. Further developments include refined models of the host suspension beyond that of a Newtonian-fluid continuum, and the investigation of probe-size effects. Active microrheology is described starting from microscopic equations of motion for the whole system including both the host-fluid particles and the tracer; the many-body Smoluchowski equation for the case of colloidal suspensions. At low fluid densities, this can be simplified to a two-particle equation that allows the calculation of the friction coefficient with the input of the density distribution around the tracer, as shown by Brady and coworkers. The results need to be upscaled to agree with simulations at moderate density, in both the case of pulling the tracer with a constant force or dragging it at a constant velocity. The full many-particle equation has been tackled by Fuchs and coworkers, using a mode-coupling approximation and the scheme of integration through transients, valid at high densities. A localization transition is predicted for a probe embedded in a glass-forming host suspension. The nonlinear probe-friction coefficient is calculated from the tracers position correlation function. Computer simulations show qualitative agreement with the theory, but also some unexpected features, such as superdiffusive motion of the probe related to the breaking of nearest-neighbor cages. We conclude with some perspectives and future directions of theoretical models of microrheology.

Nanoemulsion stability: experimental evaluation of the flocculation rate from turbidity measurements

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≤[NaCl]≤600 mM), providing a method of appraisal of the flocculation rate in nanoemulsions.

Active and Nonlinear Microrheology in Dense Colloidal Suspensions

We present a first-principles theory for the active nonlinear microrheology of colloidal model system; for a constant external force on a spherical probe particle embedded in a dense host dispersion, neglecting hydrodynamic interactions, we derive an exact expression for the friction. Within mode-coupling theory, we discuss the threshold external force needed to delocalize the probe from a host glass, and its relation to strong nonlinear velocity-force curves in a host fluid. Experimental microrheology data and simulations, which we performed, are explained with a simplified model.

Tagged-particle dynamics in a hard-sphere system: mode-coupling theory analysis.

The predictions of the mode-coupling theory of the glass transition (MCT) for the tagged-particle density-correlation functions and the mean-squared displacement curves are compared quantitatively and in detail to results from Newtonian- and Brownian-dynamics simulations of a polydisperse quasi-hard-sphere system close to the glass transition. After correcting for a 17% error in the dynamical length scale and for a smaller error in the transition density, good agreement is found over a wide range of wave numbers and up to five orders of magnitude in time. Deviations are found at the highest densities studied, and for small wave vectors and the mean-squared displacement. Possible error sources not related to MCT are discussed in detail, thereby identifying more clearly the issues arising from the MCT approximation itself. The range of applicability of MCT for the different types of short-time dynamics is established through asymptotic analyses of the relaxation curves, examining the wave-number and density-dependent characteristic parameters. Approximations made in the description of the equilibrium static structure are shown to have a remarkable effect on the predicted numerical value for the glass-transition density. Effects of small polydispersity are also investigated, and shown to be negligible.

Theory and simulation of gelation, arrest and yielding in attracting colloids

We present some recent theory and simulation results addressing the phenomena of colloidal gelation at both high and low volume fractions, in the presence of short-range attractive interactions. We discuss the ability of mode-coupling theory and its adaptations to address situations with strong heterogeneity in density and/or dynamics. We include a discussion of the effect of attractions on the shear-thinning and yield behaviour under flow.

Colloidal aggregation induced by attractive interactions

Colloidal aggregation induced by attractive interactions is tackled experimentally and by Brownian dynamics simulations using a mixture of positive and negative particles. The structure of the aggregates and the aggregation kinetics are used to characterize the aggregation behavior. The clusters show uniform internal structures, with a fractal dimension lower than that of clusters formed in diffusion, indicating a more branched architecture. The aggregation kinetics also differs from the diffusive one, slowing down as time proceeds. Both results are totally confirmed by simulation. The transition from the attractive driven to the diffusion controlled regimes is studied varying the range of interaction. Continuous transitions are observed both for the aggregation kinetics and cluster structure.

Colloidal aggregation under steric interactions: Simulation and experiments

The influence of steric interactions in the initial stages of aggregation kinetics in colloidal systems has been studied by simulation and experiments. A simulation model has been proposed to study the initial stages of aggregation under short range repulsive potentials. A polystyrene latex was used as model colloid and the steric interaction was provided by adsorption of a nonionic surfactant. Depending on the range or strength of the interactions, sensitive or insensitive systems to electrolyte concentration can be observed. At low κa, the long-range electrostatic repulsion dominates the system behavior, stabilizing the colloidal system. In conditions of screened electrostatic potential, particle collision is the result of a competition between van der Waals attraction and steric repulsion, leading to a decrease in the dimer formation constant as the range or strength of the steric interaction increases. The steric interaction energy has been included in the theoretical calculation of the aggregation ra...