The effect of chemical disorder on defect formation and migration in disordered max phases

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 effects on the structural-stability, energy-stability, electronic-structure, and diffusion barrier for point defects in MAX phases within a first-principles density functional theory framework. The vacancy (VM, VA, VX) 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 VA formation energies compared to VM and VX. The VA diffusion barrier is also significantly reduced for M-site disorder compared to their ordered counterpart. This is a very important finding because the reduced barrier height will ease the Al diffusion at high-operating temperatures, which will help the formation of passivating oxide layer (i.e., Al2O3 in aluminum-based MAX phases) and will slow down or stop the material degradation. We believe that our study provides a fundamental understanding and an approach to tailor the key properties that can lead to the discovery of new MAX phases.