Colloids coupled to a bath of swimming cells generically display enhanced diffusion. This transport dynamics stems from a subtle interplay between the active and passive particles that still resists our understanding despite decades of intense research. Here, we tackle the root of the problem by providing a quantitative characterisation of the single scattering events between a colloid and a bacterium. Based on our experiments, we build a minimal model that quantitatively predicts the geometry of the scattering trajectories, and enhanced colloidal diffusion at long times. This quantitative confrontation between theory and experiments elucidates the microscopic origin of enhanced transport. Collisions are solely ruled by stochastic contact interactions responsible both for genuine anomalous diffusion at short times and enhanced diffusion at long times with no ballistic regime at any scale.
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.
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 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 …
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 …
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…
Molecular dynamics (MD) simulations are used to determine the diffusion coefficients, electrophoretic mobilities and electrical conductivity of a charged colloidal suspension in the salt-free regime as a function of the colloid charge. The behavior of the colloidal particles' diffusion constant can be well understood in terms of two coupled effects: counterion 'condensation' and slowdown due to the relaxation effect. We find that the conductivity exhibits a maximum which approximately separates the regimes of counterion-dominated and colloid-dominated conduction. We analyze the electrophoretic…
We introduce a renormalized Jellium model to calculate the equation of state for charged colloidal suspensions. An almost perfect agreement with Monte Carlo simulations is found. Our self-consistent approach naturally allows to define the effective charge of particles {\em at finite colloidal density}. Although this quantity may differ significantly from its counterpart obtained from the standard Poisson-Boltzmann cell approach, the osmotic pressures for both models are in good agreement. We argue that by construction, the effective charge obtained using the Jellium approximation is more appro…
We study the order-disorder transition in colloidal suspensions under shear flow by performing Brownian dynamics simulations. We characterize the transition in terms of a statistical property of time-dependent maximum value of the structure factor. We find that its power spectrum exhibits the power-law behaviour only in the ordered phase. The power-law exponent is approximately -2 at frequencies greater than the magnitude of the shear rate, while the power spectrum exhibits the $1 / f$-type fluctuations in the lower frequency regime.
There is now convincing evidence that inter-particle frictional contacts are essential for observing shear-thickening in concentrated suspensions of compact particles. While this has inspired many strategies to tailor the rheology in these systems, in the more general case, viz-a-viz suspensions of anisotropic particles, the mechanism of shear-thickening remains unclear. Here through simultaneous measurements of the bulk viscosity and the first Normal stress difference, we show that strong shear thickening in suspensions of colloidal rods is accompanied by large positive normal stresses, indic…
Using a carefully justified development of Debye-Huckel theory for highly asymmetric electrolytes, one finds that a region of expanded phase instability, or miscibility gap, can appear for charge-stabilised colloidal suspensions at high charges and low ionic strengths. It is argued that this is offers a straightforward explanation for the observations of void structures and other anomalies in such suspensions in this region. The nature of the interface between coexisting phases, and general arguments that many-body attractions form a key part of the underlying physical picture, are also examin…
Our interest goes to the different virial contributions to the equation of state of charged colloidal suspensions. Neglect of surface effects in the computation of the colloidal virial term leads to spurious and paradoxical results. This pitfall is one of the several facets of the danger of a naive implementation of the so called One Component Model, where the micro-ionic degrees of freedom are integrated out to only keep in the description the mesoscopic (colloidal) degrees of freedom. On the other hand, due incorporation of wall induced forces dissolves the paradox brought forth in the naive…
We derive an expression for the static dielectric constant of the colloidal susp ensions based on the electrokinetic equations. The analysis assumes that the ions have the same diffusivity, and that the double layer is much thinner than the radius of curvature of the particles. It is shown that the dielectric increment of the double layer polarization mechanism is originated from the free energy stored in the salt concentration inhomogeniety. We also show that the dominant polarization charges in the theory are at the electrodes, rather than close to the particles.
