Rheological methods have been used to study the influence of the liquor cation (sodium versus potassium) on the time-dependent gibbsite particle interactions that occur during Bayer process crystallisation. The temperature, supersaturation and seeding levels investigated simulate those experienced in industrial crystallisers. Gibbsite agglomeration was shown to occur by reversible aggregation followed by irreversible cementation. These two sub-steps were individually characterised by careful choice of seed surface area and liquor supersaturation during batch crystallisation. At seed loading levels less than 10% w/w aggregates are rapidly cemented into agglomerates, this is more pronounced in sodium than potassium-based liquors. These suspensions were Newtonian and the extent of agglomeration correlated with their viscosity. At seed loading levels greater than 20% w/w particle aggregation resulted in extensively time-dependent and non-Newtonian rheology. However, the aggregates did not undergo cementation into agglomerates and no irreversible size enlargement was evident. Yield stress development with time was used to probe the kinetics of aggregation and quantify the particle interaction behaviour. The rate and extent of the particle network formation is more pronounced in sodium rather than potassium-based liquors, supersaturation dependent, alkali concentration dependent, but only weakly temperature dependent. These findings are discussed with respect to the chemical and physical mechanisms of agglomeration in Bayer crystallisation and the role of cation.