The design of thermomechanical processing
of non-eqiatomic FeMnNiCoMo high entropy alloy
for critical applications based on CALPHAD
and ab-inito calculations
Krzysztof Muszka1, Kamil Cichocki1, Paulina Lisiecka-Graca1, Piotr Bała1,
Lutz Krüger2, Sebastian Henschel2, Javier Dominguez3
1
AGH University of Krakow, Faculty of Metals Engineering and Industrial Computer Science,
30 Mickiewicza Ave., 30-059 Kraków, Poland
2
TU Bergakademie Freiberg, Institute of Materials Engineering,
Gustav-Zeuner-Str. 5, 095999 Freiberg, Sachsen, Germany
3
National Center for Nuclear Research,
Andrzeja Sołtana St., 05-400 Otwock-Świerk. Poland
[email protected],
[email protected],
[email protected],
[email protected],
[email protected],
[email protected],
[email protected]Keywords: High Entropy Alloy, Ab-initio Modelling, CALPHAD Method,
Molecular Dynamics, Mechanical Response
1. Introduction
Structural materials with high impact fracture toughness, enabled by twinning mechanisms, are
of significant interest for extreme-environment applications at low temperatures, such as transportation
and storage of liquefied gases, cryogenic technologies, and structural components in space vehicles.
Besides the already well-known, the new class of metallic high entropy alloys (HEAs) offer
new potentials for possible applications up to extreme loading conditions [1-2]. High-entropy ef-
fects, including the „cocktail effect” and sluggish diffusion, offer additional potential advantages
i.e. excellent combination of strength and ductility. In the present work, the numerical tools were
employed to design (FeMnNiCo)1-xMox alloy where x=<0-10>. The special focus was put on
assessment of the effect of Mo addition on the Stacking Fault Energy (SFE), strength and suscepti-
bility to twinning at room and cryogenic temperatures.
2. Materials and procedures
The development of a stable (FeMnNiCo)1-xMox high entropy alloy (HEA) with a Face-Cen-
tered-Cubic (FCC) solid solution was investigated using a combination of basic parameter calcula-
tions, CALPHAD, Density Functional Theory (DFT), and Molecular Dynamics (MD) simulations
to explore plastic deformation in the studied systems. This methodology is valuable for predicting
the properties of new alloys or modifying existing ones.
To achieve a single-phase solid solution, multicomponent alloys must satisfy specific criteria.
A critical requirement is achieving a sufficiently high mixing entropy, greater than 1.5R (where R
is the gas constant). Other important parameters include mixing enthalpy and the Valence Electron
The project is co-financed by funds from the state budget,
The project is co-financed by funds from the state budget, granted by the Minister of Science as part
granted by the Minister of Science as part of the Excellent Science II Program,
of the Excellent Science II Program, project no. KONF/SP/0109/2024/02, subsidy amount 67 870 PLN.
project no. KONF/SP/0109/2024/02, subsidy amount 67 870 PLN
1
Concentration (VEC). This study examines these parameters in detail, using them to determine the
phase composition of the studied HEAs in the initial design phase. Model alloys from the (FeMnNi-
Co)100-90(Mo)0-10 system were produced using an arc furnace, and phase composition was analysed
through microstructural and X-ray diffraction (XRD) techniques. The (FeMnNiCo)90Mo10 alloy was
found to contain molybdenum-rich µ-phase precipitates, while the other alloys exhibited stable solid
solutions in the RSC lattice. The alloys were hot rolled, followed by microstructural analysis, and
tensile and compressive test specimens were prepared for mechanical property evaluation. Basic pa-
rameter-based design proved insufficient for establishing clear correlations between thermodynamic
functions and material structure. Therefore, the CALPHAD method was employed, with thermody-
namic calculations performed using Thermo-Calc software and the TCHEA-5.4 database for high
entropy alloys. However, results were imprecise, particularly regarding the identification and extent
of precipitates. To refine phase stability predictions, DFT calculations were employed, enabling insi-
ghts into phase stability as a function of temperature, without experimental data. DFT also predicted
mechanical properties such as elasticity tensor, Young’s modulus, shear modulus, and thermodynamic
properties like specific heat, offering valuable insights into material behaviour before production [3].
Molecular dynamics simulations were conducted using Lennard-Jones potentials, as no existing po-
tentials for these alloys were available. While simple potentials like Lennard-Jones provide a general
understanding of material properties, more sophisticated potentials are required for accurate property
predictions. In this work, Embedded Atom Model (EAM) potentials, enhanced with Ziegler-Biersack-
-Littmark (ZBL) corrections, were used in LAMMPS software. These simulations revealed that mo-
lybdenum addition reduces stacking fault energy (SFE), promoting deformation via twinning, which
was a key objective of the study.
Experimental studies on plastic deformation followed, including compression tests at hot pla-
stic working temperatures using an ASP thermomechanical simulator. These results were used to
design hot-forming processes by analysing stress-strain curves and dynamic recrystallization ki-
netics. Further tests on cold-rolled alloys with varying degrees of deformation were conducted,
including microstructural and texture evolution analysis, which showed strain twinning and cha-
racteristic texture formation. The final phase involved evaluating mechanical properties at room
temperature and liquid nitrogen temperatures, with compression tests conducted at various strain
rates, from quasi-static to dynamic. Microstructural, texture, and XRD analyses confirmed that
molybdenum enhances the material’s tendency to deform via twinning.
This study provides valuable insights into the FeMnNiCoMo high entropy alloy system’s po-
tential in modern materials engineering. The computational and experimental results offer a de-
eper understanding of the thermodynamics, microstructure, and mechanical properties of high-
-entropy alloys, highlighting the challenges in HEA design. The addition of molybdenum improves
strength properties with minimal impact on ductility and promotes twinning deformation. Cryoge-
nic strength tests indicate that these Mo alloys are suitable for low-temperature applications, even
under dynamic loading conditions.
References
1. Grässel O.; Krüger L.; Frommeyer G.; Meyer L. W.: High strength Fe-Mn-(Al, Si) TRIP/TWIP steels
development – properties – application, International Journal of Plasticity, 16, 2000, 1391–1409.
2. Cantor B., Chang I.T.H., Knight P., Vincent A.J.B., Microstructural development in equiatomic multi-
component alloys, Materials Science & Engineering A, 375–377, 2004, 213–18.
3. Cichocki, K., Bała, P., Koziel, T. et al., Effect of Mo on Phase Stability and Properties in FeMnNiCo
High-Entropy Alloys, Metallurgical and Materials Transactions A, 53, 2022, 1749–1760.
Acknowledgements. The authors acknowledge the research project supported by the program
“Excellence initiative—research university” for the AGH University of Science and Technology.
