Dynamical density functional theory: phase separation in a cavity and the influence of symmetry

Consider a fluid composed of two species of particles, where the interparticle pair potentials $u_{11} = u_{22} \neq u_{12}$. On confining an equal number of particles from each species in a cavity, one finds that the average one body density profiles of each species are constrained to be exactly the same due to the symmetry, when both external cavity potentials are the same. For a binary fluid of Brownian particles interacting via repulsive Gaussian pair potentials that exhibits phase separation, we study the dynamics of the fluid one body density profiles on breaking the symmetry of the external potentials, using the dynamical density functional theory of Marconi and Tarazona [{\it J. Chem. Phys.}, {\bf 110}, 8032 (1999)]. On breaking the symmetry we see that the fluid one body density profiles can then show the phase separation that is present.Comment: 7 pages, 4 figures. Accepted for the proceedings of the Liquid Matter conference 2005, to be publication in J. Phys.: Condens. Matte

Microscopic theory of solvent mediated long range forces: influence of wetting

We show that a general density functional approach for calculating the force between two big particles immersed in a solvent of smaller ones can describe systems that exhibit fluid-fluid phase separation: the theory captures effects of strong adsorption (wetting) and of critical fluctuations in the solvent. We illustrate the approach for the Gaussian core model, a simple model of a polymer mixture in solution and find extremely attractive, long ranged solvent mediated potentials between the big particles for state points lying close to the binodal, on the side where the solvent is poor in the species which is favoured by the big particles.Comment: 7 pages, 3 figures, submitted to Europhysics Letter

Dynamical density functional theory analysis of the laning instability in sheared soft matter

Using dynamical density functional theory (DDFT) methods we investigate the laning instability of a sheared colloidal suspension. The nonequilibrium ordering at the laning transition is driven by non-affine particle motion arising from interparticle interactions. Starting from a DDFT which incorporates the non-affine motion, we perform a linear stability analysis that enables identification of the regions of parameter space where lanes form. We illustrate our general approach by applying it to a simple one-component fluid of soft penetrable particles

Mean-field dynamical density functional theory

We examine the out-of-equilibrium dynamical evolution of density profiles of ultrasoft particles under time-varying external confining potentials in three spatial dimensions. The theoretical formalism employed is the dynamical density functional theory (DDFT) of Marini Bettolo Marconi and Tarazona [J. Chem. Phys. {\bf 110}, 8032 (1999)], supplied by an equilibrium excess free energy functional that is essentially exact. We complement our theoretical analysis by carrying out extensive Brownian Dynamics simulations. We find excellent agreement between theory and simulations for the whole time evolution of density profiles, demonstrating thereby the validity of the DDFT when an accurate equilibrium free energy functional is employed.Comment: 8 pagers, 4 figure

Solvent mediated interactions close to fluid-fluid phase separation: microscopic treatment of bridging in a soft core fluid

Using density functional theory we calculate the density profiles of a binary solvent adsorbed around a pair of big solute particles. All species interact via repulsive Gaussian potentials. The solvent exhibits fluid-fluid phase separation and for thermodynamic states near to coexistence the big particles can be surrounded by a thick adsorbed `wetting' film of the coexisting solvent phase. On reducing the separation between the two big particles we find there can be a `bridging' transition as the wetting films join to form a fluid bridge. The potential between the two big particles becomes long ranged and strongly attractive in the bridged configuration. Within our mean-field treatment the bridging transition results in a discontinuity in the solvent mediated force. We demonstrate that accounting for the phenomenon of bridging requires the presence of a non-zero bridge function in the correlations between the solute particles when our model fluid is described within a full mixture theory based upon the Ornstein-Zernike equations.Comment: 28 pages, 8 figure

Solidification in soft-core fluids: disordered solids from fast solidification fronts

