Computational modelling studies of FeAl-X ALLOYS(X: Pt, Ru, Pd and Ag)

Abstract

In this work, we present first-principles calculation on the structural, thermodynamic, mechanical and electronic stabilities of Fe-Al and FeAl-X (X: Pt, Pd, Ru and Ag) alloys at lower and high temperatures. These systems have recently attracted a lot of attention for both scientific and possible technological application in turbines, Steel-It coating, energy sector, boilers, pipes and automotive parts as a potential replacement of steel due to their excellent resistance to oxidation at high temperatures. However, they suffer limited room temperature ductility and a sharp drop in strength above 873 K. We determined the lattice parameters, heats of formation, elastic constants, bulk to shear moduli, density of states, phonon dispersion curve and X-ray diffraction pattern for binary and ternary system at various concentrations between 0 ≤ x ≤ 10. Furthermore, the lattice expansion, elastic constants, Gibbs free energy, X-ray diffraction pattern and radial distribution function were done on the most stable systems to determine the melting point of FeAl-X ternary systems. A systematic investigation was performed on the stability of the Fe-Al alloys at zero K. We employed CASTEP code to evaluate the thermodynamic, elastic and electronic stability. Virtual crystal approximation was used to determine various atomic concentrations (0 ≤ x ≤ 5) of both Pt and Ru; this allowed more precise predictions on the materials’ behaviour. Further analysis was done on the density of states to describe the behaviour of each phase near the Fermi level; these phases were observed at different percentage compositions. A supercell approach, DMol3 was also used to evaluate these systems at a larger scale (0 ≤ x ≤ 50). VASP and LAMMPS codes were used to determine the stability of these FeAl-X ternary systems at concentrations (0 ≤ x ≤ 10). It was found that the equilibrium lattice parameters of the binary systems are in good agreement to within 2% with the available experimental data. The heats of formation showed that β2 FeAl phase was the most energetically stable system since it displayed the lowest value compared to all other binary systems. This observation accord well with the experimental phase diagram. It was also confirmed from the corresponding electronic DOS behaviour near the Fermi level.

Furthermore, the shear modulus (C’) of these Fe-Al binary systems, i.e. FeAl, Fe2Al5, Fe4Al13, Fe5Al8, Fe2Al and FeAl3 were found to be positive fulfilling the condition of stability. The Fe2Al5 system was found to be the second most stable phase, followed by the monoclinic structure Fe4Al13. This observation was confirmed from the total DOS (where the Fermi level falls in the pseudogap, condition of stability). We further employed virtual crystal approximation and supercell approaches to model various atomic compositions at 0 ≤ x ≤1 and 0 ≤ x ≤ 50 for Ag, Pt, Pd and Ru. The heats of formation, density of states and elastic constants were determined to describe the structural, thermodynamic and mechanical stability of these systems. It was found that the addition of Ag, Pt, Pd and Ru enhances the stability at lower atomic percentage composition below 0.5%. Interestingly, the addition of Pt and Ru was found to significantly improve the ductility of the ternary FeAl-X compound for 0.2 and 0.5 at. % compositions. These systems showed that the Fe-sublattice was the preferred doping site with promising improvement in strength on the properties. It was further deduced that Ag and Pd stabilize the FeAl-X system at atomic percentage compositions of 0.5 and 0.7 respectively. Furthermore, a molecular dynamics-based LAMMPS-EAM was employed to model Fe50-XXXAl doped systems with either Ag, Pt or Pd. The lattice site preferences of the dopant were deduced from their energy landscape. More importantly, Ag and Pd doped systems gave comparable transition temperatures to experimental findings of 1273 K and 1073 K, respectively. Their thermodynamic and mechanical stability trends showed promising properties for industrial applications, displaying stability at a high temperature below 1300 K. This was evident for Ag, Pt (0.5 at %) and Pd (0.7 at %) doping as was the most stable systems with respect to Cij, ΔG, and RDF’s which indicated to influence the elastic instability above 1200 K as well as the ductility of these systems. The XRD confirmed that the doped systems preserved the structural symmetry as expected.