Modeling of continuum transport and meso-scale kinetics during solution crystal growth

Abstract

Solution crystal growth is widely applied in many industries and fundamental research, and it is employed to crystallize materials ranging from inorganic molecules, small organic molecules, to large organic molecules. However, despite the broad application, fundamental factors regarding this crystal growth process are not well understood. In this thesis, numerical models are developed to study the influences of macro-scale mass transfer limitations and meso-scale growth kinetics on solution crystal growth. A parallel, finite element model is implemented to compute three-dimensional fluid flow and mass transfer during crystal growth and is especially applied to the growth systems in Atomic Force Microscopy fluid cells. This work assesses the parametric sensitivity of growth conditions to factors such as the strength of flow, the frequency of scanning motion, the size of the crystal, and the kinetics of the growing surface. Accounting for such effects will be very important to understand solution crystal growth and to interpret AFM measurements of growth dynamics. Additionally, a simplified two-dimensional numerical model focused on the region near the growing crystal surface and the AFM cantilever was developed based on the calculated results of the three-dimensional model. With this two-dimensional model, we provide basic understanding of the fluid flow and mass transfer where the AFM measurements were made, and simplified the revision of AFM measurements interpretation.A fundamental theoretical model based on the phase-field approach is developed to simulate nano-scale island growth and spiral step growth on crystal surfaces in a supersaturated liquid and is validated by comparison to zinc oxide nanowires synthesis experiments. Results obtained by this work help to explain how experimental factors affect the crystal growth and crystal microstructures and the correlation between island growth and spiral growth mechanisms.