Despite the omnipresence of colloidal suspensions, little is known about the influence of shape on phase transformations, especially in nonequilibrium. To date, real-space imaging results are limited to systems composed of spherical colloids. In most natural and technical systems, however, particles are non-spherical and their structural dynamics are determined by translational and rotational degrees of freedom. Using confocal microscopy, we reveal that suspensions of ellipsoidal colloids form an unexpected state of matter, a liquid glass in which rotations are frozen while translations remain fluid. Image analysis unveils hitherto unknown nematic precursors as characteristic structural elements of this state. The mutual obstruction of these ramified clusters prevents liquid crystalline order. Our results give unique insight into the interplay between local structures and phase transformations. This helps to guide applications such as self-assembly of colloidal superstructures and also gives first evidence of the importance of shape on the glass transition in general.
We show that geometric confinement dramatically affects the shear-induced configurations of dense mono-disperse colloidal suspensions; a new structure emerges, where layers of particles buckle to stack in a more efficient packing. The volume fraction in the shear zone is controlled by a balance between the viscous stresses and the osmotic pressure of a contacting reservoir of unsheared particles. We present a model that accounts for our observations and helps elucidate the complex interplay between particle packing and shear stress for confined suspensions.
Interfacial undercooling is of significant importance on microscopic pattern formation in the solidification of colloidal suspensions. Two kinds of interfacial undercooling are supposed to be involved in freezing colloidal suspensions, i.e. solute constitutional supercooling (SCS) caused by additives in the solvent and particulate constitutional supercooling (PCS) caused by particles. However, quantitatively identification of the interfacial undercooling of freezing colloidal suspensions is still absent and it is still unknown which undercooling is dominant. The revealing of interfacial underc…
The authors previously introduced an activation model for the onset of shear thickening in electrically stabilized colloidal suspensions. It predicts that shear thickening occurs, when particles arranged along the compression axis in a sheared suspension do overcome the electrostatic repulsion at a critical shear stress, and are captured in the primary minimum of the DLVO interaction potential. A comparison with an experimental investigation on non-aqueous silica suspensions, carried out by Maranzano and Wagner, is performed. For particle systems that fall into the applicability range of the t…
Freezing colloidal suspensions widely exists in nature and industry. Interface instability has attracted much attention for the understandings of the pattern formation in freezing colloidal suspensions. However, the interface instability modes, the origin of the ice banding or ice lamellae, are still unclear. In-situ experimental observation of the onset of interface instability is still absent up to now. Here, by directly imaging the initial transient stage of planar interface instability in directional freezing colloidal suspensions, we proposed three interface instability modes, Mullins-Sek…
This paper adopts a previously developed activation model of shear thickening, published by the authors, to sterically stabilized colloidal suspensions. When particles arranged along the compression axis of a sheared suspension, they may overcome the repulsive interaction and form hydroclusters associated with shear thickening. Taking advantage of the total interaction potential of polymeric brush coating and van der Waals attraction, the applicability of the activation model is shown within the validity range of a continuum theory. For the comparison with an extensive experimental investigati…
The mechanical non-linear response of dense Brownian suspensions of polymer gel particles is studied experimentally and by means of numerical simulations. It is shown that the response to the application of a constant shear rate depends on the previous history of the suspension. When the flow starts from a suspension at rest, it exhibits an elastic response followed by a stress overshoot and then a plastic flow regime. Conversely, after flow reversal, the stress overshoot does not occur, and the apparent elastic modulus is reduced while numerical simulations reveal that the anisotropy of the l…
Based on renormalization group concepts and explicit mean field calculations we study the universal contribution to the effective force and torque acting on an ellipsoidal colloidal particle which is dissolved in a critical fluid and is close to a homogeneous planar substrate. At the same closest distance between the substrate and the surface of the particle, the ellipsoidal particle prefers an orientation parallel to the substrate and the magnitude of the fluctuation induced force is larger than if the orientation of the particle is perpendicular to the substrate. The sign of the critical tor…
An ultra-fast quench is applied to binary mixtures of superparamagnetic colloidal particles confined at a two-dimensional water-air interface by a sudden increase of an external magnetic field. This quench realizes a virtually instantaneous cooling which is impossible in molecular systems. Using real-space experiments, the relaxation behavior after the quench is explored. Local crystallites with triangular and square symmetry are formed on different time scales and the correlation peak amplitude of the small particles evolves nonmonotonically in time in agreement with Brownian dynamics compute…
This is a comment on the recent letter by Wang and Brady on "Constant stress and pressure rheology of colloidal suspensions", Phys. Rev. Lett. 115, 158301 (2015).
