Dendritic growth of protein gel in the course of sweat pore plugging by aluminium salts under physiological conditions.

Are aluminium ions unavoidable in antiperspirants? To answer this question, we present confocal microscopy images of dendritic plugs appearing in sweat flowing across a microfluidic channel in the presence of aluminium salts. By comparing with numerical simulations, we identify the mechanisms forming this structured protein gel inside the pore.

Real time observation of the interaction between aluminium salts and sweat under microfluidic conditions.

Aluminium salts such as aluminium chlorohydrate (ACH) are the active ingredients of antiperspirant products. Their mechanism of action involves a temporary and superficial plugging of eccrine sweat pores at the skin surface. We developed a microfluidic system that allows the real time observation of the interactions between sweat and ACH in conditions mimicking physiological sweat flow and pore dimensions. Using artificial sweat containing bovine serum albumin as a model protein, we performed experiments under flowing conditions to demonstrate that pore clogging results from the aggregation of proteins by aluminium polycations at specific location in the sweat pore. Combining microfluidic experiments, confocal microscopy and numerical models helps to better understand the physical chemistry and mechanisms involved in pore plugging. The results show that plugging starts from the walls of sweat pores before expanding into the centre of the channel. The simulations aid in explaining the influence of ACH concentration as well as the impact of flow conditions on the localization of the plug. Altogether, these results outline the potential of both microfluidic confocal observations and numerical simulations at the single sweat pore level to understand why aluminium polycations are so efficient for sweat channel plugging.

Apollonian packing in polydisperse emulsions.

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 organise themselves according to Apollonian packing rules. These polydisperse HIPEs are formed by emulsifying oil dropwise in a surfactant-poor aqueous continuous phase. After stirring has ceased, their droplet size distributions begin to evolve spontaneously and continuously through coalescence towards well-defined power laws with the Apollonian exponent. Small-angle X-ray Scattering performed on aged HIPEs demonstrate that the droplet packing structure agrees with that of a numerically simulated random Apollonian packing. We argue that when such concentrated emulsions are allowed to evolve, the coalescing droplets must obey volume and sphericity conservation. This leads to a mechanism that differs from typical coalescence in dilute emulsions.

Packing Polydisperse Colloids into Crystals: When Charge-Dispersity Matters.

Monte Carlo simulations, fully constrained by experimental parameters, are found to agree well with a measured phase diagram of aqueous dispersions of nanoparticles with a moderate size polydispersity over a broad range of salt concentrations, c_{s}, and volume fractions, ϕ. Upon increasing ϕ, the colloids freeze first into coexisting compact solids then into a body centered cubic phase (bcc) before they melt into a glass forming liquid. The surprising stability of the bcc solid at high ϕ and c_{s} is explained by the interaction (charge) polydispersity and vibrational entropy.

Hiding in Plain View: Colloidal Self-Assembly from Polydisperse Populations.

We report small-angle x-ray scattering experiments on aqueous dispersions of colloidal silica with a broad monomodal size distribution (polydispersity, 14%; size, 8 nm). Over a range of volume fractions, the silica particles segregate to build first one, then two distinct sets of colloidal crystals. These dispersions thus demonstrate fractional crystallization and multiple-phase (bcc, Laves AB_{2}, liquid) coexistence. Their remarkable ability to build complex crystal structures from a polydisperse population originates from the intermediate-range nature of interparticle forces, and it suggests routes for designing self-assembling colloidal crystals from the bottom up.

How do polydisperse repulsive colloids crystallize?

A modified version of the Gibbs-ensemble Monte-Carlo method reveals how polydisperse charged colloidal particles can build complex colloidal crystals. It provides general rules that are applicable to this fractionated crystallization that stems from size segregation. It explains the spontaneous formation of complex crystals with very large unit-cells in suspensions of nanoparticles with a broad size distribution.

Colloidal aggregation and dynamics in anisotropic fluids.

We present experiments and numerical simulations to investigate the collective behavior of submicrometer-sized particles immersed in a nematic micellar solution. We use latex spheres with diameters ranging from 190 to 780 nm and study their aggregation properties due to the interplay of the various colloidal forces at work in the system. We found that the morphology of aggregates strongly depends on the particle size, with evidence for two distinct regimes: the biggest inclusions clump together within minutes into either compact clusters or V-like structures that are completely consistent with attractive elastic interactions. On the contrary, the smallest particles form chains elongated along the nematic axis, within comparable timescales. In this regime, Monte Carlo simulations, based on a modified diffusion-limited cluster aggregation model, strongly suggest that the anisotropic rotational Brownian motion of the clusters combined with short-range depletion interactions dominate the system coarsening; elastic interactions no longer prevail. The simulations reproduce the sharp transition between the two regimes on increasing the particle size. We provide reasonable estimates to interpret our data and propose a likely scenario for colloidal aggregation. These results emphasize the growing importance of the diffusion of species at suboptical-wavelength scales and raise a number of fundamental issues.

