Critical behavior of colloid-polymer mixtures in random porous media

We show that the critical behavior of a colloid-polymer mixture inside a random porous matrix of quenched hard spheres belongs to the universality class of the random-field Ising model. We also demonstrate that random-field effects in colloid-polymer mixtures are surprisingly strong. This makes these systems attractive candidates to study random-field behavior experimentally.     

Phase behaviour of colloid-polymer mixtures

Summary We review the phase behaviour of mixtures of colloids and non-adsorbing polymers. The exclusion of polymer molecules from overlapping ?depletion zones? between two neighbouring colloidal particles results in an unbalanced osmotic pressure pushing the particles together. This depletion potential is separately tunable in range and depth. Theory predicts that the resulting phase behaviour is sensitive to ξ=r _g/R, the ratio of the radius of gyration of a polymer molecule, to the radius of the colloid. At large ξ, a stable colloidalliquid phase becomes possible. This has been confirmed by recent experiments. The formation of non-equilibrium ?transient gel? states when the size ratio is small (≈0.08) is also introduced briefly. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Life at ultralow interfacial tension: wetting, waves and droplets in demixed colloid-polymer mixtures

Mixtures of colloids and polymers display a rich phase behavior, involving colloidal gas (rich in polymer, poor in colloid), colloidal liquid (poor in polymer, rich in colloid) and colloidal crystal phases (poor in polymer, highly ordered colloids). Recently, the colloidal gas-colloidal liquid interface received considerable attention as well. Due to the colloidal length scale the interfacial tension is much lower than in the atomic or molecular analog (nN/m instead of mN/m). This ultra-low interfacial tension has pronounced effects on the kinetics of phase separation, the colloidal gas-liquid profile near a single wall and the thermally induced fluctuations of the interface. The amplitudes of these thermally excited capillary waves are restrained by the interfacial tension and are for that reason of the order of the particle diameter. Therefore, in molecular systems, the capillary waves can only be seen indirectly in scattering experiments. In colloidal systems, however, the wave amplitudes are on a (sub) micrometer scale. This fact enables the direct observation of capillary waves in both real space and real time using confocal scanning laser microscopy. Moreover, the real space technique enables us to demonstrate the strong influence of interface fluctuations on droplet coalescence and droplet break up.     

Entropic wetting and many-body induced layering in a model colloid-polymer mixture

We develop an efficient simulation scheme to study a model suspension of equally sized colloidal hard spheres and nonadsorbing ideal polymer coils, both in bulk and adsorbed against a planar hard wall. The many-body character of the polymer-mediated effective interactions between the colloids yields a bulk phase diagram and adsorption phenomena that differ substantially from those found for pairwise simple fluids; e.g., we find an anomalously large bulk liquid regime and, far from the bulk triple point, three layering transitions in the partial wetting regime prior to a transition to complete wetting by colloidal liquid.     

Ultrasoft colloid-polymer mixtures: structure and phase diagram

Binary mixtures of ultrasoft colloids and linear polymer chains were investigated by small-angle neutron scattering and liquid state theory. We show that experimental data can be described by employing recently developed effective interactions between the colloid and the polymer chains, in which both components are modeled as point particles in a coarse-grained approach, in which the monomers have been traced out. Quantitative, parameter-free agreement between experiment and theory for the pair correlations, the phase behavior and the concentration dependence of the interaction length is achieved.     

Fluctuation forces and wetting layers in colloid-polymer mixtures

We present confocal microscopy experiments on the wetting of phase-separated colloid-polymer mixtures. We observe that an unusually thick wetting layer of the colloid-rich phase forms at the walls of the glass container that holds the mixture. Because of the ultralow interfacial tension between the colloid-rich and the polymer-rich phases, the thermally activated roughness of the interfaces becomes very big and measurable. We observe that close to the critical point the roughness of the interface between the wetting layer and the polymer-rich phase decreases with decreasing layer thickness: large excursions of the interface are confined in the wetting layer. The measured relationship between the roughness and the thickness of the wetting layer is in qualitative agreement with the predictions of renormalization group theory for short-range forces and complete wetting.     

Influence of polymer-excluded volume on the phase-behavior of colloid-polymer mixtures

We determine the depletion-induced phase-behavior of hard-sphere colloids and interacting polymers by large-scale Monte Carlo simulations using very accurate coarse-graining techniques. A comparison with standard Asakura-Oosawa model theories and simulations shows that including excluded-volume interactions between polymers leads to qualitative differences in the phase diagrams. These effects become increasingly important for larger relative polymer size. Our simulation results agree quantitatively with recent experiments.     