Recent experiments have shown that various structures may be formed during the evaporative dewetting of thin films of colloidal suspensions. Nano-particle deposits of strongly branched `flower-like', labyrinthine and network structures are observed. They are caused by the different transport processes and the rich phase behaviour of the system. We develop a model for the system, based on a dynamical density functional theory, which reproduces these structures. The model is employed to determine the influences of the solvent evaporation and of the diffusion of the colloidal particles and of the…
We investigate colloidal suspensions under shear flow through numerical experiments. By measuring the time-correlation function of a bond-orientational order parameter, we find a divergent time scale near a transition point from a disordered fluid phase to an ordered fluid phase, where the order is characterized by a nonzero value of the bond-orientational order parameter. We also present a phase diagram in the $(ρ, \dotγ^{\mathrm{ex}})$ plane, where $ρ$ is the density of the colloidal particles and $\dotγ^{\mathrm{ex}}$ is the shear rate of the solvent. The transition line in the phase diagra…
The emergence of particle irreversibility in periodically driven colloidal suspensions has been interpreted as resulting either from a nonequilibrium phase transition to an absorbing state or from the chaotic nature of particle trajectories. Using a simple model of a driven suspension we show that a nonequilibrium phase transition is accompanied by hyperuniform static density fluctuations in the vicinity of the transition, where we also observe strong dynamic heterogeneities reminiscent of dynamics in glassy materials. We find that single particle dynamics becomes intermittent and strongly non…
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.
We consider the nonlinear rheology of dense colloidal suspensions under a time-dependent simple shear flow. Starting from the Smoluchowski equation for interacting Brownian particles advected by shearing (ignoring fluctuations in fluid velocity) we develop a formalism which enables the calculation of time-dependent, far-from-equilibrium averages. Taking shear-stress as an example we derive exactly a generalized Green-Kubo relation, and an equation of motion for the transient density correlator, involving a three-time memory function. Mode coupling approximations give a closed constitutive equa…
We develop a thermodynamic description of particles held at a fixed surface potential. This system is of particular interest in view of the continuing controversy over the possibility of a fluid-fluid phase separation in aqueous colloidal suspensions with monovalent counterions. The condition of fixed surface potential allows in a natural way to account for the colloidal charge renormalization. In a first approach, we assess the importance of the so called ``volume terms'', and find that in the absence of salt, charge renormalization is sufficient to stabilize suspension against a fluid-fluid …
The HNC Ornstein-Zernike integral equations are used to determine the properties of simple models of colloidal solutions where the colloids and ions are immersed in a solvent considered as a dielectric continuum and have a size ratio equal to 80 and a charge ratio varying between 1 and 4000. At an infinite dilution of colloids, the effective interactions between colloids and ions are determined for ionic concentrations ranging from 0.001 to 0.1 mol/l and compared to those derived from the Poisson-Boltzmann theory. At finite concentrations, we discuss on the basis of the HNC results the possibi…
Several statistical mechanical theories predict that colloidal suspensions of highly charged macroions and monovalent microions can exhibit unusual thermodynamic phase behavior when strongly deionized. Density-functional, extended Debye-Hückel, and response theories, within mean-field and linearization approximations, predict a spinodal phase instability of charged colloids below a critical salt concentration. Poisson-Boltzmann cell model studies of suspensions in Donnan equilibrium with a salt reservoir demonstrate that effective interactions and osmotic pressures predicted by such theories c…
We report the nematic and smectic ordering in a new aqueous suspension of monolayer $α$-Zirconium phosphate platelets possessing a high polydispersity in diameter but uniform thickness. We observe an isotropic--nematic transition as the platelet volume fraction increases, followed by the formation of a smectic, an elusive phase that has been rarely seen in discotic liquid crystals. The smectic phase is characterized by X-ray diffraction, high-resolution transmission electron microscopy, and optical microscopy. The phase equilibria in this highly polydisperse suspension is rationalized in terms…
Mixtures of active and passive particles are predicted to exhibit a variety of nonequilibrium phases. Here we report a dynamic clustering phase in mixtures of colloids and motile bacteria. We show that colloidal clustering results from a balance between bond breaking due to persistent active motion and bond stabilization due to torques that align active particle velocity tangentially to the passive particle surface. Furthermore, dynamic clustering spans a broad regime between diffusivity-based and motility-induced phase separation that subsumes typical bacterial motility parameters.
