Simulation and theory of fluid demixing and interfacial tension of mixtures of colloids and nonideal polymers.

An extension of the Asakura-Oosawa-Vrij model of hard sphere colloids and non-adsorbing polymers, that takes polymer non-ideality into account through a repulsive stepfunction pair potential between polymers, is studied with grand canonical Monte Carlo simulations and density functional theory. Simulation results validate previous theoretical findings for the shift of the bulk fluid demixing binodal upon increasing strength of polymer-polymer repulsion, promoting the tendency to mix. For increasing strength of the polymer-polymer repulsion, simulation and theory consistently predict the interfacial tension of the free colloidal liquid-gas interface to decrease significantly for fixed colloi…

Capillary Waves in a Colloid-Polymer Interface

The structure and the statistical fluctuations of interfaces between coexisting phases in the Asakura-Oosawa (AO) model for a colloid--polymer mixture are analyzed by extensive Monte Carlo simulations. We make use of a recently developed grand canonical cluster move with an additional constraint stabilizing the existence of two interfaces in the (rectangular) box that is simulated. Choosing very large systems, of size LxLxD with L=60 and D=120, measured in units of the colloid radius, the spectrum of capillary wave-type interfacial excitations is analyzed in detail. The local position of the interface is defined in terms of a (local) Gibbs surface concept. For small wavevectors capillary wa…

From capillary condensation to interface localization transitions in colloid-polymer mixtures confined in thin-film geometry.

Monte Carlo simulations of the Asakura-Oosawa (AO) model for colloid-polymer mixtures confined between two parallel repulsive structureless walls are presented and analyzed in the light of current theories on capillary condensation and interface localization transitions. Choosing a polymer to colloid size ratio of q=0.8 and studying ultrathin films in the range of D=3 to D=10 colloid diameters thickness, grand canonical Monte Carlo methods are used; phase transitions are analyzed via finite size scaling, as in previous work on bulk systems and under confinement between identical types of walls. Unlike the latter work, inequivalent walls are used here: while the left wall has a hard-core rep…

Finite-size scaling in Ising-like systems with quenched random fields: Evidence of hyperscaling violation

In systems belonging to the universality class of the random field Ising model, the standard hyperscaling relation between critical exponents does not hold, but is replaced by a modified hyperscaling relation. As a result, standard formulations of finite size scaling near critical points break down. In this work, the consequences of modified hyperscaling are analyzed in detail. The most striking outcome is that the free energy cost \Delta F of interface formation at the critical point is no longer a universal constant, but instead increases as a power law with system size, \Delta F proportional to $L^\theta$, with $\theta$ the violation of hyperscaling critical exponent, and L the linear ex…

Simulation of Transport in Partially Miscible Binary Fluids: Combination of Semigrandcanonical Monte Carlo and Molecular Dynamics Methods

Binary Fluids that exhibit a miscibility gap are ubiquitous in nature (glass melts, polymer solutions and blends, mixtures of molten metals, etc.) and exhibit a delicate interplay between static and dynamic properties. This is exemplified for a simple model system, the symmetrical AB Lennard-Jones mixture. It is shown how semigrandcanonical Monte Carlo methods, that include A→B (B→A) identity switches as Monte Carlo moves, can yield the phase diagram, the interfacial tension between coexisting phases, and various pair correlation functions and structure factors. In addition to the build-up of long-ranged concentration correlations near the critical point, unmixing is also accompanied by the…

Critical phenomena in colloid-polymer mixtures: interfacial tension, order parameter, susceptibility, and coexistence diameter.

The critical behavior of a model colloid-polymer mixture, the so-called AO model, is studied using computer simulations and finite size scaling techniques. Investigated are the interfacial tension, the order parameter, the susceptibility and the coexistence diameter. Our results clearly show that the interfacial tension vanishes at the critical point with exponent 2\nu ~ 1.26. This is in good agreement with the 3D Ising exponent. Also calculated are critical amplitude ratios, which are shown to be compatible with the corresponding 3D Ising values. We additionally identify a number of subtleties that are encountered when finite size scaling is applied to the AO model. In particular, we find …

Monte Carlo simulations of phase transitions of systems in nanoscopic confinement

Abstract When simple or complex fluids are confined to ultrathin films or channels or other cavities of nanoscopic linear dimensions, the interplay of finite size and surface controls the phase behavior, and may lead to phase transitions rather different from the corresponding phenomena in the bulk. Monte Carlo simulation is a very suitable tool to clarify the complex behavior of such systems, since the boundary conditions providing the confinement can be controlled and arbitrarily varied, and detailed structural information on the inhomogeneous states of the considered systems is available. Examples used to illustrate these concepts include simple Ising models in pores and double-pyramid-s…

Monolayer curvature stabilizes nanoscale raft domains in mixed lipid bilayers

According to the lipid raft hypothesis, biological lipid membranes are laterally heterogeneous and filled with nanoscale ordered "raft" domains, which are believed to play an important role for the organization of proteins in membranes. However, the mechanisms stabilizing such small rafts are not clear, and even their existence is sometimes questioned. Here we report the observation of raft-like structures in a coarse-grained molecular model for multicomponent lipid bilayers. On small scales, our membranes demix into a liquid ordered (lo) and a liquid disordered (ld) phase. On large scales, phase separation is suppressed and gives way to a microemulsion-type state that contains nanometer si…

Statics and dynamics of colloid-polymer mixtures near their critical point of phase separation: A computer simulation study of a continuous Asakura–Oosawa 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 …

Monte Carlo Study of the Isotropic-Nematic Interface in Suspensions of Spherocylinders

The isotropic to nematic transition in suspensions of anisotropic colloids is studied by means of grand canonical Monte Carlo simulation. From measurements of the grand canonical probability distribution of the particle density, the coexistence densities of the isotropic and the nematic phase are determined, as well as the interfacial tension.

