Evidence of Multiple Crystallization Pathways in Lithium Disilicate: A Metadynamics Investigation

Metadynamics simulations driven by using two X-ray diffraction peaks identified three alternative crystallization pathways of the lithium disilicate crystal from the melt. The most favorable one passes through the formation of disordered layered structures undergoing internal ordering in a second step. The second pathway involves the formation of phase-separated structures composed of nuclei of beta-cristobalite crystals surrounded by lithium -rich phases in which metasilicate chains are formed. The conversion of these structures to the stable lithium disilicate crystal involves an intermediate structure whose silicate layers are connected by silicate rings with the energy barrier of 2.5 kJ/mol per formula unit (f.u.). The third pathway is highly unlikely because of the huge energy barrier involved (20 kJ/mol per f.u.). This path also involves the passage through a phase-separated structure of an indefinite silica region surrounded mainly by amorphous lithium oxide.

Automated summary

Metadynamics simulations revealed three alternative pathways for the crystallization of lithium disilicate crystal from the melt. The most favorable one involves the formation of disordered layered structures followed by internal ordering. The second pathway includes the formation of phase-separated structures composed of beta-cristobalite nuclei surrounded by lithium-rich phases. The third pathway is highly unlikely due to the large energy barrier involved.