32 research outputs found
Density profiles of a colloidal liquid at a wall under shear flow
Using a dynamical density functional theory we analyze the density profile of
a colloidal liquid near a wall under shear flow. Due to the symmetries of the
system considered, the naive application of dynamical density functional theory
does not lead to a shear induced modification of the equilibrium density
profile, which would be expected on physical grounds. By introducing a
physically motivated dynamic mean field correction we incorporate the missing
shear induced interparticle forces into the theory. We find that the shear flow
tends to enhance the oscillations in the density profile of hard-spheres at a
hard-wall and, at sufficiently high shear rates, induces a nonequilibrium
transition to a steady state characterized by planes of particles parallel to
the wall. Under gravity, we find that the center-of-mass of the density
distribution increases with shear rate, i.e., shear increases the potential
energy of the particles
Density functional theory and demixing of binary hard rod-polymer mixtures
A density functional theory for a mixture of hard rods and polymers modeled
as chains built of hard tangent spheres is proposed by combining the functional
due to Yu and Wu for the polymer mixtures [J. Chem. Phys. {\bf 117}, 2368
(2002)] with the Schmidt's functional [Phys. Rev. E {\bf 63}, 50201 (2001)] for
rod-sphere mixtures. As a simple application of the functional, the demixing
transition into polymer-rich and rod-rich phases is examined. When the chain
length increases, the phase boundary broadens and the critical packing fraction
decreases. The shift of the critical point of a demixing transition is most
noticeable for short chains.Comment: 4 pages,2 figures, in press, PR
Capillary Condensation and Interface Structure of a Model Colloid-Polymer Mixture in a Porous Medium
We consider the Asakura-Oosawa model of hard sphere colloids and ideal
polymers in contact with a porous matrix modeled by immobilized configurations
of hard spheres. For this ternary mixture a fundamental measure density
functional theory is employed, where the matrix particles are quenched and the
colloids and polymers are annealed, i.e. allowed to equilibrate. We study
capillary condensation of the mixture in a tiny sample of matrix as well as
demixing and the fluid-fluid interface inside a bulk matrix. Density profiles
normal to the interface and surface tensions are calculated and compared to the
case without matrix. Two kinds of matrices are considered: (i) colloid-sized
matrix particles at low packing fractions and (ii) large matrix particles at
high packing fractions. These two cases show fundamentally different behavior
and should both be experimentally realizable. Furthermore, we argue that
capillary condensation of a colloidal suspension could be experimentally
accessible. We find that in case (ii), even at high packing fractions, the main
effect of the matrix is to exclude volume and, to high accuracy, the results
can be mapped onto those of the same system without matrix via a simple
rescaling.Comment: 12 pages, 9 figures, submitted to PR
Flow curves of colloidal dispersions close to the glass transition: Asymptotic scaling laws in a schematic model of mode coupling theory
The flow curves, viz. the curves of stationary stress under steady shearing,
are obtained close to the glass transition in dense colloidal dispersions using
asymptotic expansions in a schematic model of mode coupling theory. The shear
thinning of the viscosity in fluid states and the yielding of glassy states is
discussed. At the transition between fluid and shear-molten glass, simple and
generalized Herschel-Bulkley laws are derived with power law exponents that can
be computed for different particle interactions from the equilibrium structure
factor.Comment: 14 pages, 14 figures, 4 tables, Eur. Phys. J. E (submitted
Mechanical Responses and Stress Fluctuations of a Supercooled Liquid in a Sheared Non-Equilibrium State
A steady shear flow can drive supercooled liquids into a non-equilibrium
state. Using molecular dynamics simulations under steady shear flow
superimposed with oscillatory shear strain for a probe, non-equilibrium
mechanical responses are studied for a model supercooled liquid composed of
binary soft spheres. We found that even in the strongly sheared situation, the
supercooled liquid exhibits surprisingly isotropic responses to oscillating
shear strains applied in three different components of the strain tensor. Based
on this isotropic feature, we successfully constructed a simple two-mode
Maxwell model that can capture the key features of the storage and loss moduli,
even for highly non-equilibrium state. Furthermore, we examined the correlation
functions of the shear stress fluctuations, which also exhibit isotropic
relaxation behaviors in the sheared non-equilibrium situation. In contrast to
the isotropic features, the supercooled liquid additionally demonstrates
anisotropies in both its responses and its correlations to the shear stress
fluctuations. Using the constitutive equation (a two-mode Maxwell model), we
demonstrated that the anisotropic responses are caused by the coupling between
the oscillating strain and the driving shear flow. We measured the magnitude of
this violation in terms of the effective temperature. It was demonstrated that
the effective temperature is notably different between different components,
which indicates that a simple scalar mapping, such as the concept of an
effective temperature, oversimplifies the true nature of supercooled liquids
under shear flow. An understanding of the mechanism of isotropies and
anisotropies in the responses and fluctuations will lead to a better
appreciation of these violations of the FDT, as well as certain consequent
modifications to the concept of an effective temperature.Comment: 15pages, 17figure
Macromolecular theory of solvation and structure in mixtures of colloids and polymers
The structural and thermodynamic properties of mixtures of colloidal spheres
and non-adsorbing polymer chains are studied within a novel general
two-component macromolecular liquid state approach applicable for all size
asymmetry ratios. The dilute limits, when one of the components is at infinite
dilution but the other concentrated, are presented and compared to field theory
and models which replace polymer coils with spheres. Whereas the derived
analytical results compare well, qualitatively and quantitatively, with
mean-field scaling laws where available, important differences from ``effective
sphere'' approaches are found for large polymer sizes or semi-dilute
concentrations.Comment: 23 pages, 10 figure