The effect of ion specificity on the slow aggregation of silica nanoparticles with various initial morphology was investigated with an electrospray-scanning mobility particle sizer (ES-SMPS) and time-resolved synchrotron radiation-small-angle X-ray scattering (SR-SAXS). This combination provides a unique tool to monitor and resolve the early aggregate development in detail. Aggregation was induced by varying the K(2)CO(3) or KCl concentration to obtain a fixed gelation time of ∼40 min, and the results were compared with those obtained in a previous paper (Johnsson et al. J. Phys. Chem. B 2011, 115, 765-775) for NaCl. All dispersions produced gels that contained free primary particles well past the point of gelation (PoG). The initial aggregate formation and obtained gel morphologies were independent of the aggregation initiator. Nevertheless, ion-specific effects were observed for the rate of the stability increase of the 3-dimensional (3D) gel structure. The formation of a stable structure was fastest in the presence of the strongly hydrated counterions, and a clear anion effect was observed. The obtained gel stabilities were interpreted by relating the rate of formation of covalent siloxane bonds to the polarization of the water molecules surrounding structure-maker ions.
© 2011 American Chemical Society