Theoretical calculations for colloidal charge-stabilized and hard sphere suspensions show that hydrodynamic interactions yield a qualitatively different particle concentration dependence of the short-time self-diffusion coefficient. The effect, however, is numerically small and hardly accessible by conventional light scattering experiments. Applying multiple-scattering decorrelation equipment and a careful data analysis we show that the theoretical prediction for charged particles is in agreement with our experimental results from aqueous polystyrene latex suspensions.
Concentrated particulate suspensions, commonplace in the pharmaceutical, cosmetic and food industries, display intriguing rheology. In particular, the dramatic increase in viscosity with strain rate (shear thickening and jamming) which is often observed at high volume fractions, is of strong practical and fundamental importance. Yet manufacture of these products and their subsequent dispensing often involves flow geometries substantially different from that of simple shear flow experiments. Here we show that the elongation and breakage of a filament of a colloidal fluid under tensile loading i…
We report a numerical study of the rate of crystal nucleation in a binary suspension of oppositely charged colloids. Two different crystal structures compete in the thermodynamic conditions under study. We find that the crystal phase that nucleates is metastable and, more surprisingly, its nucleation free energy barrier is not the lowest one. This implies that, during nucleation, there is insufficient time for sub-critical nuclei to relax to their lowest free-energy structure. Such behavior is in direct contradiction with the common assumption that the phase that crystallizes most readily is t…
Equilibrium sedimentation density profiles of charged binary colloidal suspensions are calculated by computer simulations and density functional theory. For deionized samples, we predict a colloidal ``brazil nut'' effect: heavy colloidal particles sediment on top of the lighter ones provided that their mass per charge is smaller than that of the lighter ones. This effect is verifiable in settling experiments.
Depending on the pH value and salt concentration of Al2O3 suspensions different microstructures can form. Especially the clustered one is of major interest for industrial purposes as found in the production of ceramics. In this paper we investigate the clustered microstructure by means of a coupled Stochastic Rotation Dynamics (SRD) and Molecular Dynamics (MD) simulation. In order to gain statistics within a system containing numerous clusters, large simulation volumes are needed. We present our parallel implementation of the simulation algorithm as well as a newly developed cluster detection …
The deviatoric stresses of colloidal suspensions are routinely calculated using the expression introduced by Batchelor [J. Fluid Mech. 83, 97--117 (1977)]. We show by example that the central feature in its derivation, the thermodynamic force driving particles down the density gradient, is inconsistent with the motion of the colloids. A new expression for the stress is proposed.
We study the phase behavior of colloidal suspensions the solvents of which are considered to be binary liquid mixtures undergoing phase segregation. We focus on the thermodynamic region close to the critical point of the accompanying miscibility gap. There, due to the colloidal particles acting as cavities in the critical medium, the spatial confinements of the critical fluctuations of the corresponding order parameter result in the effective, so-called critical Casimir forces between the colloids. Employing an approach in terms of effective, one-component colloidal systems, we explore the pos…
We investigate the non-equilibrium fluid structure mediated forces between two colloids driven through a suspension of mutually non-interacting Brownian particles as well as between a colloid and a wall in stationary situations. We solve the Smoluchowski equation in bispherical coordinates as well as with a method of reflections, both in linear approximation for small velocities and numerically for intermediate velocities, and we compare the results to a superposition approximation considered previously. In particular we find an enhancement of the friction (compared to the friction on an isola…
A first principles approach to the nonlinear flow of dense suspensions is presented which captures shear thinning of colloidal fluids and dynamical yielding of colloidal glasses. The advection of density fluctuations plays a central role, suppressing the caging of particles and speeding up structural relaxation. A mode coupling approach is developed to explore these effects.
