A comprehensive study was carried out on the dynamic viscosity of X30 silica dispersions at both high and low volume fractions of colloidal silica particles at various electrolyte ionic strength and pH values. Booth and Ruiz-Reina and Carrique theoretical models (R-R&C) were compared in predicting the primary electroviscous effect (PEE) for viscosity at low volume fractions. To this respect the colloidal dispersion was well characterised with regards to electrolyte properties such as the Debye length, κ-1, calculated from the ionic strength, and zeta potential, ζ, calculated from the electrophoretic mobility using the full numerical model by O'Brien and White (O'B&W). R-R&C hard sphere model (which is a modified version of Simha hard sphere model that includes a boundary condition by Happel on the outer radius of the cell) and the semi-empirical Krieger-Dougherty (K-D) models were fitted to the experimental data at high volume fractions. At both low and high volume fractions the viscosity increased with pH and decreased with ionic strength. At low volume fractions both theoretical models significantly underestimated the experimental dynamic viscosities obtained in this work. This could be attributed to the fuzzy structures for silica particles in aqueous conditions reported previously in the literature, where a significantly larger electroviscous parameter, p, was obtained experimentally for silica particles. The experimental electroviscous parameter, pexp, in this work was found to be roughly an order of magnitude up to 26 times larger than that predicted by Booth and around 5 ± 1 times larger than the predicted p by R-R&C model allowing the introduction of a correction factor in the PEE coefficient obtained from R-R&C model enabling good prediction for X30 silica dispersions by the latter model. The significant improvement of the electroviscous effect predictions by R-R&C model compared to Booth model may be attributed to the limitations invalidating the Booth model at the electrolyte conditions in this study. At high volume fractions, the R-R&C hard sphere cell model, gave a much better fit to the experimental data compared to the K-D model, which also had the advantage of being only dependent on a coefficient that linearly relates an effective volume fraction postulated for the fuzzy silica particles to the experimental. The K-D model however, depends on the intrinsic viscosity, [η], which requires the calculation of the experimental slope of the dynamic viscosity against volume fraction in the dilute limit, and also on a maximum packing fraction as a fitting parameter. Due to the effect of the fuzzy structures on the viscosity, the latter effective volume fraction ϕeff was calculated using two approaches: (i) as a fitting parameter by fitting the R-R&C hard sphere model to the experimental viscosity data over the entire volume fraction range, and (ii) by fitting only the linear part of the experimental viscosity at low volume fractions, It is concluded that the R-R&C hard sphere model with the effective volume fraction accounting for the fuzzy structures fits reasonably well the full range of experimental results at low and high volume fractions. When the model was used with the Adamczyk effective volume fraction (i.e., considering only the dilute region in the fitting procedure), the predictions became worse at high volume fractions where significant deviations from the experimental results were found upon the increase of pH.
Keywords: Cell model; Core shell model; Dynamic viscosity; Primary electroviscous effect (PEE); Silica dispersion.
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