From Equilibrium to Steady State: The Transient Dynamics of Colloidal Liquids under Shear

We investigate stresses and particle motion during the start up of flow in a colloidal dispersion close to arrest into a glassy state. A combination of molecular dynamics simulation, mode coupling theory and confocal microscopy experiment is used to investigate the origins of the widely observed stress overshoot and (previously not reported) super-diffusive motion in the transient dynamics. A link between the macro-rheological stress versus strain curves and the microscopic particle motion is established. Negative correlations in the transient auto-correlation function of the potential stresses are found responsible for both phenomena, and arise even for homogeneous flows and almost Gaussian particle displacements.Comment: 24 pages, 14 figures, J. Phys.: Condens. Matter, in pres

Residual Stresses in Glasses

The history dependence of the glasses formed from flow-melted steady states by a sudden cessation of the shear rate $\dot\gamma$ is studied in colloidal suspensions, by molecular dynamics simulations, and mode-coupling theory. In an ideal glass, stresses relax only partially, leaving behind a finite persistent residual stress. For intermediate times, relaxation curves scale as a function of $\dot\gamma t$, even though no flow is present. The macroscopic stress evolution is connected to a length scale of residual liquefaction displayed by microscopic mean-squared displacements. The theory describes this history dependence of glasses sharing the same thermodynamic state variables, but differing static properties.Comment: submitted to Physical Revie

Mobility and Diffusion of a Tagged Particle in a Driven Colloidal Suspension

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 'effective temperature'. Such a phenomenological effective temperature recovers the Einstein relation in nonequilibrium. We show that our data is well described by two expansions to lowest order in the strain rate.Comment: submitted to EP

Controlling colloidal sedimentation using time dependent shear

Employing a recently developed dynamical density functional theory we study the response of a colloidal sediment above a wall to shear, demonstrating the time dependent changes of the density distribution and its center-of-mass after switching shear either on or off and under oscillatory shear. Following the onset of steady shear we identify two dynamical mechanisms, distinguished by their timescales. Shortly after the onset, a transient enhancement of the packing structure at the wall reflects the self-organization into lanes. On a much longer timescale these effects are transmitted to the bulk, leading to migration away from the wall and an increase in the center-of-mass. Under oscillatory shear flow the center-of-mass enters a stationary state, reminiscent of a driven damped oscillator.Comment: 6 pages, 4 figure

Crowding of Polymer Coils and Demixing in Nanoparticle-Polymer Mixtures

The Asakura-Oosawa-Vrij (AOV) model of colloid-polymer mixtures idealizes nonadsorbing polymers as effective spheres that are fixed in size and impenetrable to hard particles. Real polymer coils, however, are intrinsically polydisperse in size (radius of gyration) and may be penetrated by smaller particles. Crowding by nanoparticles can affect the size distribution of polymer coils, thereby modifying effective depletion interactions and thermodynamic stability. To analyse the influence of crowding on polymer conformations and demixing phase behaviour, we adapt the AOV model to mixtures of nanoparticles and ideal, penetrable polymer coils that can vary in size. We perform Gibbs ensemble Monte Carlo simulations, including trial nanoparticle-polymer overlaps and variations in radius of gyration. Results are compared with predictions of free-volume theory. Simulation and theory consistently predict that ideal polymers are compressed by nanoparticles and that compressibility and penetrability stabilise nanoparticle-polymer mixtures.Comment: 18 pages, 4 figure

Statics and Dynamics of Colloid-Polymer Mixtures Near Their Critical Point of Phase Separation: A Computer Simulation Study of a Continuous AO Model

