Ab initio Investigation of Face-centered cubic High-Entropy Alloys

Abstract: High-entropy alloys (HEAs) represent a special group of solid solutions containing five or more principal elements. The new design strategy has attracted extensive attention from the materials science community. The design and development of HEAs with desired properties have become an important subject in materials science and technology. Herein this case, I investigate the basic properties of paramagnetic (PM) HEAs, including the magnetic properties, Curie temperatures, electronic structures, phase stabilities, and elastic properties using the first-principles exact muffin-tin orbitals (EMTO) method in combination with the coherent potential approximation (CPA) for dealing with the chemical and magnetic disorder. To understand and model the mechanical properties of face-centered cubic (fcc) HEAs, I also study the generalized stacking fault energy (GSFE), negative stacking fault energy (SFE) and twinning mechanism of various HEAs. Thesis focuses mainly on AlxCrMnFeCoNi (0 ≤ x ≤ 5, in molar fraction) and related HEAs.Whenever possible, I compare the theoretical predictions to the available experimental data in order to verify the employed ab initio methodology. I make use of the previous theoretical investigations carried out on AlxCrFeCoNi HEAs to reveal and understand the role of Mn in AlxCrMnFeCoNi HEAs. The theoretical lattice constants are found to increase with increasing x, which is in good agreement with the available experimental data. The magnetic transition temperature for the body-centered cubic (bcc) structure strongly decreases with x, whereas that for the fcc structure shows a weak composition dependence. Within their own stability fields, both structures are predicted to be PM at ambient conditions. Upon Al addition, the crystal structure changes from fcc to bcc with a broad two-phase field region, in line with the observations. Bain path calculations suggest that within the duplex region both phases are dynamically stable.Comparison with available experimental data demonstrates that the employed approach describes accurately the elastic moduli of the present HEAs. The elastic parameters exhibit complex composition dependences and the elastic anisotropy is unusually high for both cubic phases. The brittle/ductile transitions formulated in terms of Cauchy pressure and Pugh ratio become consistent only when the strong elastic anisotropy is accounted for. The negative Cauchy pressure of CrMnFeCoNi is found to be due to the relatively low bulk modulus and C12 elastic constant, which in turn are consistent with the relatively low cohesive energy. Our findings in combination with the experimental data suggest anomalous metallic character for the present HEAs system.The negative SFE of fcc medium-entropy alloys (MEAs) and HEAs originate from the metastable character of the fcc phase. I argue that the common models underlying the experimental measurements of SFE fail in metastable alloys. Considering various metals including concentrated solid solutions, I demonstrate that in contrast to the experimentally measured SFEs, the SFEs obtained by DFT calculations correlate well with the primary deformation mechanisms observed experimentally in these alloys. In the case of negative SFE (or in metastable fcc alloys), the transformation-mediated twinning (TMT) is the predominant mechanism instead of the layer-by-layer twinning mechanism. It provides a continuous avenue for strain accommodation and strain hardening, realizing the joint transformation-induced plasticity and twinning-induced plasticity in the same system, and thus enabling the simultaneous improvement of strength and ductility. For the fcc CrMnFeCoNi HEA, upon Al addition or temperature increase, the intrinsic and extrinsic stacking fault energies increase, whereas the hexagonal close packed (hcp)/fcc interfacial energy stays almost constant.The work and results presented in this thesis give a good background to go further and study the plasticity of fcc HEAs as a function of chemistry and temperature. This is a very challenging task and only a very careful pre-study concerning the phase stability, magnetism, elasticity and GSFE can provide enough information to turn my plan regarding ab initio description of the thermo-plastic deformation mechanisms in fcc HEAs into a successful research. The novel TMT mechanism disclosed for the first time by myself and my colleagues advances our knowledge in plasticity and paves the road to design novel alloys with outstanding mechanical properties using quantum metallurgy.

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