Anthony D. Dinsmore

Grain Boundary Scars and Spherical Crystallography

We describe experimental investigations of the structure of two-dimensional spherical crystals. The crystals, formed by beads self-assembled on water droplets in oil, serve as model systems for exploring very general theories about the minimum-energy configurations of particles with arbitrary repulsive interactions on curved surfaces. Above a critical system size we find that crystals develop distinctive high-angle grain boundaries, or scars, not found in planar crystals. The number of excess defects in a scar is shown to grow linearly with the dimensionless system size. The observed slope is expected to be universal, independent of the microscopic potential.

Three-dimensional confocal microscopy of colloids

Confocal microscopy is used in the study of colloidal gels, glasses, and binary fluids. We measure the three-dimensional positions of colloidal particles with a precision of approximately 50 nm (a small fraction of each particles radius) and with a time resolution sufficient for tracking the thermal motions of several thousand particles at once. This information allows us to characterize the structure and the dynamics of these materials in qualitatively new ways, for example, by quantifying the topology of chains and clusters of particles as well as by measuring the spatial correlations between particles with high mobilities. We describe our experimental technique and describe measurements that complement the results of light scattering.

Adsorption Energy of Nano- and Microparticles at Liquid-Liquid Interfaces

We study experimentally the energy of adsorption, DeltaE, of nanoparticles and microparticles at the oil-water interface by monitoring the decrease of interfacial tension as the particles bind. For citrate-stabilized gold nanoparticles assembling on a droplet of octafluoropentyl acrylate, we find DeltaE = -5.1 k(B)T for particle radius R = 2.5 nm and DeltaE proportional, variant R(2) for larger sizes. Gold nanoparticles with (1-mercaptoundec-11-yl)tetra(ethylene glycol) ligand have a much larger binding energy (DeltaE = -60.4 k(B)T) and an energy barrier against adsorption. For polystyrene spheres with R = 1.05 microm, we find DeltaE = -0.9 x 10(6) k(B)T. We also find that the binding energy depends on the composition of the oil phase and can be tuned by the salt concentration of the nanoparticle suspension. These results will be useful for controlling the assembly of nanoparticles at liquid interfaces, and the method reported here should be broadly useful for quantitative measurements of binding energy.

The effect of particle size on the structural transitions in zinc sulfide

Studies of pressure induced phase transformations of ZnS nanoparticles using diamond anvil cells and synchrotron radiation were carried out to 20.0 GPa. Nanoparticles initially in the zinc-blende and wurtzite phases both transformed to the NaCl phase under the application of pressure. The zinc-blende particles, which were of 2.8 nm size, and the wurtzite particles, which were of 25.3 nm size, transformed to the NaCl phase at 19.0 and 15.0 GPa, respectively. Nanoparticles of the wurtzite phase never regained their initial wurtzite structure but returned to the zinc-blende phase upon downloading the pressure. The resultant zinc-blende nanoparticles transformed to the NaCl phase upon the reapplication of a pressure of 15.0 GPa. Nanoparticles initially in the zinc-blende phase returned to their original phase.

Structure and luminescence of annealed nanoparticles of ZnS:Mn

Structural and light-emitting properties of nanoparticles of ZnS:Mn annealed in vacuum at temperatures up to 525 °C are presented. Annealing the 3.5 nm particles at temperatures up to 350 °C caused growth of some particles without substantial change in the luminescence or ZnS lattice. After annealing at 400–525 °C, the high-temperature wurtzite phase of ZnS appeared, accompanied by an increase of the average particle diameter to approximately 100 nm and a rearrangement of the Mn ions. Dramatic increase in cathodoluminescence emission was also observed and is compared to the structural information obtained from electron microscopy, x-ray diffraction, x-ray absorption fine structure, and electron paramagnetic resonance measurements.

Self-assembly of colloidal crystals

Recently, there has been much progress in the self-assembly of colloidal crystals. Major advances include the growth of colloidal crystals on lithographically templated substrates, the synthesis of ordered macroporous materials starting with crystalline emulsions, the investigation of the role of entropy in hard sphere colloids in space and on earth, and the use of electrohydrodynamic forces to create ordered structures.

Entropically driven self–assembly and interaction in suspension

In this paper we present fundamental studies elucidating the role of entropy in particle suspensions. We focus on systems composed of large colloidal particles along with a second, usually smaller species such as a particle or polymer. We describe direct measurements of these interactions in suspension, and we systematically show how these forces can be used to control the self–assembly of colloidal particles. The paper provides a unified review of the experiments from our laboratory, and in a few cases touches on very recent results.

Hard Spheres in Vesicles: Curvature-Induced Forces and Particle-Induced Curvature

We explore the interplay of membrane curvature and nonspecific binding due to excluded-volume effects among colloidal particles inside lipid bilayer vesicles. We trapped submicron spheres of two different sizes inside a pear-shaped, multilamellar vesicle and found the larger spheres to be pinned to the vesicles surface and pushed in the direction of increasing curvature. A simple model predicts that hard spheres can induce shape changes in flexible vesicles. The results demonstrate an important relationship between the shape of a vesicle or pore and the arrangement of particles within it.

Direct imaging of three-dimensional structure and topology of colloidal gels

We present novel measurements of the structure of colloidal gels. Using confocal microscopy, we obtain the precise three-dimensional positions of a large number of particles. We develop quantitative descriptions of the topology of the gel, including the number of bonds per particle, the chemical or bond fractal dimension, the number of flexible pivot points and other topological parameters that describe the chainlike structure. We investigate the dependence of these parameters on the particle volume fraction and the strength of the attraction that holds the particles together. While all samples have approximately the same fractal and chemical dimensions, we find that gels formed with stronger attraction or larger volume fraction have fewer bonds per particle, more filamentous chains and a greater number of flexible pivot points. Finally, we discuss the topological results in the context of the gels elasticity. Measurements of the elastic constants of individual chainlike segments are explained with a simple model. The distribution of elastic constants, however, has a general form that is not understood.

Measurement of Forces Inside a Three-Dimensional Pile of Frictionless Droplets

We present systematic and detailed measurements of interparticle contact forces inside three-dimensional piles of frictionless liquid droplets. We measured long-range chainlike correlations of the directions and magnitudes of large forces, thereby establishing the presence of force chains in three dimensions. Our correlation definition provides a chain persistence length of 10 mean droplet diameters, decreasing as load is applied to the pile. We also measured the angles between contacts and showed that the chainlike arrangement arises from the balance of forces. Moreover, we found that piles whose height was comparable to the chain persistence length exhibited substantially greater strain hardening than did tall piles, which we attributed to the force chains. Together, the results establish a connection between the microscopic force network and the elastic response of meso- or macroscopic granular piles. The conclusions drawn here should be relevant in jammed systems generally, including concentrated emulsions and piles of sand or other heavy particles.