Formation and structure of self-assembled silica nanoparticles in basic solutions of organic and inorganic cations

The phase behavior of silica solutions containing organic and inorganic cations was studied at room temperature using conductivity, pH, and small-angle scattering experiments. A critical aggregation concentration (cac) was observed at similar to 1:1 ratio of SiO2/OH- for all cation solutions from conductivity and pH studies. From this cac, a phase diagram of the system was developed with three distinct phase regions in pseudoequilibrium: a monomer/oligomer region (I), a monomer/oligomer/nanoparticle region (II), and a gel region (III). Small-angle X-ray and neutron scattering (SAXS and SANS) on solutions of region II formed with tetrapropylammonium hydroxide (TPAOH) revealed that the nanoparticles have a core-shell structure. Structure analysis of the SAXS and SANS data was best fit by a core-shell oblate ellipsoid model. A polydisperse set of core-shell spheres also fit the data well although with lower agreement factors. Similar nanoparticle morphologies were found in solutions of TMAOH, CsOH, and NaOH.