MetE203: Thermodynamics of Materials

Bonus Term Project

High-Entropy Alloys
• Instructor: Assist. Prof. Dr. Simge Çınar Aygün

• Asmin Zengin
• ID: 2448017
High-entropy alloys
Easo P. George, Dierk Raabe and Robert O. Ritchie
https://doi.org/10.1038/s41578-019-0121-4

I found the article very interesting when I first read the abstract of it.
Alloying was a familiar concept to me however conducting an alloying
process with at least 5 principal elements was something else. I
wondered how it could be possible, so I started researching.
Alloying:
• From ancient times, human civilization has striven to develop new materials,
discovering new metals and inventing new alloys that have played a pivotal role
for more than thousands of years. Since the Bronze Age, alloys have traditionally
been developed according to a ‘base element’ paradigm. This strategy begins
with one and rarely two principal elements, such as iron in steels or nickel in
superalloys, and a minor alloying approach is used to obtain alloys with enhanced
properties.
• With few exceptions, the basic alloying strategy of adding relatively small
amounts of secondary elements to a primary element has remained unchanged
over millennia.
• However, new approaches are needed if the compositional space to explore is to
be significantly enlarged.
High-Entropy
Alloys (HEA):
• One approach is based on mixing together
multiple principal elements in relatively
high (often equiatomic) concentrations.
• These designed multicomponent alloys
were termed as ‘high-entropy alloys’
(HEAs) by Yeh et al., which suggests the
high configurational entropy of the
random mixing of elements in these
alloys.
• There are two definitions of HEAs by
composition and entropy.
Composition-based definition:
• HEAs are preferentially defined as alloys containing at least
5 principal elements, each with an atomic percentage
(at.%) between 5% and 35%.
• From this definition, HEAs need not to be equimolar or
near-equimolar, and even contain minor elements to
balance various materials properties, such as the ductility,
toughness, strength, creep, oxidation, etc.
Entropy-based definition:
• Entropy is a thermodynamic state function, and the essence of
entropy is “inherent chaos” of the system.
• The total mixing entropy has four contributions: configurational
entropy, vibrational entropy, magnetic dipole entropy, and electronic
randomness entropy.

• The configurational entropy is dominant over the other three

contributions. Hence, the configurational entropy often represents
the mixing entropy. HEAs have a configurational entropy in a random
state larger than 1.5R, where R is gas constant, no matter they are
single phase or multiphases at room temperature.
Some Properties of HEAs
Hardness:
• HEAs possess high hardness and strength. Compared with
other traditional alloys, such as the 316 stainless steel,
Hastelloy, HEAs have higher hardness and better anti-
annealing softening performance.
Compressive Property:
• The HEA systems generally possess an FCC phase and have
great combination of strength and ductility in compression,
when compared to those with a BCC phase.
Tensile Property:
• The crystal structure of the HEAs has a large influence on the tensile
properties.
• The excellent mechanical properties of HEAs over a wide range of
temperatures under tensile loading is evident, promising them ideal
candidates for structural applications, compared to conventional
superalloys and stainless steels.
Corrosion Resistance:
• Under high concentrations of sulfuric acid, hydrochloric acid, nitric
acid and other corrosive solution condition, HEAs show excellent
corrosion resistance.
Thermoelectric Property:
• HEAs have a high degree of chaos in its atomic arrangement, resulting
in the enhanced scattering of phonon and effectively reducing its
lattice thermal conductivity.
Future Opportunities
Further opportunities lie in the exploration of thermodynamics,
microstructure evolution and properties of HEAs with near-zero
stacking-fault energies.

Most efforts in the field are focused on mechanical properties but

recent works also revealed unexpected features of HEAs that might be
interesting for magnetic, invar or catalytic applications. Particularly,
HEAs with multi-functional properties might lead to new processes or
products.
References
George, E.P., Raabe, D. & Ritchie, R.O. High-entropy alloys. Nat Rev
Mater 4, 515–534 (2019).
https://doi.org/10.1038/s41578-019-0121-4
Ye, Y. F., Wang, Q., Lu, J., Liu, C. T., & Yang, Y. (2016). High-entropy
alloy: challenges and prospects. Materials Today, 19(6), 349-362.
https://doi.org/10.1016/j.mattod.2015.11.026
Zhang, W., Liaw, P.K. & Zhang, Y. Science and technology in high-
entropy alloys. Sci. China Mater. 61, 2–22 (2018).
https://doi.org/10.1007/s40843-017-9195-8