Visible Mie Scattering from Hollow Silica Particles with Particulate Shells

A series of colloidal nanocomposite dispersions are synthesized by alcoholic dispersion polymerization of styrene in the presence of an ultrafine silica sol. The original core/shell polystyrene/silica nanocomposite particles have mean diameters ranging from 321 to 471 nm, as determined by dynamic light scattering. Upon calcination of the polystyrene cores, some shrinkage occurs but intact hollow silica shells are observed by transmission electron microscopy. On visual inspection, these silica residues display remarkable colors that vary depending on the particle diameter. When examined in transmittance mode (i.e., with an illuminated background) the silica powders appear yellow to red in color, but when viewed in reflectance (i.e., with a dark background) relatively intense blue/green colors are observed. The latter phenomenon has been analyzed by visible reflectance spectroscopy and the reflectance maximum depends on the dimensions of the silica shell, which are in turn dictated by the initial nanocomposite particle diameter. Small-angle X-ray scattering is used to determine the packing density of the silica nanoparticles, both in the original polystyrene/silica nanocomposite particles and in the calcined silica shells. Combined with geometrical considerations, this allows the equivalent uniform silica shell thickness to be calculated for a particulate silica shell and this parameter is then related to the theoretical predictions made by Retsch et al. for hollow particles comprising uniform silica shells (see Retsch, M.; Schmelzeisen, M.; Butt, H. J.; Thomas, E. L. Nano Lett., 2011, 11, 1389).