Chemical interactions of solute atoms during L12 cluster formation in Mg–Zn–Gd alloys with long-period stacking ordered structure

Magnesium-based alloys containing transition metal (TM) and rare-earth (RE) atoms form L12-type TM6RE8 clusters, which are regularly arranged into long-period stacking ordered (LPSO) structures. X-ray absorption spectroscopy (XAS) and ab initio calculations were performed on the solution-treated Mg97Zn1Gd2 alloy before and after aging at 673 K to understand the L12 cluster formation mechanism and the interactions between the TM and RE atoms. Ab initio simulations of Zn K X-ray absorption near edge structure (XANES) spectra showed that the sharpness of the white line depended on the number of Gd atoms. The fine spectral structure changed with the local structure around the Zn atom. The measured XANES spectrum indicated that the Zn in the solution-treated Mg97Zn1Gd2 alloy was initially dissolved in Mg3Gd and then incorporated within L12 clusters after aging. Furthermore, an analysis of the l-projected density of states showed that the sharp white line peak in the XANES spectrum resulted from the interaction of Zn p and Gd f states, which occurred with spinodal decomposition and structural relaxation of L12 clusters. This spinodal decomposition and structural relaxation, caused by the electronic interaction between the RE and TM atoms, may be one of the reasons why rare-earth elements are indispensable for forming an LPSO structure. [Display omitted] •X-ray absorption spectroscopy is useful for studying solute atoms' local structure and interactions in alloys.•Spinodal decomposition and structural relaxation may be caused by the electronic interaction between the Zn p and Gd f states.•The f-electron states of rare earth elements play an essential role in forming LPSO structures.