Using dynamical density functional theory we calculate the speed of solidification fronts advancing into a quenched two-dimensional model fluid of soft-core particles. We find that solidification fronts can advance via two different mechanisms, depending on the depth of the quench. For shallow quenches, the front propagation is via a nonlinear mechanism. For deep quenches, front propagation is governed by a linear mechanism and in this regime we are able to determine the front speed via a marginal stability analysis. We find that the density modulations generated behind the advancing front have a characteristic scale that differs from the wavelength of the density modulation in thermodynamic equilibrium, i.e., the spacing between the crystal planes in an equilibrium crystal. This leads to the subsequent development of disorder in the solids that are formed. For the one-component fluid, the particles are able to rearrange to form a well-ordered crystal, with few defects. However, solidification fronts in a binary mixture exhibiting crystalline phases with square and hexagonal ordering generate solids that are unable to rearrange after the passage of the solidification front and a significant amount of disorder remains in the system.Comment: 18 pages, 14 fig

Dynamical density functional theory for the dewetting of evaporating thin films of nanoparticle suspensions exhibiting pattern formation

Recent experiments have shown that the striking structure formation in dewetting films of evaporating colloidal nanoparticle suspensions occurs in an ultrathin `postcursor' layer that is left behind by a mesoscopic dewetting front. Various phase change and transport processes occur in the postcursor layer, that may lead to nanoparticle deposits in the form of labyrinthine, network or strongly branched `finger' structures. We develop a versatile dynamical density functional theory to model this system which captures all these structures and may be employed to investigate the influence of evaporation/condensation, nanoparticle transport and solute transport in a differentiated way. We highlight, in particular, the influence of the subtle interplay of decomposition in the layer and contact line motion on the observed particle-induced transverse instability of the dewetting front.Comment: 5 pages, 5 figure

Modelling the evaporation of nanoparticle suspensions from heterogeneous surfaces

We present a Monte Carlo (MC) grid-based model for the drying of drops of a nanoparticle suspension upon a heterogeneous surface. The model consists of a generalised lattice-gas in which the interaction parameters in the Hamiltonian can be varied to model different properties of the materials involved. We show how to choose correctly the interactions, to minimise the effects of the underlying grid so that hemispherical droplets form. We also include the effects of surface roughness to examine the effects of contact-line pinning on the dynamics. When there is a `lid' above the system, which prevents evaporation, equilibrium drops form on the surface, which we use to determine the contact angle and how it varies as the parameters of the model are changed. This enables us to relate the interaction parameters to the materials used in applications. The model has also been applied to drying on heterogeneous surfaces, in particular to the case where the suspension is deposited on a surface consisting of a pair of hydrophilic conducting metal surfaces that are either side of a band of hydrophobic insulating polymer. This situation occurs when using inkjet printing to manufacture electrical connections between the metallic parts of the surface. The process is not always without problems, since the liquid can dewet from the hydrophobic part of the surface, breaking the bridge before the drying process is complete. The MC model reproduces the observed dewetting, allowing the parameters to be varied so that the conditions for the best connection can be established. We show that if the hydrophobic portion of the surface is located at a step below the height of the neighbouring metal, the chance of dewetting of the liquid during the drying process is significantly reduced.Comment: 14 pages, 14 figure

Soft core fluid in a quenched matrix of soft core particles: A mobile mixture in a model gel

We present a density-functional study of a binary phase-separating mixture of soft core particles immersed in a random matrix of quenched soft core particles of larger size. This is a model for a binary polymer mixture immersed in a crosslinked rigid polymer network. Using the replica `trick' for quenched-annealed mixtures we derive an explicit density functional theory that treats the quenched species on the level of its one-body density distribution. The relation to a set of effective external potentials acting on the annealed components is discussed. We relate matrix-induced condensation in bulk to the behaviour of the mixture around a single large particle. The interfacial properties of the binary mixture at a surface of the quenched matrix display a rich interplay between capillary condensation inside the bulk matrix and wetting phenomena at the matrix surface.Comment: 20 pages, 5 figures. Accepted for Phys. Rev.