In many colloidal suspensions, the dispersed colloidal particles are amorphous solids resulting from vitrification. A crucial open problem is understanding how colloidal stability is affected by the intra-particle glass transition. By dealing with the latter process from a solid-state perspective, we estabilish a proportionality relation between the intra-particle glass transition temperature, $T_{\textrm{g}},$ and the Hamaker constant, $A_\textrm{H},$ of a generic suspension of nanoparticles. It follows that $T_\textrm{g}$ can be used as a convenient parameter (alternative to $A_\textrm{H}$) for controlling the stability of colloidal systems. Within DLVO theory, we show that the novel relationship, connecting $T_\textrm{g}$ to $A_\textrm{H},$ implies the critical coagulation ionic strength (CCIS) to be a monotonically decreasing function of $T_{\textrm{g}}.$ We connect our predictions to recent experimental findings.
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…
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).
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…
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…
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…
The fracture mechanics was widely employed to explain the crack propagation in the deposition produced by drying colloidal suspension. However, more complex than conventional fracture, those cracks periodically distribute and make up a unique pattern. This still remains mysterious so far. Inspired by the concept of spinodal decomposition, here, we develop the theory to elucidate the spatial arrangement of the cracks, which indicates that the crack pattern is generated by the phase separation of colloidal clusters and water. It concludes that the crack spacing results from the wavelength of the…
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.
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.
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…
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.
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 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.
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.
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…
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.
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…
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…
The creation of disordered hyperuniform materials with potentially extraordinary optical properties requires a capacity to synthesize large samples that are effectively hyperuniform down to the nanoscale. Motivated by this challenge, we propose a fabrication protocol using binary superparamagnetic colloidal particles confined in a 2D plane. The strong and long-ranged dipolar interaction induced by a tunable magnetic field is free from screening effects that attenuates long-ranged electrostatic interactions in charged colloidal systems. Specifically, we find a family of optimal size ratios that…
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.
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.
We report Brownian dynamics simulation of the out-of-equilibrium dynamics (aging) in a colloidal suspension composed of rigid charged disks, one possible model for Laponite, a synthetic clay deeply investigated in the last few years by means of various experimental techniques. At variance with previous numerical investigations, mainly focusing on static structure and equilibrium dynamics, we explore the out-of-equilibrium aging dynamics. We analyze the wave-vector and waiting time dependence of the dynamics, focusing on the single-particle and collective density fluctuations (intermediate scat…
We study bidisperse colloidal suspensions confined within glass microcapillary tubes to model the glass transition in confined cylindrical geometries. We use high speed three-dimensional confocal microscopy to observe particle motions for a wide range of volume fractions and tube radii. Holding volume fraction constant, we find that particles move slower in thinner tubes. The tube walls induce a gradient in particle mobility: particles move substantially slower near the walls. This suggests that the confinement-induced glassiness may be due to an interfacial effect.
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 reversible aggregates formation in a shear thickening, concentrated colloidal suspension is investigated through speckle visibility spectroscopy, a dynamic light scattering technique recently introduced [P.K. Dixon and D.J. Durian, Phys. Rev. Lett. 90, 184302 (2003)]. Formation of particles aggregates is observed in the jamming regime, and their relaxation after shear cessation is monitored as a function of the applied shear stress. The aggregates relaxation time increases when a larger stress is applied. Several phenomena have been proposed to interpret this behavior: an increase of the a…
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 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 in industrial processes often exhibit shear thickening that is difficult to control actively. Here, we use piezoelectric transducers to apply acoustic perturbations to dynamically tune the suspension viscosity in the shear-thickening regime. We attribute the mechanism of dethickening to the disruption of shear-induced force chains via perturbations that are large relative to the particle roughness scale. The ease with which this technique can be adapted to various flow geometries makes it a powerful tool for actively controlling suspension flow properties and investigatin…
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…
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…
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…
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…
The response of a suspension under a variety of static or alternating external fields strongly depends on the equilibrium electric double layer that surrounds the colloidal particles in the suspension. The theoretical models for salt-free suspensions can be improved by incorporating non-uniform size effects and orientational ordering of water dipoles neglected in previous mean-field approaches, which are based on the Poisson-Boltzmann approach. Our model including non-uniform size effects and orientational ordering of water dipoles seems to have quite a promising effect because the model can p…
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.