We theoretically investigate general properties of driven (sheared) colloidal suspensions in confinement, based on methods of classical density functional theory. In the absence of an exact closed (Smoluchowski-) equation for the one-particle density under shear, we formulate a set of general conditions for approximations, and show that a simple closure fulfills them. The exact microscopic stress tensor is identified. Exemplifying the situation near a wall (oriented parallel to the direction of shear), we note that the microscopic shear stress is not necessarily homogeneous. Formulating a seco…
We study numerically the influence of density and strain rate on the diffusion and mobility of a single tagged particle in a sheared colloidal suspension. We determine independently the time-dependent velocity autocorrelation functions and, through a novel method, the response functions with respect to a small force. While both the diffusion coefficient and the mobility depend on the strain rate the latter exhibits a rather weak dependency. Somewhat surprisingly, we find that the initial decay of response and correlation functions coincide, allowing for an interpretation in terms of an 'effect…
We study the dynamic yield stress in dense colloidal suspensions by analyzing the time evolution of the pair distribution function for colloidal particles interacting through a Lennard-Jones potential. We find that the equilibrium pair distribution function is unstable with respect to a certain anisotropic perturbation in the regime of low temperature and high density. By applying a bifurcation analysis to a system near the critical state at which the stability changes, we derive an amplitude equation for the critical mode. This equation is analogous to order parameter equations used to descri…
The effective interaction between charged colloidal particles confined between two planar like-charged walls is investigated using computer simulations of the primitive model describing asymmetric electrolytes. In detail, we calculate the effective force acting onto a single macroion and onto a macroion pair in the presence of slit-like confinement. For moderate Coulomb coupling, we find that this force is repulsive. Under strong coupling conditions, however, the sign of the force depends on the distance to the plates and on the interparticle distance. In particular, the particle-plate interac…
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 study numerically the crystallization process in a supersaturated suspension of repulsive colloidal particles driven by simple shear flow. The effect of the shear flow on crystallization is two-fold: while it suppresses the initial nucleation, once a large enough critical nucleus has formed its growth is enhanced by the shear flow. Combining both effects implies an optimal strain rate at which the overall crystallization rate has a maximum. To gain insight into the underlying mechanisms, we employ a discrete state model describing the transitions between the local structural configurations …
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.
Surface effects are generally prevailing in confined colloidal systems. Here we report on dispersed nanoparticles close to a fluid membrane. Exact results regarding the static organization are derived for a dilute solution of non-adhesive colloids. It is shown that thermal fluctuations of the membrane broaden the density profile, but on average colloids are neither accumulated nor depleted near the surface. The radial correlation function is also evaluated, from which we obtain the effective pair-potential between colloids. This entropically-driven interaction shares many similarities with the…
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.
One possible framework to interpret the irreversibility transition observed in periodically driven colloidal suspensions is that of a non-equilibrium phase transition towards an absorbing reversible state at low amplitude of the driving force. We consider a simple numerical model for driven suspensions which allows us to characterize in great detail a large body of physical observables that can be experimentally determined to assess the existence and universality class of such a non-equilibrium phase transition. Characterizing the behaviour of static and dynamic correlation functions both in r…
The phase behavior of colloidal particles embedded in a binary fluid is influenced by wetting layers surrounding each particle. The free energy of the fluid film depends on its morphology, i.e., on size, shape and connectivity. Under rather natural assumptions a general expression for the Hamiltonian can be given extending the model of hard spheres to partially penetrable shapes including energy contributions related to the volume, surface area, mean curvature, and Euler characteristic of the wetting layer. The complex spatial structure leads to multi-particle interactions of the colloidal par…
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.
