Daniel de las Heras

Floating nematic phase in colloidal platelet-sphere mixtures

The phase behaviour of colloidal dispersions is interesting for fundamental reasons and for technological applications such as photonic crystals and electronic paper. Sedimentation, which in everyday life is relevant from blood analysis to the shelf life of paint, is a means to determine phase boundaries by observing distinct layers in samples that are in sedimentation-diffusion equilibrium. However, disentangling the effects due to interparticle interactions, which generate the bulk phase diagram, from those due to gravity is a complex task. Here we show that a line in the space of chemical potentials µi, where i labels the species, represents a sedimented sample and that each crossing of this sedimentation path with a binodal generates an interface under gravity. Complex phase stacks can result, such as the sandwich of a floating nematic layer between top and bottom isotropic phases that we observed in a mixture of silica spheres and gibbsite platelets.

Properties of patchy colloidal particles close to a surface: A Monte Carlo and density functional study

We investigate the behavior of a patchy particle model close to a hard-wall via Monte Carlo simulation and density functional theory (DFT). Two DFT approaches, based on the homogeneous and inhomogeneous versions of Wertheims first order perturbation theory for the association free energy are used. We evaluate, by simulation and theory, the equilibrium bulk phase diagram of the fluid and analyze the surface properties for two isochores, one of which is close to the liquid side of the gas-liquid coexistence curve. We find that the density profile near the wall crosses over from a typical high-temperature adsorption profile to a low-temperature desorption one, for the isochore close to coexistence. We relate this behavior to the properties of the bulk network liquid and find that the theoretical descriptions are reasonably accurate in this regime. At very low temperatures, however, an almost fully bonded network is formed, and the simulations reveal a second adsorption regime which is not captured by DFT. We trace this failure to the neglect of orientational correlations of the particles, which are found to exhibit surface induced orientational order in this regime.

Computing the phase diagram of binary mixtures: A patchy particle case study

We investigate the phase behaviour of 2D mixtures of bi-functional and three-functional patchy particles and 3D mixtures of bi-functional and tetra-functional patchy particles by means of Monte Carlo simulations and Wertheim theory. We start by computing the critical points of the pure systems and then we investigate how the critical parameters change upon lowering the temperature. We extend the successive umbrella sampling method to mixtures to make it possible to extract information about the phase behaviour of the system at a fixed temperature for the whole range of densities and compositions of interest.

Confinement of two-dimensional rods in slit pores and square cavities

Using Monte Carlo simulation, we analyse the behaviour of two-dimensional hard rods in four different types of geometric confinement: (i) a slit pore where the particles are confined between two parallel walls with homeotropic anchoring; (ii) a hybrid slit pore formed by a planar and a homeotropic wall; square cavities that frustrate the orientational order by imposing either (iii) homeotropic or (iv) planar wall anchoring. We present results for the state diagram as a function of the packing fraction and the degree of confinement. Under extreme confinement, unexpected states appear with lower symmetries than those of the corresponding stable states in bulk, such as the formation of states that break the anchoring constraints or the symmetry imposed by the surfaces. In both types of square cavities, the particles form disclinations at intermediate densities. At high densities, however, the elastic stress is relaxed via the formation of domain walls where the director rotates abruptly by 90°.

Bulk fluid phase behaviour of colloidal platelet-sphere and platelet-polymer mixtures

Using a geometry-based fundamental measure density functional theory, we calculate bulk fluid phase diagrams of colloidal mixtures of vanishingly thin hard circular platelets and hard spheres. We find isotropic–nematic phase separation, with strong broadening of the biphasic region, upon increasing the pressure. In mixtures with large size ratio of platelet and sphere diameters, there is also demixing between two nematic phases with differing platelet concentrations. We formulate a fundamental measure density functional for mixtures of colloidal platelets and freely overlapping spheres, which represent ideal polymers, and use it to obtain phase diagrams. We find that, for low platelet–polymer size ratio, in addition to isotropic–nematic and nematic–nematic phase coexistence, platelet–polymer mixtures also display isotropic–isotropic demixing. By contrast, we do not find isotropic–isotropic demixing in hard-core platelet–sphere mixtures for the size ratios considered.

Superadiabatic forces in Brownian many-body dynamics.

