Materials Science and Technology

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High entropy alloys

H. K. D. H. Bhadeshia

To cite this article: H. K. D. H. Bhadeshia (2015) High entropy alloys, Materials Science and
Technology, 31:10, 1139-1141, DOI: 10.1179/0267083615Z.000000000969

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Published online: 18 Jun 2015.

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 Editorial
High entropy alloys
H. K. D. H. Bhadeshia

This issue of Materials Science and Technology is, I think, going to be seminal in defining the way forward
for the so-called high entropy alloys (HEAs). We identified and invited as many of the people involved in
HEA research as the databases listed. Not everyone was able to contribute. But those who did have written
in the best traditions of science and I thank them for their efforts. We invite discussion and further individual
contributions on this rapidly developing subject.
The maximum amount of configurational disorder, whether that is in the context of atomic solutions1 or mix-
tures of discrete particles,2 is obtained when the components are mixed in equal quantities. This follows
directly from Boltzmann’s classical relationship for configurational entropy, klnw. Consider a mole of atoms
made up of a mixture of n different types of particles, with the number of atoms in a particular species of par-
ticle being mi. Then the configurational entropy of mixing in its general form is given by2
Pn ( Pn )
DS M X n  x i  N a x i 
i¼1 x i mi i¼1 x i m i
¼ Qn ln N a Qn 2 i¼1 ln ð1Þ
kN a i¼1 m i i¼1 m i mi mi

P k is the Boltzmann constant, Na is Avogadro’s number and xi is the mole fraction of particle type i, so
where
that ni¼1 x i ¼ 1. For an atomic solution this reduces to the familiar form

DS M Xn
¼ 2 i¼1 x i ln x i ð2Þ
kN a

In the case of mixtures of particles, the configurational entropy would peak for particles of equal size and concen-
tration,
P and for solutions when the mole fractions of components are equal. Since the same basic form,
2 ni¼1 V i ln V i , applies to microstructural entropy,3,4 the most heterogeneous microstructurePis one where the
volume fractions Vi of all the phases are equal. Similarly, with information entropy we have 2 ni¼1 p i ln p i , where
pi is the probability of an independent event i, the value of which peaks when all probabilities are equal.5
Why is this peaking at equal concentrations (probabilities,...) important in the context of making the so-called
high entropy alloys? The argument is that if one introduces sufficient confusion into the alloy, then the ten-
dency for the precipitation of compounds is reduced because the product 2TDSM may dominate other ther-
modynamic terms such as the enthalpy of mixing. Such a system will at equilibrium tend to remain a random
mixture over a greater temperature range, extending it is hoped to ambient temperature, thus avoiding the
clustering or ordering of atoms that sometimes causes a deterioration of properties. Any ordering or cluster-
ing would reduce the configurational entropy.
Maximising the number of components (different species of atoms) helps. If in equation (2) all the concentrations
of n components are set to be equal, then the configurational entropy of mixing becomes R lnn, where R is the
gas constant.6 For a typical value for HEAs of n ¼ 5, assuming all elements are in equal concentration,
DSM ¼ 1?61R; thus at ambient temperature 2TDSM&24000 J mol21. This contribution to the free energy of mix-
ing is very large; a typical driving force for solid-state phase transformation is about one-tenth of this value.
The one caveat to this discussion is that the DSM equations illustrated here and in publications on HEAs assume
ideal solution, i.e. that the atoms are all dispersed at random. This is most unlikely, there are no ideal solutions; a
proper treatment of configurational entropy that accounts for the preferences of atoms to have particular
neighbours would lead to a reduction in the entropy of mixing. Someone needs to study the distribution of
atoms in HEA; the atomic structure of a solid solution can easily be investigated using the atom-probe technique
(e.g. Ref. 7). Specific studies focusing on this point are not available in the literature, nor does there
seem to have been any attempt to design HEAs in which the variety of atoms are indifferent to their neighbours
(i.e. interatomic bonding does not change much when compared with the pure species). However, Singh et al.8
characterised splat-quenched and ordinarily cast AlCoCrCuFeNi HEAs and found that the former was partly
ordered, and the latter a two-phase mixture. In other words, the assumptions of random distributions of atoms
used to justify the HEA concept are not correct and the configurational entropy term will make a correspondingly
smaller contribution. The paper by Tomilin and Kaloshkin9 is particularly worthy of study in the context of the
thermodynamics of HEAs – the neglect of strong interactions between components is a major shortcoming in the
literature.