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 develop a fully continuous model for colloidal suspensions with hydrodynamic interactions. The Navier Stokes Phase Field Crystal (NS-PFC) model combines ideas of dynamic density functional theory with particulate flow approaches and is derived in detail and related to other dynamic density functional theory approaches with hydrodynamic interactions. The derived system is numerically solved using adaptive finite elements and used to analyse colloidal crystallization in flowing environments demonstrating a strong coupling in both directions between the crystal shape and the flow field. We fur…
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.
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…
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…
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.
Coalescence event in pendant and sessile drop is distinguished by the formation and evolution of the liquid bridge created upon singular contact. The bridge radius, $R$, is known to evolve as $R\sim t^b$, with power-law exponent, $b$, signifying the dominant governing forces. In this work, we experimentally explore the phenomenon in sub-classes of complex fluids namely, colloidal and non-colloidal suspensions that have particle hydrodynamic interactions as origin of viscoelasticity. Our observations suggest that such fluids have flow dependent thinning response with finite elasticity in shear …
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.
The freezing of colloidal suspensions is encountered in many natural and engineering processes such as the freezing of soils, food engineering, and cryobiology. It can also be used as a bio-inspired, versatile, and environmentally-friendly processing route for porous materials and composites. Yet, it is still a puzzling phenomenon with many unexplained features, due to the complexity of the system and the space and time scales at which the process should be investigated. We demonstrate here the interest of fast X-ray computed tomography to provide time-lapse, three-dimensional, in situ imaging…
Exploring structural order in disordered systems including liquids and glasses is an intriguing but challenging issue in condensed matter physics. Here we construct a new parameter based on the angular distribution function of particles and show that this new orientational order has significantly higher correlation with dynamic heterogeneity compared to a translational parameter based on the radial distribution functions in colloidal glasses. The gradual development of orientational and translational order in supercooled liquids shows that the higher correlation between orientational order and…
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…
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 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.
We discuss the peculiarities of the Seebeck effect in stabilized electrolytes containing the colloidal particles. Its unusual feature is the two-stage character, with the linear increase of differential thermopower as the function of colloidal particles concentration $n_{\odot}$ during the first stage and dramatic drop of it at small $n_{\odot}$ during the second one (steady state). We show that the properties of the initial state are governed by the thermo-diffusion flows of the mobile ions of the stabilizing electrolyte medium itself and how the colloidal particles participate in formation o…
The key parameter controlling the glass transition of colloidal suspensions is $φ$, the fraction of the sample volume occupied by the particles. Unfortunately, changing $φ$ by varying an external parameter, \textit{e.g.} temperature $T$ as in molecular glass formers, is not possible, unless one uses thermosensitive colloidal particles, like the popular poly(N-isopropylacrylamide) (PNiPAM) microgels. These however have several drawbacks, including high deformability, osmotic deswelling and interpenetration, which complicate their use as a model system to study the colloidal glass transition. He…
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…
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…
We image the flow of a nearly random close packed, hard-sphere colloidal suspension (a `paste') in a square capillary using confocal microscopy. The flow consists of a `plug' in the center while shear occurs localized adjacent to the channel walls, reminiscent of yield-stress fluid behavior. However, the observed scaling of the velocity profiles with the flow rate strongly contrasts yield-stress fluid predictions. Instead, the velocity profiles can be captured by a theory of stress fluctuations originally developed for chute flow of dry granular media. We verified this behavior both for smooth…
