Structure of long-period stacking/order Mg-Zn-RE (RE: rare-earth and Y) phases with extended non-stoichiometry ranges

TL;DR

This study models the structure of long-period stacking/order (LPSO) phases in Mg-Zn-RE alloys, revealing detailed atomic arrangements, chemical ordering, and the effects of disorder on phase stability using microscopy and first-principles calculations.

Contribution

It provides new structure models for LPSO phases in Mg-Zn-RE alloys, highlighting the role of Zn-RE interactions and non-stoichiometry in phase stability.

Findings

LPSO structures are derived from hcp-Mg with local fcc-stacking.

Chemical order is prominent in specific Mg-Zn-RE alloys.

LPSO phases tolerate significant disorder at Zn and RE sites.

Abstract

We propose structure models of the unique long-period stacking/order (LPSO) phases formed in the Mg-Zn-RE alloys, based on Z-contrast scanning transmission electron microscopy (STEM) observations and first-principles calculations. The LPSO structures are long-period stacking derivatives of the hcp-Mg structure, and the Zn/RE distributions are restricted at the four close-packed atomic layers forming local fcc-stacking (i.e., a local ABCA stacking). Chemical order is well developed for the LPSO phases formed in Mg97Zn1Er2 (14H-type) and Mg85Zn6Y9 (18R-type) alloys with pronounced superlattice reflections, and the relevant Zn/RE distributions are clearly emerged in the Z-contrast atomic images. Initial ternary-ordered models are constructed by placing all the atoms at the ideal honeycomb sites, leading to plausible space groups of P63/mcm for 14H-type and C2/m, P3112 or P3212 for 18R-type. Characteristic ordered feature is well represented by the local Zn6RE8 clusters, which are embedded in the fcc-stacking layers in accordance with the L12-type short-range order. Energy-favored structural relaxations of the initial model cause significant displacements of the Zn/RE positions, implying that strong Zn-RE interactions may play a critical role for the phase stability. The LPSO phases seem to tolerate a considerable degree of disorder at the Zn and RE sites with statistical co-occupations by Mg, extending the non-stoichiometry phase region bounded along the Zn/RE equi-atomic line from ~Mg94.0Zn2.0Y4.0 to ~Mg83.3Zn8.3Y8.3.