Binary granular gas mixtures: Theory,layering effects and some open questions

A theory of dilute binary granular gas mixtures comprising smooth spheres, which is formally valid for all physical values of the pertinent coefficients of restitution, is presented. Constitutive relations are obtained using the Chapman Enskog procedure, in the framework of which relatively high orders in the Sonine polynomial expansion are employed. The latter is made possible by a computer-aided method. The transport coefficients are shown to converge as a function of the number of Sonine polynomials employed, typically requiring 3 polynomials, but in some cases up to 6 polynomials are required for convergence to within 1%. A comparison with results obtained using the Grad method helps reveal the limitations of the Chapman-Enskog expansion. In particular, in some cases both the Chapman Enskog expansion and the Grad method give unphysical results, though they agree with each other. These issues are related to the lack of scale separation in granular gases. Using the constitutive relations we obtain a novel segregation pattern in vertically vibrated granular mixtures, which comprises up to five layers; this is an extension of a previously obtained three-layer configuration. Finally, the question of effective hydrodynamic boundary conditions at the transition to the Knudsen regime is discussed: in particular, it seems that in some cases the boundary condition for the heat flux in the hydrodynamic regime is “unphysical”.     

Simulation of wetting and drying at solid-fluid interfaces on the Delft Molecular Dynamics Processor

The adsorption is studied of a fluid at a structured solid substrate by means of computer simulations on the Delft Molecular Dynamics Processor. Two types of particles are present, 2904 of one type for building a three-layer substrate and about 8500 of another type for composing the fluid. Interactions between like and unlike atoms are modeled by pair potentials of Lennard-Jones form cut off at 2.5. Simulations are performed at constant temperature and variable ratio of substrate-adsorbate to adsorbate-adsorbate attraction. On the basis of measurements of density profiles, coverages, surface tensions, and contact angles, a wetting as well as a drying phase transition have been identified. Both transitions are of first order.     

Fluid-fluid phase separation in colloid-polymer mixtures studied with small angle light scattering and light microscopy

Mixtures of colloidal silica spheres and polydimethylsiloxane in cyclohexane with a colloid-polymer size ratio of about one were found to phase separate into two fluid phases, one which is colloid-rich and one which is colloid-poor. In this work the phase separation kinetics of this fluid-fluid phase separation is studied for different compositions of the colloid-polymer mixtures, and at several degrees of supersaturation, with small angle light scattering and with light microscopy. The small angle light scattering curve exhibits a peak that grows in intensity and that shifts to smaller wave vector with time. The characteristic length scale that is obtained from the scattering peak is of the order of a few μm, in agreement with observations by light microscopy. The domain size increases with time as , which might be an indication of coarsening by diffusion and coalescence, like in the case of binary liquid mixtures and polymer blends. For sufficiently low degrees of supersaturation the angular scattering intensity curves satisfy dynamical scaling behavior.     

Wetting and phase separation at surfaces

We study the problem ofsurfacedirected spinodal decomposition, viz., the dynamical interplay of wetting and phase separation at surfaces. In particular, we focus on the kinetics of wetting-layer growth in a semi-infinite geometry for arbitrary surface potentials and mixture compositions. We also present representative results for phase separation in confined geometries, e.g., cylindrical pores, thin films, etc.     

Self-affinity study of nanostructured porous silicon-crystalline silicon interfaces

Self-affinity was used to analyze the roughness at the porous silicon (PS)-crystalline Si (cSi) interfaces fabricated under different conditions. Using the variable bandwidth method, the self-affinity behavior was, qualitatively and quantitatively, analyzed from the cross-section micrographs of the PS samples obtained by field emission scanning electron microscope. The results show that correlation length is related with the average pore width. Roughness exponent is found to be correlated with the interface roughness. In addition, similar experimental roughness exponents were obtained for several interfaces grown by different methods, indicating the intrinsic fractal nature of the PS-cSi interfaces. The results were confirmed through the self-affinity analysis done on the atomic force microscopy profiles.     

Dynamics of drying in 3D porous media

The drying dynamics in three dimensional porous media are studied with confocal microscopy. We observe abrupt air invasions in size from single particle to hundreds of particles. We show that these result from the strong flow from menisci in large pores to menisci in small pores during drying. This flow causes air invasions to start in large menisci and subsequently spread throughout the entire system. We measure the size and structure of the air invasions and show that they are in accord with invasion percolation. By varying the particle size and contact angle we unambiguously demonstrate that capillary pressure dominates the drying process.     

Magnetism at surfaces and interfaces

The current state-of-the-art of ab-initio calculations of the magnetic structures of surfaces and interfaces is highlighted by presenting results obtained with the recently developed full-potential linearized augmented plane wave method for thin films. In particular, spin density maps, (induced) magnetic moments and hyperfine-fields are presented for the clean metal surfaces Fe(001), Ni(001) and Pt(001). The magnetic moments on an interface are discussed for the prototypical case Ni/Cu.     

Hyperfine fields at surfaces and interfaces

Magnetism and hyperfine fields at transition metal surfaces are discussed using state-of-the-art local spin density methods. Emphasis is placed on recent results obtained for the Fe(001), Ni(001), Cr(001) and Ag/Fe(001) ferromagnetic surfaces, and for the Knight shift in Pt(001).