Pia Ruckdeschel

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.

Monodisperse hollow silica spheres: An in-depth scattering analysis

Herein, we fabricate hollow silica nanoparticles with exceptionally narrow size distributions that inherently possess two distinct length scales—tens of nanometers with regards to the shell thickness, and hundreds of nanometers in regards to the total diameter. We characterize these structures using dynamic and static light scattering (DLS and SLS), small angle X-ray scattering (SAXS), and transmission electron microscopy (TEM), and we demonstrate quantitative agreement among all methods. The ratio between the radius of gyration (SLS) and hydrodynamic radius (DLS) in these particles equals almost unity, corresponding to ideal capsule behavior. We are able to resolve up to 20 diffraction orders of the hollow sphere form factor in SAXS, indicating a narrow size distribution. Data from light and X-ray scattering can be combined to a master curve covering a q-range of four orders of magnitude assessing all hierarchical length scales of the form factor. The measured SLS intensity profiles noticeably change when the scattering contrast between the interior and exterior is altered, whereas the SAXS intensity profiles do not show any significant change. Tight control of the aforementioned length scales in one simple and robust colloidal building block renders these particles suitable as future calibration standards.

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.

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.