The interplay between nucleation and patterning during shear-induced crystallization from solution in a parallel...

Cooling crystallization of small organic molecules from solution is an important operation for the separation and purification of drug products. In this research, shear-induced nucleation from a supersaturated solution is studied in a parallel plate geometry. Under conditions of shear and small gap sizes, narrow mesoscale circular bands of small crystals appeared spontaneously and reproducibly on the plate's surface. We have investigated the connection between nucleation and the emergence of these circular patterns. Our results show that nucleation occurs preferably in zones with high local shear rate (located at the outer edges of the plates), compared to zones with low local shear rate (at the center of the plates). The time before nucleation occurs decreases significantly for increasing mean shear rate and time. The circular crystalline patterns appear at the plate's surface, where heterogeneous nucleation first occurs. Multiple hypotheses are explored to understand the pattern formation in crystallization. Since no satisfactory explanation is found, a new mechanism is proposed. This hypothesis involves crystals initially forming on the surface of the plates and undergoing stick-slip motion, which influences the local nucleation kinetics. This results in an interplay between (secondary) nucleation and stick-slip motion at the start of the crystallization process. By modifying the surface of the plates, their ability to act as a heterogeneous nucleation site can be altered, allowing control over the formation of patterns.