Nucleation of solid solutions crystallizing from aqueous solutions

The study of nucleation and growth mechanisms of salts from aqueous solutions, as a function of supersaturation, is described using both macroscopic and microscopic experiments. In situ observations in a fluid cell in an atomic force microscope (AFM) reveal phenomena not accounted for in standard crystal-growth theories, specifically on the role of the crystal structure of the substrate in controlling spiral growth and two-dimensional nucleation. As a model example, the crystallization of two isostructural salts, BaSO₄ and SrSO₄, is described. The growth of solid-solution crystals is considerably more complex. The supersaturation of a given aqueous solution relative to a solid solution is different with respect to each solid composition, and it leads to the possibility that different compositions can simultaneously grow by different mechanisms on the same crystal face. Oscillatory compositional zoning is another consequence of the interplay between the thermodynamics and the kinetics of nucleation. The factors which control nucleation and growth of the solid solution (Ba,Sr)SO ₄ from an aqueous solution are described. The predictions made from the theory are compared with direct observations of crystal growth in an AFM.