Yield stress of oxide dispersions—intermolecular forces of adsorbed small ionic additives and particle surface roughness

The yield stress‐pH and zeta potential‐pH behaviour of α‐alumina and zirconia dispersions with adsorbed small ionic molecular additives such as phosphate and pyrophosphate were determined. The result for adsorbed citrate was included for comparison. Adsorbed phosphate at high surface coverage increased the maximum yield stress of low surface area α‐Al₂O₃ (AKP30 and AA07) dispersions slightly. This increase is attributed to the intermolecular hydrogen bonding between phosphates adsorbed on interacting particles. With high surface area ZrO₂ (Tosoh) dispersions, however, the adsorbed phosphate decreased the maximum yield stress. This is due to its very rough surface morphology limiting the extent of intermolecular hydrogen bonding between adsorbed phosphate layers. Unlike phosphate, pyrophosphate reduces the maximum yield stress of AKP30 α‐Al₂O₃. This is due to the presence of intramolecular hydrogen bonding, thereby impeding effective bridging. A similar result is observed with citrate. The adsorbed pyrophosphate acts as an effective steric barrier keeping interacting particles further apart, thereby weakening the van de Waals attraction. These dispersions with the presence of non‐DLVO forces, that is bridging and steric, did not affect the linear relationship between yield stress and the square of the zeta potential as predicted by the yield stress–DLVO force model. However the relative importance of these non‐DLVO forces affect the value of the critical zeta potential at the point of transition from flocculated to dispersed state. © 2011 Canadian Society for Chemical Engineering