Shear-induced glass-to-crystal transition in anisotropic clay-like suspensions.

A new numerical framework based on Stokesian dynamics is used to study a shear-induced glass-to-crystal transition in suspensions of clay-like anisotropically charged platelets. The structures obtained in quiescent conditions are in agreement with previous Monte Carlo results: a liquid phase at very short interaction range (high salt concentration), phase separation and a gel without large scale density fluctuations at intermediate interaction ranges, and glassy states at very large interaction ranges. When initially glassy suspensions are sheared, hydrodynamic torques first rotate platelets so they can reach a transient quasi-nematic disordered state. These orientational correlations permit to unlock translational degrees of freedom and the platelets then form strings aligned with the velocity direction and hexagonally packed in the gradient-vorticity plane. Under steady shear, platelet orientations are correlated but the system is not nematic. After flow cessation and relaxation in quiescent conditions, positional and orientational order are further improved as the platelet suspension experiences a transition to a nematic hexagonal crystal. Energy calculations and the existence of residual stress anisotropy after relaxation show that this final structure is not an equilibrium state but rather a new ordered, arrested state. The transient, nematic, disordered state induced by shear immediately after startup and unlocking translational degrees of freedom is thought to be an initial step that may be generic for other suspensions of strongly anisotropic colloids with important translation-orientation coupling induced by long-range interactions.

Surface and extrapolated point charge renormalizations for charge-stabilized colloidal spheres.

The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory is widely used to model interactions between weakly charged spheres in dilute suspensions. For particles bearing a higher charge, the linearized electrostatics underlying the DLVO theory is no longer valid but it is possible to map the real colloidal system to an auxiliary one that still obeys linear electrostatics but which involves a different, effective pair potential. This procedure, termed renormalization, can be performed in various ways, the most widely used being surface charge renormalization (SCR) based on the cell model. SCR is still limited to dilute suspensions since the auxiliary system is made of spheres interacting through a DLVO-like pair potential. The recent extrapolated point charge (EPC) renormalization overcomes this limitation by using point charges in the auxiliary system and has indeed been shown to produce better results than the SCR in dense suspensions. Here, we recall that the DLVO-like potential used in the SCR can be modified to account for many-body ion-colloid core exclusion effects (a model termed SCRX here); we show that the accuracy of the EPC and SCRX renormalizations is virtually identical, and conclude by explaining why the EPC method is still the most attractive option of the two in many cases.

Drying colloidal systems: Laboratory models for a wide range of applications.

The drying of complex fluids provides a powerful insight into phenomena that take place on time and length scales not normally accessible. An important feature of complex fluids, colloidal dispersions and polymer solutions is their high sensitivity to weak external actions. Thus, the drying of complex fluids involves a large number of physical and chemical processes. The scope of this review is the capacity to tune such systems to reproduce and explore specific properties in a physics laboratory. A wide variety of systems are presented, ranging from functional coatings, food science, cosmetology, medical diagnostics and forensics to geophysics and art.

Fast, Robust Evaluation of the Equation of State of Suspensions of Charge-Stabilized Colloidal Spheres.

Increasing demand is appearing for the fast, robust prediction of the equation of state of colloidal suspensions, notably with a view to using it as input data to calculate transport coefficients in complex flow solvers. This is also of interest in rheological studies, industrial screening tests of new formulations, and the real-time interpretation of osmotic compression experiments, for example. For charge-stabilized spherical particles, the osmotic pressure can be computed with standard liquid theories. However, this calculation can sometimes be lengthy and/or unstable under some physicochemical conditions, a drawback that precludes its use in multiscale flow simulators. As a simple, fast, and robust replacement, the literature reports estimations of the osmotic pressure that have been built by adding the Carnahan-Starling and the cell model pressures (CSCM model). The first contribution is intended to account for colloid-colloid contacts, and the second, for electrostatic effects. This approximation has not yet been thoroughly tested. In this work, the CSCM is evaluated by comparison with data from experiments on silica particles, Monte Carlo simulations, and solutions of the accurate Rogers-Young integral equation scheme with a hard-sphere Yukawa potential obtained from the extrapolated point-charge renormalization method for a wide range of volume fractions, surface charge densities, and interaction ranges. We find that the CSCM is indeed perfectly adequate in the electrostatically concentrated regime, where it can be used from vanishingly small to high surface charge because there is error cancellation between the Carnahan-Starling and cell model contributions at intermediate charge. The CSCM is thus a nice extension of the cell model to liquid-like dense suspensions, which should find application in the domains mentioned above. However, it fails for dilute suspensions with strong electrostatics. In this case, we show that, and explain why, perturbation methods and the rescaled mean spherical approximation are good alternatives in terms of precision, ease of implementation, computational cost, and robustness.

