Differences between Colloidal and Crystalline Evaporative Deposits

Evaporative deposits from drops are widely studied due to their numerous applications in low-effort self-assembly, including for inkjet printing, microscale separations, and sensing/diagnostics. This phenomenon has been broadly explored for drops containing suspended colloidal particles but has been less quantified for drops with dissolved solutes. When a drop of solute/solvent mixture is evaporated on a substrate, nonvolatile solutes become supersaturated as the solvent evaporates, which then leads to crystal nucleation at the substrate-drop contact line. Emerging crystals alter the local wettability and fundamentally alter the dynamics of evaporation, which, in turn, influences the resultant evaporative deposit. Here we investigate the role of interactions between the substrate, crystals, and solution by comparing the evaporative deposition of three different salts as solutes against an evaporating colloidal solution. We show that nucleation effects can cause crystalline deposits to have a temperature relationship that is opposite to that of colloidal deposits and demonstrate how a balance between the contact-line pinning force and nucleation controls the deposit size.