Cross-Nucleation between Polymorphs: Quantitative Modeling of Kinetics and Morphology

Cross-nucleation is defined as the nucleation of one polymorph on the surface of another polymorph of the same substance. Although the description of this particular form of heterogeneous nucleation is mainly phenomenological, recently dedicated quantitative studies are performed on several systems. In this work we propose a model framework that captures the phenomenon of cross-nucleation for a spherulitic seed-surface geometry, as well as the kinetic competition between the seed growth and the cross-nucleus formation, by the introduction of a tangential growth rate of the daughter polymorph. Regardless of the growth rate of the parent spherulite, this model describes the experimental data up to and including the final amount of cross-nuclei on its periphery, solely based on one parameter, the cross-nucleation rate. Furthermore, a strong temperature dependency of the kinetic competition between concomitantly growing α- and β-phase isotactic polypropylene is observed and related to the previously reported anomalous behavior of this cross-nucleating system.