We investigate the assembly of colloidal ellipsoids in ac electric fields. Polystyrene latex ellipsoids with aspect ratios 3.0, 4.3, and 7.6 orient with the applied field and, at sufficient field strengths, interact to form particle chains at an angle with respect to the field. The characteristic chain angle decreases with increasing aspect ratio. The angled chains combine laterally to form an open centered rectangular two-dimensional structures belonging to the c2mm plane group. This chaining and assembly behavior is explained based on calculations of the particle pair interactions explicitly accounting for the electric field and shape of the ellipsoids.
We have characterized a montmorillonite-based organoclay dispersed in three different nonaqueous solvents using a combination of x-ray scattering, small-angle neutron scattering (SANS), and ultrasmall angle neutron scattering (USANS), together with rheological measurements. Consistent with these measurements, we present a structural model for the incompletely dispersed clay as consisting of randomly oriented tactoids made of partially overlapping clay sheets, with transverse dimensions of several microns. Intersheet correlation peaks are visible in x-ray scattering, and quantitatively fit by our model structure factor. SANS and USANS together show a power law of about -3 over a wide range of wave numbers below the intersheet correlation peak. Our model relates this power law to a power law distribution of the number of locally overlapping layers in a tactoid. The rheology data show that both storage and loss moduli, as well as yield stress, scale with a power law in volume fraction of about three. Equating the gel onset composition with the overlap of randomly oriented tactoids and taking into account the large transverse dimensions of the tactoids, we predict the gel point to be at or below 0.006 volume fraction organoclay. This is consistent with the rheology data.
We study the buoyancy-driven motion of two-dimensional bubbles and droplets in a Bingham fluid using a regularization method. The finite-element computations are carried out using the method of level sets to track the interface. We find that multiple bubbles and droplets can move in a body force field under conditions where a single bubble or droplet with the same physical properties would be unable to overcome the integrated yield stress and would be trapped. The finite yielded region around a single bubble or droplet in a Bingham fluid causes a backflow, resulting in unyielded “ears” that rotate and exchange material points with the yielded fluid to maintain a fixed position on the equatorial plane as the bubble rises or the droplet falls. The backflow flattens the tail of the trailing bubble or droplet in a pair and, at a sufficiently high level of interfacial tension, causes a splitting of the tail and the creation of a cusp. Three bubbles in a triangular configuration interact in a manner that is qualitatively predictable by considering pair interactions. Despite important differences in detail, the general shape evolution of bubbles and droplets in a Bingham fluid is similar to that in a Newtonian liquid when time scales are considered on a comparable basis.
Solvent-free polymer-grafted nanoparticle fluids consist of inorganic core particles fluidized by polymers tethered to their surfaces. The attachment of the suspending fluid to the particle surface creates a strong penalty for local variations in the fluid volume surrounding the particles. As a model of such a suspension we perform Brownian dynamics of an equilibrium system consisting of hard spheres which experience a many-particle potential proportional to the variance of the Voronoi volumes surrounding each particle (E = α(Vi-V0)(2)). The coefficient of proportionality α can be varied such that pure hard sphere dynamics is recovered as α → 0, while an incompressible array of hairy particles is obtained as α → ∞. As α is increased the distribution of Voronoi volumes becomes narrower, the mean coordination number of the particle increases and the variance in the number of nearest neighbors decreases. The nearest neighbor peaks in the pair distribution function are suppressed and shifted to larger radial separations as the constraint acts to maintain relatively uniform interstitial regions. The structure factor of the model suspension satisfies S(k=0) → 0 as α → ∞ in accordance with expectation for a single component (particle plus tethered fluid) incompressible system. The tracer diffusivity of the particles is reduced by the volume constraint and goes to zero at ϕ ∼ 0.52, indicating an earlier glass transition than has been observed in hard sphere suspensions. The total pressure of the suspension grows in proportion to (αkBT)(1/2) as the strength of the volume-constraint potential grows. This stress arises primarily from the interparticle potential forces, while the hard-sphere collisional contribution to the stress is suppressed by the volume constraint.
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