Hypothesis: Aging in colloidal suspensions manifests as a reduction in kinetic freedom of the colloids. In aqueous suspensions of charged colloids, the role of inter-particle electrostatics interactions on the aging dynamics is well debated. Despite water being the dispersion medium, the influence of water structure on the physicochemical properties of aging colloids has never been considered before. Laponite, a model hectorite clay, could be used to evaluate the relative contributions of medium structure and electrostatics in determining the physicochemical properties of aging colloidal suspe…
In this review article, we focus on collective motion in externally driven colloidal suspensions, as well as how these collective effects can be harnessed for use in microfluidic applications. We highlight the leading role of hydrodynamic interactions in the self-assembly, emergent behavior, transport, and mixing properties of colloidal suspensions. A special emphasis is given to recent numerical methods to simulate driven colloidal suspensions at large scales. In combination with experiments, they help us to understand emergent dynamics and to identify control parameters for both individual a…
A model of shear thickening in dense suspensions of Brownian soft sphere colloidal particles is established. It suggests that shear thickening in soft sphere suspensions can be interpreted as a shear induced phase transition. Based on a Landau model of the coagulation transition of stabilized colloidal particles, taking the coupling between order parameter fluctuations and the local strain-field into account, the model suggests the occurrence of clusters of coagulated particles (subcritical bubbles) by applying a continuous shear perturbation.The critical shear stress of shear thickening in so…
The ionic composition and pair correlations in fluid phases of realistically salt-free charged colloidal sphere suspensions are calculated in the primitive model. We obtain the number densities of all ionic species in suspension, including low-molecular weight microions, and colloidal macroions with acidic surface groups, from a self-consistent solution of a coupled physicochemical set of nonlinear algebraic equations and non-mean-field liquid integral equations. Here, we study suspensions of colloidal spheres with sulfonate or silanol surface groups, suspended in demineralized water that is s…
We show that the shear-induced solidification of dilute charge-stabilized (DLVO) colloids is due to the interplay between the shear-induced formation and breakage of large non-Brownian clusters. While their size is limited by breakage, their number density increases with the shearing-time. Upon flow cessation, the dense packing of clusters interconnects into a rigid state by means of grainy bonds, each involving a large number of primary colloidal bonds. The emerging picture of shear-driven solidification in dilute colloidal suspensions combines the gelation of Brownian systems with the jammin…
Using grand-canonical Monte Carlo simulations we investigate the impact of charged walls on the crystallization properties of charged colloidal suspensions confined between these walls. The investigations are based on an effective model focussing on the colloids alone. Our results demonstrate that the fluid-wall interaction stemming from charged walls has a crucial impact on the fluid's high-density behavior as compared to the case of uncharged walls. In particular, based on an analysis of in-plane bond order parameters we find surface-charge-induced freezing and melting transitions.
An approach is proposed which allows to self-consistently calculate the structural and thermodynamic properties of highly charged aqueous colloidal suspensions. The method is based on the renormalized Jellium model with the background charge distribution related to the colloid-colloid correlation function. The theory is used to calculate the correlation functions and the effective colloidal charges for suspension containing additional monovalent electrolyte. The predictions of the theory are in excellent agreement with the Monte Carlo simulations.