Coalescence of repelling colloidal droplets: a route to monodisperse populations.

Populations of droplets or particles dispersed in a liquid may evolve through Brownian collisions, aggregation, and coalescence. We have found a set of conditions under which these populations evolve spontaneously toward a narrow size distribution. The experimental system consists of poly(methyl methacrylate) (PMMA) nanodroplets dispersed in a solvent (acetone) + nonsolvent (water) mixture. These droplets carry electrical charges, located on the ionic end groups of the macromolecules. We used time-resolved small angle X-ray scattering to determine their size distribution. We find that the droplets grow through coalescence events: the average radius (R) increases logarithmically with elapsed time while the relative width σR/(R) of the distribution decreases as the inverse square root of (R). We interpret this evolution as resulting from coalescence events that are hindered by ionic repulsions between droplets. We generalize this evolution through a simulation of the Smoluchowski kinetic equation, with a kernel that takes into account the interactions between droplets. In the case of vanishing or attractive interactions, all droplet encounters lead to coalescence. The corresponding kernel leads to the well-known "self-preserving" particle distribution of the coalescence process, where σR/(R) increases to a plateau value. However, for droplets that interact through long-range ionic repulsions, "large + small" droplet encounters are more successful at coalescence than "large + large" encounters. We show that the corresponding kernel leads to a particular scaling of the droplet-size distribution-known as the "second-scaling law" in the theory of critical phenomena, where σR/(R) decreases as 1/√(R) and becomes independent of the initial distribution. We argue that this scaling explains the narrow size distributions of colloidal dispersions that have been synthesized through aggregation processes.

Restructuring of colloidal aggregates in shear flow: coupling interparticle contact models with Stokesian dynamics.

A method to couple interparticle contact models with Stokesian dynamics (SD) is introduced to simulate colloidal aggregates under flow conditions. The contact model mimics both the elastic and plastic behavior of the cohesive connections between particles within clusters. Owing to this, clusters can maintain their structures under low stress while restructuring or even breakage may occur under sufficiently high stress conditions. SD is an efficient method to deal with the long-ranged and many-body nature of hydrodynamic interactions for low Reynolds number flows. By using such a coupled model, the restructuring of colloidal aggregates under shear flows with stepwise increasing shear rates was studied. Irreversible compaction occurs due to the increase of hydrodynamic stress on clusters. Results show that the greater part of the fractal clusters are compacted to rod-shaped packed structures, while the others show isotropic compaction.

Reverse buoyancy in a vibrated granular bed: Computer simulations.

We have performed molecular dynamics simulations of an intruder in a vibrated granular bed including interstitial fluid effects to account for the phenomenon of reverse buoyancy. We show that our model is able to reproduce the overall behaviour observed by previous experimental works and is the first finite-elements simulation to show the sinking of intruders lighter than the granular bed. To further advance our comprehension of this phenomenon, we studied the motion of the intruders in a single vibration cycle with respect to the bottom of the granular column, finding a substantial qualitative difference for heavy and light intruders and we compare these results with experiments using fine-sized glass beads. We show that, though heavy intruders seem unaffected by the force due to the fluid, the effect on light intruders is remarkable.

Hydrodynamic stress on small colloidal aggregates in shear flow using Stokesian dynamics.

The hydrodynamic properties of rigid fractal aggregates have been investigated by considering their motion in shear flow in the Stokesian dynamics approach. Due to the high fluid viscosity and small particle inertia of colloidal systems, the total force and torque applied to the aggregate reach equilibrium values in a short time. Obtaining equilibrating motions for a number of independent samples, one can extract the average hydrodynamic characteristics of the given fractal aggregates. Despite the geometry of these objects being essentially disordered, the average drag-force distributions for aggregates show symmetric patterns. Moreover, these distributions collapse on a single master curve, characteristic of the nature of the aggregates, provided the positions of the particles are rescaled with the geometric radius of gyration. This result can be used to explain the reason why the stress acting on an aggregate and moments of the forces acting on contact points between particles follow power-law behaviors with the aggregate size. Moreover, the values of the exponents can be explained. As a consequence, considering cohesive force typical for colloidal particles, we find that even aggregates smaller than a few dozen particles must experience restructuring when typical shear flow is applied.

