Assessment of Flocculation Using Rheological Techniques

One very important point that must be considered in any rheological measurement is the possibility of slip during the measurements. This is particularly the case with highly concentrated dispersions, whereby the flocculated system may form a plug in the gap of the platens, leaving a thin liquid film at the walls of the concentric cylinder or cone-and-plate geometry. This behaviour is caused by some syneresis of the formulation in the gap of the concentric cylinder or cone and plate. In order to reduce sHp, roughened walls should be used for the platens an alternative method would be to use a vane rheometer. 

Steady-state shear stress-shear rate measurements are by far the most commonly used method in many industrial laboratories. Basically, the dispersion is stored at various temperatures and the yield value and plastic viscosity r are measured at various intervals of time. Any flocculation in the formulation should be accompanied by an increase in tr and r. One rapid technique for studying the effect of temperature changes on the flocculation of a formulation is to perform temperature sweep experiments, running the samples from perhaps 5 to 50 °C. Any trend in the variation of tr and r with temperature can quickly provide an indication of the temperature range at which a dispersion will remain stable, since during that temperature range cr and r will remain constant. 

If Ostwald ripening occurs simultaneously, and /pi may change in a complex 

The above measurements should be supplemented by particle size distribution measurements of the diluted dispersion (ensuring that no floes are present after dilution) to assess the extent of Ostwald ripening. Another compHcation may arise from the nature of the flocculation which, if it occurs in an irregular fashion (producing strong and tight floes), may cause i (0) to be increased while cr may show some decrease, and this wiU complicate the analysis of the results. Yet, in spite of these complications, constant stress measurements may provide valuable information on the state of the dispersion on storage. 

An alternative rheological technique for assessing flocculation involves oscillatory measurements which, as noted above, can include two sets of experiments, namely strain and oscillatory sweep measurements. 

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