Determination of Crystal Growth Rates in Multi-Component Solutions

Many solid forming processes involve crystallization from multi-component solutions. In order to predict final phase assemblages, multi-component phase transfer kinetics must be known. It is not sufficient to have the kinetics of only one crystallizing component in the presence of other entities; the kinetics of concurrent crystallizing components are of interest as well. However, methods for their determination are currently lacking. We propose a new method comprising desupersaturation measurements of a 150 mu m film of supersaturated solution in contact with a planar crystalline substrate. We show that concentration measurement at a single point in the film is sufficient to retrieve the phase transfer kinetics. For this, we use a confocal micro-Raman spectroscope, which is able to distinguish between different components and has a high spatial resolution. We chose crystallization of Na2SO4 and Na2CO3 decahydrate from aqueous solution as our model system because of its well-known phase equilibrium. In binary experiments, we demonstrate the mode of operation and its ability to reproduce known kinetics from the literature. In ternary experiments, we successfully distinguish two courses of crystallization, the first of which is a preferential crystallization of one component and the second a simultaneous crystallization of both crystallizing components. In both cases, the parameters for simple power law kinetics are determined. If sodium carbonate decahydrate crystallizes while sodium sulfate remains in solution, the mean mass transfer coefficient is revealed to be k(g), CO3 = 6 x 10(-7) m s(-1), which is about an order of magnitude lower compared to binary crystallization. If sodium carbonate decahydrate crystallizes concurrently with sodium sulfate decahydrate, the crystallization kinetics are similar to binary cases. The other component tends to be significantly slower compared to its binary crystallization.

Automated summary

Many solid forming processes involve crystallization from multi-component solutions. In order to predict the final phase assemblages, it is important to know the kinetics of multi-component phase transfer. However, current methods for determining these kinetics are lacking. Researchers propose a new method using desupersaturation measurements to predict phase transfer kinetics. They successfully demonstrate the effectiveness of this method in a model system.