Structure of colloid silica determined by viscosity measurements.

The viscosity of nanosized colloid silica suspensions, used as binders in the investment casting, was determined as a function of their weight fraction reaching 52%. A new capillary viscometer was used whose construction eliminated sedimentation effects. The experiments have been carried out at fixed pH 10.0 and controlled ionic strength. It was found that for a low silica concentration range (weight fraction below 5%) the suspension viscosity increased more rapidly than the Einstein theory predicts. This anomalous behavior could not be explained in terms of the primary electroviscous effect predicted to be a few orders of magnitude smaller as observed. This discrepancy was accounted for by postulating a fuzzy, gel-like structure of colloid silicas used in our experiments. Hence, the apparent hydrodynamic radius of silica particles in aqueous suspensions was found to be larger than the primary particle size in accordance with previous observations. Based on this postulate, an apparent density of the silica sols was found to be 1.32-1.37 g/cm(3) instead of 2.2-2.32 g/cm(3) as determined from the suspension dilution method. This behavior was interpreted in terms of the core/shell model with high shell porosity, reaching 85%. Similarly, for higher concentration ranges, silica viscosity increased more rapidly with increased sol concentration than predicted by the Batchelor model derived for hard particles. The deviation was attributed to the secondary electroviscous effect stemming from the electrostatic interactions among silica particles in sheared suspensions. This effect has quantitatively been interpreted in terms of Russel's theory. On the other hand, for the high concentration range the experimental results were well accounted for by the Dougherty-Krieger model. By exploiting our experimental findings a sensitive method of determining the structure and apparent density of silica sols in aqueous media was proposed.