The effect of morphology and particle-wall interaction on colloidal near-wall dynamics.

We investigated the near-wall Brownian dynamics of different types of colloidal particles with a typical size in the 100 nm range using evanescent wave dynamic light scattering (EWDLS). In detail we studied dilute suspensions of silica spheres and shells with a smooth surface and silica particles with controlled surface roughness. While the near wall dynamics of the particle with a smooth surface differ only slightly from the theoretical prediction for hard sphere colloids, the rough particles diffuse significantly slower. We analysed the experimental data by comparison with model calculations and suggest that the deviating dynamics of the rough particles are not due to increased hydrodynamic interaction with the wall. Rather, the particle roughness significantly changes their DLVO interaction with the wall, which in turn affects their diffusion.

Thermal transport in binary colloidal glasses: Composition dependence and percolation assessment.

The combination of various types of materials is often used to create superior composites that outperform the pure phase components. For any rational design, the thermal conductivity of the composite as a function of the volume fraction of the filler component needs to be known. When approaching the nanoscale, the homogeneous mixture of various components poses an additional challenge. Here, we investigate binary nanocomposite materials based on polymer latex beads and hollow silica nanoparticles. These form randomly mixed colloidal glasses on a sub-µm scale. We focus on the heat transport properties through such binary assembly structures. The thermal conductivity can be well described by the effective medium theory. However, film formation of the soft polymer component leads to phase segregation and a mismatch between existing mixing models. We confirm our experimental data by finite element modeling. This additionally allowed us to assess the onset of thermal transport percolation in such random particulate structures. Our study contributes to a better understanding of thermal transport through heterostructured particulate assemblies.

Homogeneous Nucleation of Ice Confined in Hollow Silica Spheres.

Ice nucleation is studied in hollow silica (HS) spheres. These hierarchical materials comprise ∼3 nm pores within the silica network, which are confined to a ∼20 nm shell of a hollow sphere (with diameters in the range ∼190-640 nm). The multiple length scales involved in HS spheres affect the ice nucleation mechanism. We find homogeneous nucleation inside the water filled capsules, whereas heterogeneous nucleation prevails in the surrounding dispersion medium. We validate our findings for a series of hollow sphere sizes and demonstrate the absence of homogeneous nucleation in the case of polystyrene-silica core-shell particles. The present findings shed new light on the interplay between homogeneous and heterogeneous nucleation of ice with possible implications in undercooled reactions and the storage of reactive or biologically active substances.

Polystyrene colloidal crystals: Interface controlled thermal conductivity in an open-porous mesoparticle superstructure.

Colloidal crystals typically consist of sub-micron sized monodisperse particles, which are densely packed on a face centered cubic lattice. While many properties of this material class have been studied over the past decades, little is known about their thermal transport properties. The high amount of interfaces and their small interparticle contact area should result in efficient thermal insulation. Using laser flash analysis we report for the first time on the temperature dependent thermal conductivity of a freestanding 366 nm polystyrene (PS) colloidal crystal. Macroscopic monoliths of these samples were fabricated by colloidal self-assembly. We demonstrate a very low thermal conductivity κ of 51 mW K(-1) m(-1) (κ of bulk PS∼140 mW K(-1) m(-1)). Remarkably, this low thermal conductivity is reached at a comparatively high density of 750 kg m(-3). It can be further increased by almost 300% upon film formation and loss of the colloidal mesostructure. Additionally, this open porous structure is largely independent of the surrounding atmosphere. This can be rationalized by the small size (∼100 nm) of the pores present within this colloidal crystal.