The Effect of Chemical Disorder on Defect Formation and Migration in Disordered MAX Phases

TL;DR

This study uses first-principles calculations to explore how chemical disorder influences defect formation and migration in MAX phases, revealing that alloying can reduce defect formation energies and diffusion barriers, which impacts material stability.

Contribution

It provides new insights into the effects of alloying-induced disorder on defect energetics and migration in MAX phases, aiding the design of more stable materials.

Findings

Chemical disorder lowers A-site vacancy formation energies.

Disorder significantly reduces defect diffusion barriers.

Reduced barriers facilitate oxide layer formation at high temperatures.

Abstract

MAX phases have attracted increased attention due to their unique combination of ceramic and metallic properties. Point-defects are known to play a vital role in the structural, electronic and transport properties of alloys in general and this system in particular. As some MAX phases have been shown to be stable in non-stoichiometric compositions, it is likely that such alloying effects will affect the behavior of lattice point defects. This problem, however, remains relatively unexplored. In this work, we investigate the alloying effect on the structural-stability, energy-stability, electronic-structure, and diffusion barrier of point defects in MAX phase alloys within a first-principles density functional theory framework. The vacancy (V$_{M}$, V$_{A}$, V$_{X}$) and antisite (M-A; M-X) defects are considered with M and A site disorder in (Zr-M)$_{2}$(AA${'}$)C, where M=Cr,Nb,Ti and AA${'}$=Al, Al-Sn, Pb-Bi. Our calculations suggest that the chemical disorder helps lower the V$_{A}$ formation energies compared to V$_{M}$ and V$_{X}$. The V$_{A}$ diffusion barrier is also significantly reduced for M-site disorder compared to their ordered counterpart. This is very important finding because reduced barrier height will ease the Al diffusion at high-operating temperatures, which will help the formation of passivating oxide layer (i.e., Al$_{2}$O$_{3}$ in aluminum-based MAX phases) and will slow down or stop the material degradation. We believe that our study will provide a fundamental understanding and an approach to tailor the key properties that can lead to the discovery of new MAX phases.