Opposite Particle Size Effect on Amorphous Calcium Carbonate Crystallization in Water and during Heating in Air

Calcium carbonate is a common constituent of many natural materials, such as shells and skeletons of marine animals. While it is well-documented that additives (organic and inorganic) modulate the crystallization of amorphous calcium carbonate (ACC), the effects of the intrinsic physicochemical characteristics of ACC, such as particle size, shape, and water content on the transformation to crystalline polymorphs, are still poorly understood. Here, we investigate the effect of particle size by preparing ACC nanoparticles with an average size ranging from ∼66 to ∼196 nm using a high-resolution titration setup. Our results show that the particle size determined the polymorph selection in solution; an increasing proportion of vaterite to calcite was observed with decreasing particle size. The polymorph selection was ascribed to a higher apparent solubility of ACC with decreasing particle size, a parameter from which we could determine the surface energy of ACC to be ∼0.33 J/m2. Upon heating, particle size showed the opposite effect, as smaller particles favored a higher crystallization temperature from ACC into (only) calcite. When the particle size was large enough, crystallization occurred concomitantly with the removal of bulk water at lower temperatures, where the smallest particles transformed at ∼310 °C, only after losing the final (surface) water. Our results highlight the importance of particle size as well as the crystallization conditions on the stability and transformation mechanisms of ACC.