Pressure-induced crystallization and densification of amorphized calcium carbonate hexahydrate controlled by interfacial water

Abstract

Amorphous calcium carbonate (ACC) is widely known as a metastable precursor in the formation of crystalline calcium carbonate biominerals. However, the exact role of water during the crystallization of ACC remains elusive. Here, a novel ACC with high specific surface area and nanopores is synthesized by solvent-induced dehydration and amorphization of crystalline calcium carbonate hexahydrate (ikaite), denoted as I-ACC. Comparing I-ACC and typical spherical ACC (S-ACC) nanoparticles, it reveals that the crystallization pathways of ACC under heating or pressure are not dictated by the total amount of water in ACC as reported, but rather the interfacial water that is released from ACC bulk and adsorbed on the surface of the particles. We show that the crystallization pathways of I-ACC to calcite single crystal with high specific surface area or vaterite can be easily controlled by tuning the release of water during heating. In addition, densely packed pure vaterite can be obtained via pressured-induced transformation of I-ACC at room temperature, which is otherwise difficult to form using S-ACC. These insights contribute to the understanding of the biological control of mineral formation via amorphous precursors and offer new opportunities to bioprocess inspired fabrication of strong bulk material at room temperature.

Keywords: Amorphous calcium carbonate; Cold sintering; Crystallization; Densification; Water.