Structural evolution of calcia during calcium deoxidation in Fe–O–Ca melt

Abstract

The crystallization process of CaO in iron melt begins with nucleation, which determines the structure and size of the CaO inclusions; thus, it is important to investigate the mechanism of inclusion modification by calcium treatment. In this study, a two-step nucleation method was used to investigate the behavior during the early stages of CaO inclusion crystallization. The first principles method was applied to calculate the structures and properties of CaO crystals and CaO clusters. Then, the nucleation mechanism of CaO in the Fe–O–Ca melt has been discussed. The numerical results show that CaO clusters with cubic structures and appropriate variations are the lowest energy structures and are more stable than other isomers. The stability of the cubic (CaO)_n clusters increases with the increase in size and gradually approaches that of the CaO crystal. CaO clusters can form spontaneously in the Fe–O–Ca melt, while the transformation reaction of the CaO clusters in the Fe–O–Ca melt deeply depends on the supersaturation ratio of [Ca] and [O]. CaO clusters may remain as suspended CaO inclusions in the iron melt for a long time, and these suspensions of CaO clusters are the source of excess oxygen in the iron melt.