Disorder-to-Order Transition in Settling Suspensions of Colloidal Silica: X-ray Measurements.

Dispersions of colloidal particles exhibit thermodynamic properties similar to those of molecular systems, including a hard sphere disorder-to-order transition. In experiments with organophilic silica in cyclohexane, gravity settling was used to concentrate the particles. With small particles the slow sedimentation permits rearrangement into the iridescent ordered phase, but larger particles form amorphous sediments instead. Scanning electron microscopy of the crystalline sediment indicates hexagonally closepacked layers. X-ray attenuation measurements reveal a discontinuity coincident with the observed boundary between iridescent and opaque regions. Sediments accumulating faster than the maximum rate of crystallization produce a glass, in accord with the classical theory for crystal growth.

Nematic and almost-tetratic phases of colloidal rectangles.

Nonspherical colloids can exhibit liquid-crystalline phases with different degrees of broken orientational and translational symmetry. Here we investigate hard rectangles consisting of photolithographically prepared disks standing on edge. We observe a conventional Kosterlitz-Thouless transition from isotropic to nematic with almost smectic behavior at high density. But just on the isotropic side of the isotropic to nematic transition we observe an unusual regime where short-range tetratic correlations dominate over nematic correlations. This occurs due to the proliferation of Ising-like pi/2 grain boundaries that disrupt nematic order, but preserve tetratic correlations, at lengths shorter than the spacing between free disclinations.

Polarizability and complex conductivity of dilute suspensions of spherical colloidal particles with uncharged (neutral) polymer coatings.

The polarizability of polymer-coated colloidal particles, as measured via dielectric relaxation spectroscopy, reflects on the degree to which convection, diffusion, and electromigration deform the equilibrium double layer. With a polymer coating, convection and electro-osmosis are resisted by hydrodynamic drag on the polymer segments. The electro-osmotic flow near the underlying bare surface is therefore diminished. Characteristics of the particles and the adsorbed polymer can, in principle, be inferred by measuring the frequency-dependent polarizability. In this work, "exact" numerical solutions of the electrokinetic equations are used to examine how adsorbed polymer changes the particle polarizability and, hence, the conductivity and dielectric constant increments of dilute suspensions. For neutral polymer coatings, the conductivity and dielectric constant increments are found to be very similar to those of the underlying bare particles, so the response depends mostly on the underlying bare particles. These observations suggest that dielectric spectroscopy is best used to determine the underlying surface charge, with characteristics of the coating inferred from the electrophoretic or dynamic mobility, together with the hydrodynamic radius obtained from sedimentation or dynamic light scattering. Addressed briefly are the effects of added counterions and nonspecific adsorption. The electrokinetic model explored in this work can be used to guide experiments (frequency and ionic strength, for example) to either minimize or maximize the sensitivity of the complex conductivity to the coating thickness or permeability.

Polarizability and complex conductivity of dilute suspensions of spherical colloidal particles with charged (polyelectrolyte) coatings.

The dielectric relaxation of polyelectrolyte-coated colloidal particles is examined via "exact" numerical solutions of the governing electrokinetic equations. The charged polymer coatings are characterized by a nominal charge density, thickness, and permeability. Brush-like segment density profiles are considered here, but more sophisticated segment and charge density profiles are accommodated by the model. The role of added counterions and nonspecific adsorption is considered briefly before examining how the experimentally measured conductivity and dielectric constant increments reflect the frequency of the applied electric field, the strength of the electrolyte, and characteristics of the polymer coatings, namely the charge, charge density, and permeability. Finally, a strategy is suggested by which dielectric spectroscopy and electrophoresis can be used to characterize polymer-coated particles. This approach complements experiments where electroviscous effects such as dynamic light scattering and sedimentation are weak.

The theory of delamination during drying of confined colloidal suspensions.