Modeling the Electrostatics of Hollow Shell Suspensions: Ion Distribution, Pair Interactions, and Many-Body Effects.

Electrostatic interactions play a key role in hollow shell suspensions as they determine their structure, stability, thermodynamics, and rheology and also the loading capacity of small charged species for nanoreservoir applications. In this work, fast, reliable modeling strategies aimed at predicting the electrostatics of hollow shells for one, two, and many colloids are proposed and validated. The electrostatic potential inside and outside a hollow shell with a finite thickness and a specific permittivity is determined analytically in the Debye-Hückel (DH) limit. An expression for the interaction potential between two such hollow shells is then derived and validated numerically. It follows a classical Yukawa form with an effective charge depending on the shell geometry, permittivity, and inner and outer surface charge densities. The predictions of the Ornstein-Zernike (OZ) equation with this pair potential to determine equations of state are then evaluated by comparison to results obtained with a Brownian dynamics algorithm coupled to the resolution of the linearized Poisson-Boltzmann and Laplace equations (PB-BD simulations). The OZ equation based on the DLVO-like potential performs very well in the dilute regime as expected, but also quite well, and more surprisingly, in the concentrated regime in which full spheres exhibit significant many-body effects. These effects are shown to vanish for shells with small thickness and high permittivity. For highly charged hollow shells, we propose and validate a charge renormalization procedure. Finally, using PB-BD simulations, we show that the cell model predicts the ion distribution inside and outside hollow shells accurately in both electrostatically dilute and concentrated suspensions. We then determine the shell loading capacity as a function of salt concentration, volume fraction, and surface charge density for nanoreservoir applications such as drug delivery, sensing, or smart coatings.

Quantitative assessment of the accuracy of the Poisson-Boltzmann cell model for salty suspensions.

The cell model is a ubiquitous, fast, and relatively easily implemented model used to estimate the osmotic pressure of a colloidal dispersion. It has been shown to yield accurate approximations of the pressure in dispersions with a low salt content. It is generally accepted that it performs well when long-ranged interactions are involved and the structure of the dispersion is solidlike. The aim of the present work is to determine quantitatively the error committed by assuming the pressure computed with the cell model is the real osmotic pressure of a dispersion. To this end, cell model pressures are compared to a correct estimation of the actual pressures obtained from Poisson-Boltzmann Brownian dynamics simulations including many-body electrostatics and the thermal motion of the colloids. The comparison is performed for various colloidal sizes and charges, salt contents, and volume fractions. It is demonstrated that the accuracy of the cell model predictions is a function of only the average intercolloid distance scaled by Debye's length κd̅ and the normalized colloidal charge. The cell model is accurate for κd̅ < 1 and not reliable for κd̅ > 5 independently of the colloidal charge. In the 1 < κd̅ < 5 range, covering a wide set of experimental conditions, the colloidal surface charge has a large influence on the error associated with the cell approximation. The results presented in this article should provide a useful reference to determine a priori if the cell model can be expected to predict accurately an equation of state for a given set of physicochemical parameters.

In situ structural analysis with a SAXS laboratory beamline on a microfluidic chip.