Using a novel bi-axial confocal rheoscope, we investigate the structure and rheology of sheared colloidal suspensions under confinement. Consistent with previous work [X. Cheng \textit{et al., Proc. Natl. Acad. Sci. U. S. A.}, 2011, 109, 63], we observe a vorticity-aligned string phase in moderate concentrated colloidal suspensions under uniaxial shear. Using bi-axial shear protocols, we directly manipulate the orientation and morphology of the string structures. Simultaneously, we measure the suspension rheology along both the flow and vorticity directions with a bi-axial force measurement de…
In charge-stabilized colloidal suspensions, highly charged macroions, dressed by strongly correlated counterions, carry an effective charge that can be substantially reduced (renormalized) from the bare charge. Interactions between dressed macroions are screened by weakly correlated counterions and salt ions. Thermodynamic and structural properties of colloidal suspensions depend sensitively on the magnitudes of both the effective charge and the effective screening constant. Combining a charge renormalization theory of effective electrostatic interactions with Monte Carlo simulations of a one-…
Colloidal suspensions have a rich rheology and can exhibit shear-thinning as well as shear-thickening. Numerical simulations recently suggested that shear-thickening may be attributed to the inertia of the colloids, besides the hydrodynamic interactions between them. Here, we consider the ideal limit of a dense bath of soft colloids following an underdamped Langevin dynamics. We use a mean-field equation for the colloidal density to get an analytical expression of the drag force felt by a probe pulled at constant velocity through the suspension. Our results show that inertia can indeed induce …
Using Brownian dynamics simulations we perform a systematic investigation of the shear-induced migration of colloidal particles subject to Poiseuille flow in both cylindrical and planar geometry. We find that adding an attractive component to the interparticle interaction enhances the migration effect, consistent with recent simulation studies of platelet suspensions. Monodisperse, bidisperse and polydisperse systems are studied over a range of shear rates, considering both steady states and the transient dynamics arising from the onset of flow. For bidisperse and polydisperse systems size seg…
The solid-liquid phase-diagram of charge-stabilized colloidal suspensions is calculated using a technique that combines a continuous Poisson-Boltzmann description for the microscopic electrolyte ions with a molecular-dynamics simulation for the macroionic colloidal spheres. While correlations between the microions are neglected in this approach, many-body interactions between the colloids are fully included. The solid-liquid transition is determined at a high colloid volume fraction where many-body interactions are expected to be strong. With a view to the Derjaguin-Landau-Verwey-Overbeek theo…
Suspensions of hard colloidal particles frequently serve as model systems in studies on fundamental aspects of phase transitions. But often colloidal particles that are considered as ``hard'' are in fact weakly charged. If the colloids are spherical, weak charging has a only a weak effect on the structural properties of the suspension, which can be easily corrected for. However, this does not hold for anisotropic particles. We introduce a model for the interaction potential between charged ellipsoids of revolution (spheroids) based on the Derjaguin approximation of Debye--Hückel Theory and pre…
We explore the influence of particle softness and internal structure on both the bulk and interfacial rheological properties of colloidal suspensions. We probe bulk stresses by conventional rheology, by measuring the flow curves, shear stress vs strain rate, for suspensions of soft, deformable microgel particles and suspensions of near hard-sphere-like silica particles. A similar behavior is seen for both kind of particles in suspensions at concentrations up to the random close packing volume fraction, in agreement with recent theoretical predictions for sub-micron colloids. Transient interfac…
A scaling model is developed to correlate relaxation time distribution of soft glassy materials to ultimate recovery. We propose that in the limit of creep-recovery time smaller than age, time translational invariance can be applied to ageing soft materials. In such limit, multimode linear viscoelastic model with Spriggs relaxation spectrum predicts enhancement in the ultimate recovery with broadening of the relaxation time distribution. We analyze these results in the context of creep-recovery behavior of aqueous suspension of laponite with varying concentration of salt.
We study the fingering instability of the interface between two miscible fluids, a colloidal suspension and its own solvent. The temporal evolution of the interface in a Hele-Shaw cell is found to be governed by the competition between the non-linear viscosity of the suspension and an off-equilibrium, effective surface tension $Γ_e$. By studying suspensions in a wide range of volume fractions, $Φ_\mathrm{C}$, we show that $Γ_e \sim Φ_\mathrm{C}^2$, in agreement with Korteweg's theory for miscible fluids. The surface tension exhibits an anomalous increase with particle size, which we account fo…
Thermodynamic properties of charge-stabilised colloidal suspensions depend sensitively on the effective charge of the macroions, which can be substantially lower than the bare charge in the case of strong counterion-macroion association. A theory of charge renormalization is proposed, combining an effective one-component model of charged colloids with a thermal criterion for distinguishing between free and associated counterions. The theory predicts, with minimal computational effort, osmotic pressures of deionized suspensions of highly charged colloids in close agreement with large-scale simu…
We compute the electrostatic potential at the surface, or zeta potential $ζ$, of a charged particle embedded in a colloidal suspension using a hybrid mesoscopic model. We show that for weakly perturbing electric fields, the value of $ζ$ obtained at steady state during electrophoresis is statistically indistinguishable from $ζ$ in thermodynamic equilibrium. We quantify the effect of counterions concentration on $ζ$. We also evaluate the relevance of the lattice resolution for the calculation of $ζ$ and discuss how to identify the effective electrostatic radius.