Theoretical approaches to nonequilibrium many-body dynamics generally rest upon an adiabatic assumption, whereby the true dynamics is represented as a sequence of equilibrium states. Going beyond this simple approximation is a notoriously difficult problem. For the case of classical Brownian many-body dynamics, we present a simulation method that allows us to isolate and precisely evaluate superadiabatic correlations and the resulting forces. Application of the method to a system of one-dimensional hard particles reveals the importance for the dynamics, as well as the complexity, of these nontrivial out-of-equilibrium contributions. Our findings help clarify the status of dynamical density functional theory and provide a rational basis for the development of improved theories.

Topological protection of multiparticle dissipative transport.

Topological protection allows robust transport of localized phenomena such as quantum information, solitons and dislocations. The transport can be either dissipative or non-dissipative. Here, we experimentally demonstrate and theoretically explain the topologically protected dissipative motion of colloidal particles above a periodic hexagonal magnetic pattern. By driving the system with periodic modulation loops of an external and spatially homogeneous magnetic field, we achieve total control over the motion of diamagnetic and paramagnetic colloids. We can transport simultaneously and independently each type of colloid along any of the six crystallographic directions of the pattern via adiabatic or deterministic ratchet motion. Both types of motion are topologically protected. As an application, we implement an automatic topologically protected quality control of a chemical reaction between functionalized colloids. Our results are relevant to other systems with the same symmetry.

Sedimentation stacking diagram of binary colloidal mixtures and bulk phases in the plane of chemical potentials.

We give a full account of a recently proposed theory that explicitly relates the bulk phase diagram of a binary colloidal mixture to its phase stacking phenomenology under gravity (de las Heras and Schmidt 2013 Soft Matter 9 8636). As we demonstrate, the full set of possible phase stacking sequences in sedimentation-diffusion equilibrium originates from straight lines (sedimentation paths) in the chemical potential representation of the bulk phase diagram. From the analysis of various standard topologies of bulk phase diagrams, we conclude that the corresponding sedimentation stacking diagrams can be very rich, even more so when finite sample height is taken into account. We apply the theory to obtain the stacking diagram of a mixture of nonadsorbing polymers and colloids. We also present a catalog of generic phase diagrams in the plane of chemical potentials in order to facilitate the practical application of our concept, which also generalizes to multi-component mixtures.

The phase stacking diagram of colloidal mixtures under gravity

The observation of stacks of distinct layers in a colloidal or liquid mixture in the sedimentation–diffusion equilibrium is a striking consequence of bulk phase separation. Drawing quantitative conclusions about the phase diagram is, however, very delicate. Here we introduce the Legendre transform of the chemical potential representation of the bulk phase diagram to obtain a unique stacking diagram of all possible stacks under gravity. Simple bulk phase diagrams generically lead to complex stacking diagrams. We apply the theory to a binary hard core platelet mixture with only two-phase bulk coexistence, and find that the stacking diagram contains six types of stacks with up to four distinct layers. These results can be tested experimentally in colloidal platelet mixtures. In general, an extended Gibbs phase rule determines the maximum number of sedimented layers as a function of the number of binodals and their inflection points.

The role of sample height in the stacking diagram of colloidal mixtures under gravity

Bulk phase separation is responsible for the occurrence of stacks of different layers in sedimentation of colloidal mixtures. A recently proposed theory (de las Heras and Schmidt 2013 Soft Matter 9 8636) establishes a unique connection between the bulk phase behaviour and sedimentation-diffusion-equilibrium. The theory constructs a stacking diagram of all possible sequences of stacks under gravity in the limit of very high (infinite) sample heights. Here, we study the stacking diagrams of colloidal mixtures at finite sample height, h. We demonstrate that h plays a vital role in sedimentation-diffusion-equilibrium of colloidal mixtures. The region of the stacking diagram occupied by a given sequence of stacks depends on h. Hence, two samples with different heights but identical colloidal concentrations can develop different stacking sequences. In addition, the stacking diagrams for different heights can be qualitatively different since some stacking sequences occur only in a given interval of sample heights. We use the theory to investigate the stacking diagrams of both model bulk systems and mixtures of patchy particles that differ either by the number or by the types of patches.