Recent advances have been made in coupling microfluidic chips with X-ray equipment, enabling structural analysis of samples directly in microfluidic devices. This important step mainly took place at powerful synchrotron facilities because of the need for a beam reduced in size to fit the microfluidic channel dimensions but still intense. In this work, we discuss how improvements of an X-ray laboratory beamline and an optimal design of a microfluidic device allow reliable structural information to be obtained without the need for a synchrotron. We evaluate the potential of these new developments by probing several well known dispersions. These include dense inorganic gold and silica nanoparticles that scatter photons quite intensely, the bovine serum albumin (BSA) macromolecule, with moderate contrast, to highlight possible applications in biology, and latex nanospheres with only weak contrast with the solvent to show the limits of the setup. We established a proof of concept for a versatile setup that will open the way for more complex lab-on-a-chip devices suitable for in situ and operando structural analysis by small angle X-ray scattering analysis without the necessity for a synchrotron source.

Microfluidic model systems used to emulate processes occurring during soft particle filtration.

Cake layer formation in membrane processes is an inevitable phenomenon. For hard particles, especially cake porosity and thickness determine the membrane flux, but when the particles forming the cake are soft, the variables one has to take into account in the prediction of cake behavior increase considerably. In this work we investigate the behavior of soft polyacrylamide microgels in microfluidic model membranes through optical microscopy for in situ observation both under regular flow and under enhanced gravity conditions. Particles larger than the pore are able to pass through deformation and deswelling. We find that membrane clogging time and cake formation is not dependent on the applied pressure but rather on particle and membrane pore properties. Furthermore, we found that particle deposits subjected to low pressures and low g forces deform in a totally reversible fashion. Particle deposits subjected to higher pressures only deform reversibly if they can re-swell due to capillary forces, otherwise irreversible compression is observed. For membrane processes this implies that when using deformable particles, the pore size is not a good indicator for membrane performance, and cake formation can have much more severe consequences compared to hard particles due to the sometimes-irreversible nature of soft particle compression.

Conformational changes influence clogging behavior of micrometer-sized microgels in idealized multiple constrictions.

Clogging of porous media by soft particles has become a subject of extensive research in the last years and the understanding of the clogging mechanisms is of great importance for process optimization. The rise in the utilization of microfluidic devices brought the possibility to simulate membrane filtration and perform in situ observations of the pore clogging mechanisms with the aid of high speed cameras. In this work, we use microfluidic devices composed by an array of parallel channels to observe the clogging behavior of micrometer sized microgels. It is important to note that the microgels are larger than the pores/constrictions. We quantify the clog propensity in relation to the clogging position and particle size and find that the majority of the microgels clog at the first constriction independently of particle size and constriction entrance angle. We also quantify the variations in shape and volume (2D projection) of the microgels in relation to particle size and constriction entrance angle. We find that the degree of deformation increases with particle size and is dependent of constriction entrance angle, whereas, changes in volume do not depend on entrance angle.

Osmotic compression and expansion of highly ordered clay dispersions.

Aqueous dispersions of nanometric clay platelets (Laponite) have been dewatered through different techniques: centrifugation, mechanical compression, and osmotic stress (dialysis against a polymer solution). The positional and orientational correlations of the particles have been determined through small-angle neutron scattering. Uniaxial compression experiments produce concentrated dispersions (volume fraction > 0.03) in which the platelets have strong orientational and positional correlations. The orientational correlations cause the platelets to align with their normal along a common axis, which is the axis of compression. The positional correlations cause the platelets to be regularly spaced along this direction, with a spacing that matches the average volume per particle in the dispersion. The swelling law (volume fraction versus separation distance) is one-dimensional, as in a layered system. Changes in the applied osmotic pressure cause the water content of the dispersion to either rise or decrease, with time scales that are controlled by interparticle friction forces and by hydrodynamic drag. At long times, the dispersions approach osmotic equilibrium, which can be defined as the common limit of swelling and deswelling processes. The variation of the equilibrium water content with the applied osmotic pressure has been determined over 1 decade in volume fractions (0.03 < phi < 0.3) and 3 decades in pressures. This equation of state matches the predictions made from the knowledge of the forces and thermal agitation for all components in the dispersion (particles, ions, and water).