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In this work, we investigate crystallization from droplets formed on micro-patterned surfaces. By solvent exchange in a micro-chamber, a ternary solution consisting of a model compound beta-alanine, water, and isopropanol, was displaced by a flow of isopropanol. In the process, oiling-out droplets formed and crystallized. Our results showed that the shape and size of the crystals on micro-patterned surfaces could be simply mediated by the flow conditions of solvent exchange. Varying flow rate, concentration, or channel height led to the formation of a thin film with micro-holes, connected network of crystals, or small diamond-shaped crystals. Rough micro-structures on the surface allowed the easy detachment of crystals from the surface. Beyond oiling-out crystallization, we demonstrated that the crystal formation from another solute dissolved in the droplets could be triggered by solvent exchange. The length of crystal fibers after the solvent exchange process was shorter at a faster flow rate. This study may provide further understanding to effectively obtain crystallization from surface droplets through the solvent exchange approach., Comment: 23 pages, 11 figures

Droplet formation in oiling-out crystallization has important implication for separation and purification of pharmaceutical active ingredients by using an antisolvent. In this work, we report the crystallization processes of oiling-out droplets on surfaces during solvent exchange. Our model ternary solution is beta-alanine dissolved in isopropanol and water mixture. As the antisolvent isopropanol displaced the alanine solution pre-filled in a microchamber, liquid-liquid phase separation occurred at the mixing front. The alanine-rich subphase formed surface microdroplets that subsequently crystallized with progression of solvent exchange. We find that the flow rates have significant influence on the droplet size, crystallization process, and growth rate, and final morphology of the crystals. At fast flow rates the droplets solidified rapidly and formed spherical-cap structures resembling the shape of droplets, in contrast to crystal microdomains or thin films formed at slow flow rates. On a highly hydrophilic surface, the crystals formed thin film without droplets formed on the surface. We further demonstrated that by the solvent exchange crystals can be formed by using a stock solution with a very low concentration of the precursor, and the as-prepared crystals can be used as seeds to trigger crystallization in bulk solution. Our results suggest that the solvent exchange has the potential to be an effective approach for controlling oiling-out crystallization, which can be applied in wide areas, such as separation and purification of many food, medical, and therapeutic ingredients., Comment: Advanced Materials Interfaces (2020)