Transmission electron microscopy and thermodynamic studies of CaO-added AZ31 Mg alloys

We investigated the microstructural evolution of Mg–3Al–1Zn (AZ31) alloy systems, with Ca or CaO added, by carrying out microstructural characterizations in conjunction with thermodynamic calculations. A calculated phase diagram of the Mg–Ca–O ternary system showed that CaO can be dissolved in liquid Mg so as to have 12.6 wt.% Ca content in the liquid Mg at 700 °C. Therefore, for a 0.3 wt.% CaO-added AZ31 alloy, our thermodynamic calculation predicted a similar precipitation pathway to that of a 0.3 wt.% Ca-added AZ31 alloy during the solidification process. In fact, a thermodynamic analysis of the precipitation pathway assuming the Scheil model showed that the major precipitates in both alloys were Al8Mn5, CaMgSi, Laves C15 and Laves C36, in good agreement with our experimental observation. However, a microstructural characterization of the as-cast alloys using transmission electron microscopy revealed that the spatial distribution of the precipitates was significantly different in the two alloy systems; unlike in the Ca-added AZ31 alloy, the Ca-containing precipitates in the CaO-added AZ31 alloy exhibited strong agglomeration tendencies. Moreover, in an alloy solidified at a faster cooling rate, undissolved CaO particles were observed in the precipitate agglomerates that were connected to the other Ca-containing precipitates. These results suggest that an incomplete dissolution of CaO particles in the liquid results in the agglomeration of precipitates, as the undissolved CaO particles can act as local sources, supplying Ca to the liquid, and can thus act as preferential nucleation sites for the Ca-containing precipitates forming during the solidification of the alloy.