53 research outputs found
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 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 , 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
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