Confinement-induced solidification of colloid-polymer depletion mixtures.

Using a model colloid-polymer suspension, we show that confinement induces solidification in attractive colloidal suspensions via a fundamentally different route from that active in hard sphere colloidal suspensions. For a range of polymer concentrations, the suspensions undergo a phase transition from a colloidal fluid of clusters to a colloidal gel as confinement increases while polymer and particle concentration are held constant. In both fluid- and solidlike attractive suspensions, effects of confinement on the structure and dynamics appear at much larger thicknesses than for hard-sphere suspensions. The solidification does not originate from structuring of the colloids by the walls. Instead, by analyzing cluster size distributions in the fluid phase and particle dynamics in the gel phase as a function of confinement, we find that the strength of the effective interparticle attraction increases as the samples are confined. We show that the increase in the effective attraction can be understood as a consequence of the increasing importance of excluded volume due to the walls to the free energy of the polymer as confinement is increased.

Dynamics of colloidal particles in ice.

We use x-ray photon correlation spectroscopy (XPCS) to probe the dynamics of colloidal particles in polycrystalline ice. During freezing, the dendritic ice morphology and rejection of particles from the ice created regions of high particle density, where some of the colloids were forced into contact and formed disordered aggregates. The particles in these high density regions underwent ballistic motion, with a characteristic velocity that increased with temperature. This ballistic motion is coupled with both stretched and compressed exponential decays of the intensity autocorrelation function. We suggest that this behavior could result from ice grain boundary migration.

Confocal imaging of confined quiescent and flowing colloid-polymer mixtures.

The behavior of confined colloidal suspensions with attractive interparticle interactions is critical to the rational design of materials for directed assembly(1-3), drug delivery(4), improved hydrocarbon recovery(5-7), and flowable electrodes for energy storage(8). Suspensions containing fluorescent colloids and non-adsorbing polymers are appealing model systems, as the ratio of the polymer radius of gyration to the particle radius and concentration of polymer control the range and strength of the interparticle attraction, respectively. By tuning the polymer properties and the volume fraction of the colloids, colloid fluids, fluids of clusters, gels, crystals, and glasses can be obtained(9). Confocal microscopy, a variant of fluorescence microscopy, allows an optically transparent and fluorescent sample to be imaged with high spatial and temporal resolution in three dimensions. In this technique, a small pinhole or slit blocks the emitted fluorescent light from regions of the sample that are outside the focal volume of the microscope optical system. As a result, only a thin section of the sample in the focal plane is imaged. This technique is particularly well suited to probe the structure and dynamics in dense colloidal suspensions at the single-particle scale: the particles are large enough to be resolved using visible light and diffuse slowly enough to be captured at typical scan speeds of commercial confocal systems(10). Improvements in scan speeds and analysis algorithms have also enabled quantitative confocal imaging of flowing suspensions(11-16,37). In this paper, we demonstrate confocal microscopy experiments to probe the confined phase behavior and flow properties of colloid-polymer mixtures. We first prepare colloid-polymer mixtures that are density- and refractive-index matched. Next, we report a standard protocol for imaging quiescent dense colloid-polymer mixtures under varying confinement in thin wedge-shaped cells. Finally, we demonstrate a protocol for imaging colloid-polymer mixtures during microchannel flow.

Particle-scale structure in frozen colloidal suspensions from small-angle x-ray scattering.

During directional solidification of the solvent in a colloidal suspension, the colloidal particles segregate from the growing solid, forming high-particle-density regions with structure on a hierarchy of length scales ranging from that of the particle-scale packing to the large-scale spacing between these regions. Previous work has concentrated mostly on the medium- to large-length scale structure, as it is the most accessible and thought to be more technologically relevant. However, the packing of the colloids at the particle scale is an important component not only in theoretical descriptions of the segregation process, but also to the utility of freeze-cast materials for new applications. Here we present the results of experiments in which we investigated this structure across a wide range of length scales using a combination of small-angle x-ray scattering and direct optical imaging. As expected, during freezing the particles were concentrated into regions between ice dendrites forming a microscopic pattern of high- and low-particle-density regions. X-ray scattering indicates that the particles in the high-density regions were so closely packed as to be touching. However, the arrangement of the particles does not conform to that predicted by standard interparticle pair potentials, suggesting that the particle packing induced by freezing differs from that formed during equilibrium densification processes.