First-principle solubilities of alkali and alkaline earth metals in Mg-B alloys

TL;DR

This study uses first-principle calculations and thermodynamic modeling to predict solubilities of alkali and alkaline earth metals in Mg-B alloys, revealing key solubility trends and discovering new potential ground states.

Contribution

It introduces a novel theoretical framework considering phase boundaries for solubility prediction and identifies new stable phases in Mg-B-A systems.

Findings

Na shows the highest solubility in MgB$_7$ at 0.5-1% between 650-1000 K.

Interstitial solutes have negligible solubilities.

New potential ground states CaB$_{4}$ and RbB$_{4}$ are proposed.

Abstract

By devising a novel framework, we present a comprehensive theoretical study of solubilities of alkali (Li, Na, K, Rb, Cs) and alkaline earth (Be, Ca, Sr, Ba) metals in the he boron-rich Mg-B system. The study is based on first-principle calculations of solutes formation energies in MgB$_2$, MgB$_4$, MgB$_7$ alloys and subsequent statistical-thermodynamical evaluation of solubilities. The advantage of the approach consists in considering all the known phase boundaries in the ternary phase diagram. Substitutional Na, Ca, and Li demonstrate the largest solubilities, and Na has the highest (0.5-1 % in MgB$_7$ at $T=650-1000$ K). All the considered interstitials have negligible solubilities. The solubility of Be in MgB$_7$ can not be determined because the corresponding low-solubility formation energy is negative indicating the existence of an unknown ternary ground state. We have performed a high-throughput search of ground states in binary Mg-B, Mg-$A$, and B-$A$ systems, and we construct the ternary phase diagrams of Mg-B-$A$ alloys based on the stable binary phases. Despite its high temperature observations, we find that Sr$_{9}$Mg$_{38}$ is not a low-temperature equilibrium structure. We also determine two new possible ground states CaB$_{4}$ and RbB$_{4}$, not yet observed experimentally.