We propose a new coarse-grained model for the description of liquid-vapor phase separation of colloid-polymer mixtures. The hard-sphere repulsion between colloids and between colloids and polymers, which is used in the well-known Asakura-Oosawa (AO) model, is replaced by Weeks-Chandler-Anderson potentials. Similarly, a soft potential of height comparable to thermal energy is used for the polymer-polymer interaction, rather than treating polymers as ideal gas particles. It is shown by grand-canonical Monte Carlo simulations that this model leads to a coexistence curve that almost coincides with that of the AO model and the Ising critical behavior of static quantities is reproduced. Then the main advantage of the model is exploited - its suitability for Molecular Dynamics simulations - to study the dynamics of mean square displacements of the particles, transport coefficients such as the self-diffusion and interdiffusion coefficients, and dynamic structure factors. While the self-diffusion of polymers increases slightly when the critical point is approached, the self-diffusion of colloids decreases and at criticality the colloid self-diffusion coefficient is about a factor of 10 smaller than that of the polymers. Critical slowing down of interdiffusion is observed, which is qualitatively similar to symmetric binary Lennard-Jones mixtures, for which no dynamic asymmetry of self-diffusion coefficients occurs.Comment: 42 pages, 17 figures, submitted to J. Chem. Phy

Nonlinear rheology of colloidal dispersions

Colloidal dispersions are commonly encountered in everyday life and represent an important class of complex fluid. Of particular significance for many commercial products and industrial processes is the ability to control and manipulate the macroscopic flow response of a dispersion by tuning the microscopic interactions between the constituents. An important step towards attaining this goal is the development of robust theoretical methods for predicting from first-principles the rheology and nonequilibrium microstructure of well defined model systems subject to external flow. In this review we give an overview of some promising theoretical approaches and the phenomena they seek to describe, focusing, for simplicity, on systems for which the colloidal particles interact via strongly repulsive, spherically symmetric interactions. In presenting the various theories, we will consider first low volume fraction systems, for which a number of exact results may be derived, before moving on to consider the intermediate and high volume fraction states which present both the most interesting physics and the most demanding technical challenges. In the high volume fraction regime particular emphasis will be given to the rheology of dynamically arrested states.Comment: Review articl

The Physics of the Colloidal Glass Transition

As one increases the concentration of a colloidal suspension, the system exhibits a dramatic increase in viscosity. Structurally, the system resembles a liquid, yet motions within the suspension are slow enough that it can be considered essentially frozen. This kinetic arrest is the colloidal glass transition. For several decades, colloids have served as a valuable model system for understanding the glass transition in molecular systems. The spatial and temporal scales involved allow these systems to be studied by a wide variety of experimental techniques. The focus of this review is the current state of understanding of the colloidal glass transition. A brief introduction is given to important experimental techniques used to study the glass transition in colloids. We describe features of colloidal systems near and in glassy states, including tremendous increases in viscosity and relaxation times, dynamical heterogeneity, and ageing, among others. We also compare and contrast the glass transition in colloids to that in molecular liquids. Other glassy systems are briefly discussed, as well as recently developed synthesis techniques that will keep these systems rich with interesting physics for years to come.Comment: 56 pages, 18 figures, Revie

Thermodynamic consistent transport theory of Li-Ion batteries

We will present a rigorous derivation of the equations and interface conditions for ion, charge and heat transport in Li-ion insertion batteries. The derivation is based exclusively on universally accepted principles of nonequilibrium thermodynamics and the assumption of a one step intercalation reaction at the interface of electrolyte and active particles. Without loss of generality the transport in the active particle is assumed to be isotropic. The electrolyte is described as a fully dissociated salt in a neutral solvent. The presented theory is valid for transport on a spatial scale for which local charge neutrality holds i.e. beyond the scale of the diffuse double layer. Charge neutrality is explicitely used to determine the correct set of thermodynamically independent variables. The theory guarantees strictly positive entropy production. The various contributions to the Peltier coeficients for the interface between the active particles and the electrolyte as well as the contributions to the heat of mixing are obtained as a result of the theory

An overview on the usage of some model reduction approaches for simulations of Li-ion transport in batteries

In this work, some model reduction approaches for performing simulations with a pseudo-2D model of Li-ion battery are presented. A full pseudo-2D model of processes in Li-ion batteries is presented following [3], and three methods to reduce the order of the full model are considered. These are: i) directly reduce the model order using proper orthogonal decomposition, ii) using fractional time step discretization in order to solve the equations in decoupled way, and iii) reformulation approaches for the diffusion in the solid phase. Combinations of above methods are also considered. Results from numerical simulations are presented, and the efficiency and the accuracy of the model reduction approaches are discussed