Role of solvation forces in the gelation of fumed silica–alcohol suspensions

Aggregation and gelation kinetics of fumed silica were investigated by altering the solvent–surface interactions. Native and surface-modified (hydrophobic) fumed silica particles were dispersed in short-chain linear alcohols. Based on the kinetics of aggregation and gelation, we show that the solvent–surface interactions have a tremendous impact on the bulk suspension properties. The gelation kinetics were qualitatively similar in all of the fumed silica–alcohol samples, and the gel times for all the alcohols were captured on a master curve requiring two parameters. The two parameters, the stability ratio and critical volume fraction, describe the two regimes of gelation. At low concentrations, gelation occurs due to aggregation of the particles diffusing over a potential barrier (15–25kT15–25kT). The rate of aggregation and time to gelation then scales with the stability ratio. At high particle loadings, gelation occurs at a critical volume fraction due to localization in a secondary minimum with a depth of 3–4kT3–4kT. These observations are supported by evidence of hydrogen bonding between the solvent and the particle, creating oscillatory solvation forces that govern the magnitude of these two parameters.

Graphical abstractPrimary and secondary minimum gelation is governed by solvent–surface interactions for fumed silica–alcohol suspensions.Figure optionsDownload full-size imageDownload as PowerPoint slide