Nonclassical Crystallization: Mesocrystals and Morphology Change of CaCO3 Crystals in the Presence of a Polyelectrolyte Additive

Crystallization of calcite from differently concentrated calcium chloride solutions by the CO2 gas diffusion technique in the presence of polystyrene sulfonate yields crystal superstructures with unusual morphology. From the typical calcite rhombohedra as a starting situation, the morphology can be systematically varied via rounded edges and truncated triangles to finally concavely bended lens-like superstructures. Although these "crystals" are apparently well-faceted in light microscopy, electron microscopy analysis and BET reveal that the structures are highly porous and are composed of almost perfectly 3D-aligned calcite nanocrystals scaffolded to the final, partly nicely curved superstructures. At high supersaturations, superstructures with changed symmetry indicative of dipolar interaction potentials between the building blocks are found. The present model case also gives evidence for the importance of nonclassical, mesoscopic processes in crystallization in general.