We present molecular dynamics simulations of aggregation kinetics in a colloidal suspension modeled as a highly asymmetric binary mixture. Starting from a configuration with largely uncorrelated colloidal particles the system relaxes by coagulation-fragmentation dynamics to a structured state of low-dimensionality clusters with an exponential size distribution. The results show that short-range repulsive interactions alone can give rise to so-called cluster phases. For the present model and probably other, more common colloids, the observed clusters appear to be equilibrium phase fluctuations …
The lack of detailed balance in active colloidal suspensions allows dissipation to determine stationary states. Here we show that slow viscous flow produced by polar or apolar active colloids near plane walls mediates attractive hydrodynamic forces that drive crystallization. Hydrodynamically mediated torques tend to destabilize the crystal but stability can be regained through critical amounts of bottom-heaviness or chiral activity. Numerical simulations show that crystallization is not nucleational, as in equilibrium, but is preceded by a spinodal-like instability. Harmonic excitations of th…
We investigate the sedimentation equilibrium of a charge stabilized colloidal suspension in the regime of low ionic strength. We analyze the asymptotic behaviour of the density profiles on the basis of a simple Poisson--Boltzmann theory and show that the effective mass we can deduce from the barometric law corresponds to the actual mass of the colloidal particles, contrary to previous studies.
A theory is presented for the onset of shear thickening in colloidal suspensions of particles, stabilized by an electrostatic repulsion. Based on an activation model a critical shear stress can be derived for the onset of shear thickening in dense suspensions for a constant potential and a constant charge approach of the spheres. Unlike previous models the total interaction potential is taken into account (sum of attraction and repulsion). The critical shear stress is related to the maximum of the total interaction potential scaled by the free volume per particle. A comparison with experimenta…
We propose a model for the nonequilibrium enhancement of colloidal self-diffusion in an externally imposed shear flow in charged systems. The enhancement of diffusion is calculated in terms of the electrostatic, two--body interactions between the particles in the shear flow. In the high shear rate, low volume fraction limit in which our model is valid, we compare these calculations to the experiments of Qiu et al. [Phys. Rev. Lett. 61, 2554 (1988)].
A model is presented for the solution of electrokinetic phenomena of colloidal suspensions in fluid mixtures. We solve the discrete Boltzmann equation with a BGK collision operator using the lattice Boltzmann method to simulate binary fluid flows. Solvent-solvent and solvent-solute interactions are implemented using a pseudopotential model. The Nernst-Planck equation, describing the kinetics of dissolved ion species, is solved using a finite difference discretization based on the link-flux method. The colloids are resolved on the lattice and coupled to the hydrodynamics and electrokinetics thr…
Using memory-function formalism we show that in sheared colloidal suspensions the fluctuation-dissipation theorem for self-diffusion, i.e. Einstein's relation between self-diffusion and mobility tensors, is violated and propose a new way to measure this violation in Brownian Dynamics simulations. We derive mode-coupling expressions for the tagged particle friction tensor and for an effective, shear-rate dependent temperature.