Recent experiments on the drying of colloidal films in confined thin rectangular geometries show an interesting new phenomenon: the delamination of the colloidal suspension from the cavity wall. The theory developed in this paper explains the phenomenon by applying the Griffith energy criteria to a poroelastic film of Hertzian spheres. Prior to delamination, flow due to drying compresses the film in the direction of flow and generates tension in the transverse direction. Delamination allows relaxation in both the transverse tensile stresses and the axial compression. Preliminary numerical solutions suggest that the elastic energy recovered should increase linearly with the length of the close-packed film. That suggests a simple analytical solution that predicts the advancing of the delamination as the length of the close-packed region increases and explains qualitatively the essential features of the phenomenon.

An electric bottle for colloids.

Particle concentration is a dominant control parameter for colloids and other soft matter systems. We demonstrate a simple technique, "dielectrophoretic equilibrium," implemented as an "electric bottle," a planar capacitor in a larger volume. The uniform field in the capacitor traps particles in this force-free region at a higher density than in the zero field regions outside. We show how the technique measures the equation of state and we initiate and grow colloidal crystals. "Dielectrophoretic equilibria" enable the study of a complete concentration-dependent phase diagram from a single microscopic sample, obviating the previous need for preparing a large number of samples.

Crystallization kinetics of hard spheres in microgravity in the coexistence regime: interactions between growing crystallites.

The hard sphere disorder-order transition serves as the paradigm for crystallization. However, measurements of the crystallization kinetics for colloidal hard spheres in the coexistence regime are incomplete for early times and are affected by sedimentation. We use time resolved Bragg light scattering to characterize crystal nucleation and growth in a microgravity environment on the space shuttle. In contrast to the classical picture of the nucleation and growth of isolated crystallites, we find substantial coarsening of growing crystallites. We also observe dendritic growth and face-centered cubic as the stable structure.

Colloidal hard-sphere crystallization kinetics in microgravity and normal gravity.

The hard-sphere disorder-order transition serves as the paradigm for crystallization. We used time-resolved Bragg light scattering from the close-packed planes to measure the kinetics of nucleation and growth of colloidal hard-sphere crystals. The effects of gravity are revealed by comparison of the experiments in microgravity and normal gravity. Crystallites grow faster and larger in microgravity, and the coarsening between crystallites is suppressed by gravity. The face-centered-cubic structure was strongly indicated as being the stable structure for hard-sphere crystals. For a sample with a volume fraction of 0.552, the classic nucleation and growth picture is followed.

Linear viscoelasticity of hard sphere colloidal crystals from resonance detected with dynamic light scattering.

We present measurements of the high-frequency shear modulus and dynamic viscosity for nonaqueous hard sphere colloidal crystals both in normal and microgravity environments. All experiments were performed on a multipurpose PHaSE instrument. For the rheological measurements, we detect the resonant response to oscillatory forcing with a dynamic light scattering scheme. The resonant response for colloidal crystals formed in normal and microgravity environments was similar, indicating that the bulk rheological properties are unaffected by differing crystal structure and crystallite size within the experimental error. Our high-frequency shear modulus seems reasonable, lying close to Frenkel and Ladd's predictions [Phys. Rev. Lett. 59, 1169 (1987)] for the static modulus of hard sphere crystals. Our high-frequency dynamic viscosity, on the other hand, seems high, exceeding Shikata and Pearson [J. Rheol. 38, 601 (1994)] and van der Werff et al.'s measurements [Phys. Rev. A 39, 795 (1989)] on the high-frequency dynamic viscosity for metastable fluids. The measurements are in the linear regime for the shear modulus but may not be for the dynamic viscosity as Frith et al. [Powder Technol. 51, 27 (1987)] report that the dynamic viscosity passes through a maximum with strain amplitude.

Compact laser light-scattering instrument for microgravity research.

NASA has developed a compact laser light-scattering instrument that employs both static and dynamic light-scattering techniques for microgravity research. The first use of this instrument was to study the behavior of colloidal hard spheres in a reduced gravity environment during the Second United States Microgravity Laboratory space shuttle mission. We discuss the instrument design and possible improvements based on our observations of significant differences between hard-sphere behavior in Earth's gravity and microgravity.