Influence of Agitation and Fluid Shear on Primary Nucleation in Solution

Abstract

The influence of mechanical energy on primary nucleation of butyl paraben has been investigated through 1320 cooling crystallization experiments. The induction time has been measured at different supersaturations, temperatures, and levels of mechanical energy input, in two different flow systems. There is an overall tendency in the experiments that primary nucleation is promoted by increased input of mechanical energy. In small vials agitated by magnetic stir bars, the induction time was found to decrease with increasing agitation power input raised to 0.2 in the low agitation region. However, further increase in agitation leads to an increase again in the induction time. In a concentric cylinder apparatus of Taylor–Couette flow type, the induction time is inversely related to the shear rate. By fitting the parameters of the classical nucleation theory to experimental data, it is shown that the results can be explained as an influence on the pre-exponential factor. The treatment behind the pre-exponential factor is extended to account for the contribution of forced convection in a solution exposed to agitation and fluid shear. However, the analysis cannot verify that increased rate of mass transfer can explain the results. Alternative mechanisms are discussed based on a comprehensive review of the relevant literature. Shear-induced molecular alignment and in particular agitation-enhanced cluster aggregation are mechanisms that appear to deserve further attention.