Phase diagram and structure of colloid-polymer mixtures confined between walls

The influence of confinement, due to flat parallel structureless walls, on phase separation in colloid-polymer mixtures, is investigated by means of grand-canonical Monte Carlo simulations. Ultra-thin films, with thicknesses between $D=3-10$ colloid diameters, are studied. The Asakura-Oosawa model [J. Chem. Phys. 22, 1255 (1954)] is used to describe the particle interactions. To simulate efficiently, a ``cluster move'' [J. Chem. Phys. 121, 3253 (2004)] is used in conjunction with successive umbrella sampling [J. Chem. Phys. 120, 10925 (2004)]. These techniques, when combined with finite size scaling, enable an accurate determination of the unmixing binodal. Our results show that the critica…

Confinement effects on phase behavior of soft matter systems.

When systems that can undergo phase separation between two coexisting phases in the bulk are confined in thin film geometry between parallel walls, the phase behavior can be profoundly modified. These phenomena shall be described and exemplified by computer simulations of the Asakura-Oosawa model for colloid-polymer mixtures, but applications to other soft matter systems (e.g. confined polymer blends) will also be mentioned. Typically a wall will prefer one of the phases, and hence the composition of the system in the direction perpendicular to the walls will not be homogeneous. If both walls are of the same kind, this effect leads to a distortion of the phase diagram of the system in thin …

Colloid-polymer mixtures between asymmetric walls: Evidence for an interface localization transition

We demonstrate via computer simulation that mixtures of colloids and polymers confined to thin films have the ability to undergo an interface localization transition. While one wall of the film is assumed to be hard for both particles, at the other wall, an additional repulsive potential acts, but on the colloids only. By varying the strength of this repulsion, a crossover from capillary condensation to interface localization is found. The latter occurs under conditions where in the bulk almost complete phase separation has occurred.

Critical behavior of a colloid-polymer mixture confined between walls

We investigate the influence of confinement on phase separation in colloid-polymer mixtures. To describe the particle interactions, the colloid-polymer model of Asakura and Oosawa [J. Chem. Phys. 22, 1255 (1954)] is used. Grand canonical Monte Carlo simulations are then applied to this model confined between two parallel hard walls, separated by a distance D=5 colloid diameters. We focus on the critical regime of the phase separation and look for signs of crossover from three-dimensional (3D) Ising to two-dimensional (2D) Ising universality. To extract the critical behavior, finite size scaling techniques are used, including the recently proposed algorithm of Kim et al. [Phys. Rev. Lett. 91…

Isotropic-nematic interfacial tension of hard and soft rods: Application of advanced grand canonical biased-sampling techniques

Coexistence between the isotropic and the nematic phase in suspensions of rods is studied using grand canonical Monte Carlo simulations with a bias on the nematic order parameter. The biasing scheme makes it possible to estimate the interfacial tension gamma in systems of hard and soft rods. For hard rods with L/D=15, we obtain gamma ~ 1.4 kB T/L^2, with L the rod length, D the rod diameter, T the temperature, and kB the Boltzmann constant. This estimate is in good agreement with theoretical predictions, and the order of magnitude is consistent with experiments.

Isotropic-nematic interface and wetting in suspensions of colloidal platelets.

We study interfacial phenomena in a colloidal dispersion of sterically stabilized gibbsite platelets, exhibiting coexisting isotropic and nematic phases separated by a sharp horizontal interface. The nematic phase wets a vertical glass wall and polarized light micrographs reveal homeotropic surface anchoring both at the free isotropic-nematic interface and at the wall. On the basis of complete wetting of the wall by the nematic phase, as found in our density functional calculations and computer simulations, we analyze the balance between Frank elasticity and surface anchoring near the contact line. Because of weak surface anchoring, the director field in the capillary rise region is uniform…

Interfacial tension of the isotropic-nematic interface in suspensions of soft spherocylinders.

The isotropic to nematic transition in a system of soft spherocylinders is studied by means of grand canonical Monte Carlo simulations. The probability distribution of the particle density is used to determine the coexistence density of the isotropic and the nematic phases. The distributions are also used to compute the interfacial tension of the isotropic--nematic interface, including an analysis of finite size effects. Our results confirm that the Onsager limit is not recovered until for very large elongation, exceeding at least L/D=40, with L the spherocylinder length and D the diameter. For smaller elongation, we find that the interfacial tension increases with increasing L/D, in agreem…

Bulk and interfacial properties in colloid-polymer mixtures

Large-scale Monte Carlo simulations of a phase-separating colloid-polymer mixture are performed and compared to recent experiments. The approach is based on effective interaction potentials in which the central monomers of self-avoiding polymer chains are used as effective coordinates. By incorporating polymer nonideality together with soft colloid-polymer repulsion, the predicted binodal is in excellent agreement with recent experiments. In addition, the interfacial tension as well as the capillary length are in quantitative agreement with experimental results obtained at a number of points in the phase-coexistence region, without the use of any fit parameters.

Phase Behavior of Polymer-Containing Systems: Recent Advances Through Computer Simulation