To survive in harsh conditions, motile bacteria swim in complex environment and respond to the surrounding flow. Here we develop a PDE model describing how the flagella bending affects macroscopic properties of bacterial suspensions. First, we show how the flagella bending contributes to the decrease of the effective viscosity observed in dilute suspension. Our results do not impose tumbling (random re-orientation) as it was done previously to explain the viscosity reduction. Second, we demonstrate a possibility of bacterium escape from the wall entrapment due to the self-induced buckling of f…
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…
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…
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 study the collective dynamics of elongated swimmers in a very thin fluid layer by devising long, filamentous, non-tumbling bacteria. The strong confinement induces weak nematic alignment upon collision, which, for large enough density of cells, gives rise to global nematic order. This homogeneous but fluctuating phase, observed on the largest experimentally-accessible scale of millimeters, exhibits the properties predicted by standard models for flocking such as the Vicsek-style model of polar particles with nematic alignment: true long-range nematic order and non-trivial giant number fluct…
Bacteria suspension exhibits a wide range of collective phenomena arising from interactions between individual cells. Here we show Serratia marcescens cells near an air-liquid interface spontaneously aggregate into dynamic clusters through surface-mediated hydrodynamic interactions. These long-lived clusters translate randomly and rotate in the counter-clockwise direction; they continuously evolve, merge with others and split into smaller ones. Measurements indicate that long-ranged hydrodynamic interactions have strong influences on cluster properties. Bacterial clusters change material and f…
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…
We describe a new kind of self-propelling motion of bacteria based on the cooperative action of rotating flagella on the surface of bacteria. Describing the ensemble of rotating flagella in the framework of the hydrodynamics with spin the reciprocal theorem of Stokesian hydrodynamics is generalized accordingly. The velocity of the self-propulsion is expressed in terms of the characteristics of the vector field of flagella orientation and it is shown that unusually high velocities of \textit{Thiovulum majus} bacteria may be explained by the cooperative action of the rotating flagella. The expre…
The rheological response under simple shear of an active suspension of Escherichia coli is determined in a large range of shear rates and concentrations. The effective viscosity and the time scales characterizing the bacterial organization under shear are obtained. In the dilute regime, we bring evidences for a low shear Newtonian plateau characterized by a shear viscosity decreasing with concentration. In the semi-dilute regime, for particularly active bacteria, the suspension display a "super-fluid" like transition where the viscous resistance to shear vanishes, thus showing that macroscopic…
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-…
We study the collective dynamics of colloidal suspensions in the presence of a time-dependent potential, by means of dynamical density functional theory. We consider a non-linear diffusion equation for the density and show that spatial patterns emerge from a sinusoidal external potential with a time-dependent wavelength. These patterns are characterized by a sinusoidal density with the average wavelength and a Bessel-function envelope with an induced wavelength that depends only on the amplitude of the temporal oscillations. As a generalization of this result, we propose a design strategy to o…
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 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…
Micro- and nanoscale objects with anisotropic shape are key components of a variety of biological systems and inert complex materials, and represent fundamental building blocks of novel self-assembly strategies. The time scale of their thermal motion is set by their translational and rotational diffusion coefficients, whose measurement may become difficult for relatively large particles with small optical contrast. Here we show that Dark Field Differential Dynamic Microscopy is the ideal tool for probing the roto-translational Brownian motion of shape anisotropic particles. We demonstrate our …
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…
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.
The viscosity of an active suspension of E-Coli bacteria is determined experimentally in the dilute and semi dilute regime using a Y shaped micro-fluidic channel. From the position of the interface between the pure suspending fluid and the suspension, we identify rheo-thickening and rheo-thinning regimes as well as situations at low shear rate where the viscosity of the bacteria suspension can be lower than the viscosity of the suspending fluid. In addition, bacteria concentration and velocity profiles in the bulk are directly measured in the micro-channel.