We consider the problem of inserting a stiff chain into a colloidal suspension of particles that interact with it through excluded volume forces. The free energy of insertion is associated with the work of creating a cavity devoid of colloid and sufficiently large to accomodate the chain. The corresponding work per unit length is the force that resists the entry of the chain into the colloidal suspension. In the case of a hard sphere fluid, this work can be calculated straightforwardly within the scaled particle theory; for solutions of flexible polymers, on the other hand, we employ simple sc…
We study self-diffusion and sedimentation in colloidal suspensions of nearly-hard spheres using the multiparticle collision dynamics simulation method for the solvent with a discrete mesh model for the colloidal particles (MD+MPCD). We cover colloid volume fractions from 0.01 to 0.40 and compare the MD+MPCD simulations to Brownian dynamics simulations with free-draining hydrodynamics (BD) as well as pairwise far-field hydrodynamics described using the Rotne--Prager--Yamakawa mobility tensor (BD+RPY). The dynamics in MD+MPCD suggest that the colloidal particles are only partially coupled to the…
Aqueous suspensions of highly charged polystyrene particles with different volume fractions have been investigated for structural ordering and phase behavior using static light scattering (SLS) and confocal laser scanning microscope (CLSM). Under deionized conditions, suspensions of high charge density colloidal particles remained disordered whereas suspensions of relatively low charge density showed crystallization by exhibiting iridescence for the visible light. Though for unaided eye crystallized suspensions appeared homogeneous, static light scattering measurements and CLSM observations ha…
We present measurements of the thermal fluctuations of the free surface of an aging colloidal suspension, Laponite. The technique consists in measuring the fluctuations of the position of a laser beam that reflects from the free surface. Analysing the data statistics, we show that, as the fluid ages, the dynamics becomes intermittent. The intermittent events correspond to large changes in the local slope of the free surface over a few milliseconds. We show that those quakes are uncorrelated, although they are kept in memory by the surface over short time scales.
In this paper, we investigate experimentally the non-equilibrium steady state of an active colloidal suspension under gravity field. The active particles are made of chemically powered colloids, showing self propulsion in the presence of an added fuel, here hydrogen peroxide. The active suspension is studied in a dedicated microfluidic device, made of permeable gel microstructures. Both the microdynamics of individual colloids and the global stationary state of the suspension under gravity - density profiles, number fluctuations - are measured with optical microscopy. This allows to connect th…
We review recent experimental, numerical, and analytical results on active suspensions of self-propelled colloidal beads moving in (quasi) two dimensions. Active colloids form part of the larger theme of active matter, which is noted for the emergence of collective dynamic phenomena away from thermal equilibrium. Both in experiments and computer simulations, a separation into dense aggregates, i.e., clusters, and a dilute gas phase has been reported even when attractive interactions and an alignment mechanism are absent. Here, we describe three experimental setups, discuss the different propel…
Colloidal particles are often seen as big atoms that can be directly observed in real space. They are therefore playing an increasingly important role as model systems to study processes of interest in condensed matter physics such as melting, freezing and glass transitions. The solidification of colloidal suspensions has long been a puzzling phenomenon with many unexplained features. Here we demonstrate and rationalize the existence of instability and metastability domains in cellular solidification of colloidal suspensions, by direct in situ high-resolution X-ray radiography and tomography o…
We explore the effects of counterion condensation on fluid-fluid phase separation in charged colloidal suspensions. It is found that formation of double layers around the colloidal particles stabilizes suspensions against phase separation. Addition of salt, however, produces an instability which, in principle, can lead to a fluid-fluid separation. The instability, however, is so weak that it should be impossible to observe a fully equilibrated coexistence experimentally.
Phase transitions and collective dynamics of active colloidal suspensions are fascinating topics in soft matter physics, particularly for out-of-equilibrium systems, which can lead to rich rheological behaviours in the presence of steady shear flow. In this article, the role of self-propulsion in the rheological response of a dense colloidal suspension is investigated by using particle-resolved simulations. First, the interplay between activity and shear in the solid to the liquid transition of the suspension is analysed. While both self-propulsion and shear destroy order and melt the system b…
We present a Lattice-Boltzmann method for simulating self-propelling (active) colloidal particles in two-dimensions. Active particles with symmetric and asymmetric force distribution on its surface are considered. The velocity field generated by a single active particle, changing its orientation randomly, and the different time scales involved are characterized in detail. The steady state speed distribution in the fluid, resulting from the activity, is shown to deviate considerably from the equilibrium distribution.