Stochastic theory of the Stokes parameters in randomly twisted fiber.

We present the stochastic approach of the polarization state of an electromagnetic wave traveling through randomly twisted optical fiber. We treat the case of the weak randomness. When the geometric torsion of the fiber is distributed as a Gaussian law, we can write explicitly the Fokker-Planck equation for the Stokes parameters of the wave, and find the complete solution of the polarization-state distribution.

Polarization of an electromagnetic wave in a randomly birefringent medium: a stochastic theory of the Stokes parameters.

We present a framework for the stochastic features of the polarization state of an electromagnetic wave propagating through the optical medium with both deterministic (controlled) and disordered birefringence. In this case, the Stokes parameters obey a Langevin-type equation on the Poincaré sphere. The functional integral method provides for a natural tool to derive the Fokker-Planck equation for the probability distribution of the Stokes parameters. We solve the Fokker-Planck equation in the case of a random anisotropic active medium submitted to a homogeneous electromagnetic field. The possible dissipation and relaxation phenomena are studied in general and in various cases, and we give hints about how to validate experimentally the corresponding phenomenological equations.

No quasi-long-range order in a two-dimensional liquid crystal.

Systems with global symmetry group O(2) experience topological transition in the two-dimensional space. But there is controversy about such a transition for systems with global symmetry group O(3). As an example of the latter case, we study the Lebwohl-Lasher model for the two-dimensional liquid crystal, using three different methods independent of the proper values of possible critical exponents. Namely, we analyze the at-equilibrium order parameter distribution function with (1) the hyperscaling relation; (2) the first-scaling collapse for the probability distribution function; and (3) the Binder's cumulant. We give strong evidence for definite lack of a line of critical points at low temperatures in the Lebwohl-Lasher model, contrary to conclusions of a number of previous numerical studies.

Scanning the critical fluctuations: application to the phenomenology of the two-dimensional XY model.

We show how applying field conjugated to the order parameter may act as a very precise probe to explore the probability distribution function of the order parameter. Using this "magnetic-field scanning" on large-scale numerical simulations of the critical two-dimensional XY model, we are able to discard the conjectured double-exponential form of the large-magnetization asymptote.

Exact order-parameter distribution for critical mean-field percolation and critical aggregation.

We show that the order-parameter distribution for the mean-field percolation at the critical point is the Kolmogorov-Smirnov distribution and that it coincides with the corresponding distribution for a mean-field aggregation process at the critical time. Both processes are known to belong to the same universality class in the sense that they share the same set of critical exponents, but percolation is at the equilibrium while the aggregation is a dynamical critical process. This shows that, in this case, the probability density for order-parameter fluctuations is universal at the critical point of the infinite lattice, independent of the hypothesis of thermodynamic equilibrium.

Scaling behaviors of colloidal aggregates under uniform pressure.

We present a theoretical model for the compaction of a colloidal sediment under uniaxial mechanical pressure in the continuous three-dimensional space. The initial system is formed with aggregated particles dispersed in a fluid, and softly sedimented in a vessel. When a uniform pressure is applied, it evolves irreversibly through successive creation and destruction of bonds between the particles. The rules governing the bonds depend on both geometrical constraints and current stresses. Numerical simulations of such systems exhibit three different scenarios, corresponding, respectively, to the fragile, elastic, and plastic behaviors. In the elastic regime, where most bonds are permanent, the pressure scales as a power law of the volume fraction of particles, with a numerical exponent equal to 4.4. In the plastic regime, where many bonds are broken and many others created, the pressure also scales with volume fraction, but the exponent is much lower, equal to 1.7. These scaling behaviors agree remarkably well with recent experiments realized on the compaction of systems with aggregated silica particles in the oedometer cell. They also can be explained with simple theoretical arguments using a plausible morphology of the resistant paths acting throughout the system. Finally, at very large applied pressures, all these regimes converge to the random close packing of spheres.

Phase transitions in nonextensive spin systems.

The spherical spin model with infinite-range ferromagnetic interactions is investigated analytically in the framework of nonextensive thermostatics generalizing the Boltzmann-Gibbs statistical mechanics. We show that for repulsive correlations, a weak-ferromagnetic phase develops. There is a tricritical point separating para-, weak-ferro, and ferro regimes. The transition from paramagnetic to weak-ferromagnetic phase is an unusual first-order phase transition in which a discontinuity of the averaged order parameter appears, even for finite number of spins. This result puts in a different way the question of the stability of critical phenomena with respect to the long-ranged correlations.