Quantifying the Kinetics of Crystal Growth by Oriented Aggregation

Oriented aggregation is a nonclassical crystal growth mechanism resulting in new secondary particles composed of crystallographically aligned primary crystallites. These secondary crystals often have unique and symmetry-defying morphologies, can be twinned, and can contain stacking faults and other significant defects. A wide range of materials, such as titanium dioxide, iron oxides, selenides and sulfides, and metal oxyhydroxides, are known to grow by oriented aggregation under certain conditions. Evidence for oriented aggregation also has been observed in natural materials. Over the last decade, reports of this crystal growth mechanism have appeared with increasing frequency in the scientific literature. The development of kinetic models aimed at improving our fundamental understanding as well as facilitating purposeful control over size, size distribution, and shape has ranged from simple dimer formation models to polymeric models and population balance models. These models have enabled detection and characterization of crystal growth by oriented aggregation using methods such as small-angle x-ray scattering, among others, in addition to transmission electron microscopy. As our fundamental understanding of oriented aggregation improves, novel and complex functional materials are expected to emerge. This article presents a summary of some recent results, methods, and models for characterizing crystal growth by oriented aggregation.