Crystallisation Pathways of Polymorphic Triacylglycerols Induced by Mechanical Energy

The aim of these studies is to establish sound scientific principles to guide nucleation rate and the selection of a desired polymorph via the application of mechanical energy – ultrasound (US) irradiation. When delivered to a metastable liquid, before the offset of nucleation and under constant temperature and supercooling conditions, the wave nature of this simple form of energy should be critical for defining different crystallisation pathways of polymorphic materials including polymorph selection. To test this hypothesis, we crystallized a melt-grown trilaurin (LLL), a typical polymorphic triacylglycerols (TGA's), with and without US by using in-situ simultaneous synchrotron radiation time-resolved small-angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS), SAXS/WAXS. Without US application, both polymorphic forms β^' and β crystallized. With US treatment of the super cooled melt, the following effects were observed: (a) a marked decrease of induction times (b) an increased nucleation rate, and (c) selective crystallization of only β-form when crystallised at 25 and 30°C with input powers of 20 and 100 W and a sonication time of 2 s. Combining the existing knowledge on the dynamic nucleation of collapsing cavities and a qualitatively developed (P-T) phase diagram for the TGA's, it was possible to describe, for the first time, the behaviour of the most important parameters and the events that characterize the crystallization of these systems. It was shown that the interplay of sonication and the temperature of supercooled melts are critical to the selection of a stable β form.