Thermodynamic origin of solute-enriched stacking-fault in dilute Mg-Zn-Y alloys

TL;DR

This study reveals the thermodynamic mechanisms behind the formation of solute-enriched stacking faults in dilute Mg-Zn-Y alloys, highlighting the role of Zn-Y interactions in stabilizing these structures and their relation to LPSO phases.

Contribution

It introduces a thermodynamic analysis combining CALPHAD and first principles calculations to explain SESF formation and stability in Mg-Zn-Y alloys, a novel insight into alloy microstructure.

Findings

Zn/Y co-segregation stabilizes fcc layers over hcp Mg.

Spinodal-like decomposition reduces Gibbs energy significantly.

Zn-Y interactions are key to stabilizing SESF structures.

Abstract

We investigate thermodynamic behaviors of dilute Mg-Zn-Y ternary alloys to form a unique solute-enriched stacking-fault (SESF), which is an intrinsic-II type stacking-fault (I2-SF) enriched by the Zn and Y atoms and represents the structural-unit of the long-period stacking/order (LPSO) phase. SESF in the hexagonal-close-packed (hcp) Mg matrix forms a local face-centered-cubic (fcc) environment, and hence our thermodynamic analysis is based on the Gibbs energy comparison between hcp and fcc phases over the Mg-Zn-Y ternary composition ranges, using the calculation of phase diagrams (CALPHAD) method aided by the first principles calculations. Segregation behaviors of solute Zn/Y atoms into the SESF are firstly estimated according to the Hillert's parallel tangent law, followed by the possible disorder-order phase transformation within the SESF using the multiple-sublattice model. We find that the Zn/Y co-segregations at the SESF provide a remarkable condition that the fcc layers become more stable than the hcp-Mg matrix. Besides, within the SESF, the following spinodal-like decomposition into the Mg-rich solid-solution and the Zn/Y-rich L12-type order phase causes a significant reduction of the total Gibbs energy of the system. These thermodynamic behaviors explain fairly well a phenomenological origin of the Zn-Y clustering with the L12-type short-range order, which is known to occur for the LPSO phases and also confirmed for the present SESF by electron microscopy experiments. Therefore, strong Zn-Y interactions even in dilute conditions play a key role to stabilize firmly the SESF in the Mg-Zn-Y alloys.