Tata Steel Professor of Metallurgy, University of Cambridge, UK, and Professor of Computational Metallurgy, Graduate Institute of Ferrous
Technology, Pohang University of Science and Technology, Korea, email hkdb@cam.ac.uk

Ñ 2015 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
DOI 10.1179/0267083615Z.000000000969 Materials Science and Technology 2015 VOL 31 NO 10 1139
Editorial

Statements are sometimes made that the enthalpy of mixing is small for most metals10 and even that it is
always smaller than the entropic term for HEA.12 However, the entropic term assumed is always that for an
ideal solution which represents the greatest disorder, whereas in fact quasi-chemical theory should be
applied since the solutions are never ideal. A random dispersion of atoms can be induced by mechanical
alloying7 but the processing associated with the consolidation of powders leads to phase separation and pre-
cipitation in many HEAs (e.g. Ref. 11).
It could be argued that even if some kind of phase separation is favoured at low temperatures, it may not
actually take place if diffusion is sluggish. When many species are present in roughly equal concentrations,
there may operate a confusion principle. For example, metallic glass formation becomes easier when many
elements are involved in the crystallisation process.12 Although this may be the case, the indications are that
in many of the investigated HEAs, the diffusion may not be sufficiently sluggish to prevent a reduction in con-
figurational entropy and phase separation.13
Continuing on the theme of thermodynamics, the discussion of HEAs is often based on binary concepts.14 Gen-
eralisation from binary to multicomponent systems may be problematic. For example, a pair of the components
in a ternary may have the enthalpy of mixing DHMw0 and another pair DHMv0. The alloy behaviour would then
depend on the location on a plot of the free energy surface as a function of chemical composition.
High entropy alloys ultimately have to demonstrate a combination of properties that make them suitable for
application. Numerous studies have reported apparently good individual properties in experimental alloys.
However, as pointed out by Miracle,15 ‘there is much work between measuring a single attractive property in
a single alloy and demonstrating credibility for a particular application’. It is not clear whether the alloy con-
cept is as yet mature in this respect; indeed, as yet there does not seem to have been an application.11 Fur-
thermore, many of the mechanical properties reported are easily achieved in conventional materials so it is
necessary to reserve judgement on the ‘excellent properties’ of HEAs. Others are measured in com-
pression16 – it is probable that the definition of the combination of properties that are required will not happen
until there is a serious effort to make engineering components. In this context, the paper by Tsai et al.17 is
interesting because of the routine technology used to process an HEA and to measure tensile properties.
Miracle15 presents a convincing case that there is a need to stray away from the yearning to make single-
phase HEAs and to focus on the introduction of microstructural complexity in order to realise the potential of
alloys that still are concentrated but not single phase. The subject is young, and given that appropriate ther-
modynamic data may not exist18 to do CALPHAD type phase diagram calculations,19,20 empirical Hume-
Rothery type parameters,21 such as the number of valence electrons per atom, are being estimated to
assess the crystal structure transitions as a function of composition.18,22,23 Having said this, clever use of
available binary and ternary phase diagram data within the CALPHAD method can help alloy design.24
Neural networks25 have also been applied to assess experimental data to help predict structure, using elec-
tronegativity differences, valence electron concentration, atomic radius differences and enthalpy of mixing as
inputs.26 Another statistical approach27 has actually led to a new series of four component HEAs.
In some respects, HEAs follow the same metallurgical principles as ordinary alloys. Thus, chromium
improves the corrosion resistance28 unless precipitation leads to chromium depleted zones;29 this phenom-
enon is classically observed in stainless steels30 and is referred to as sensitisation. Since large concen-
trations of chromium (for example 32 at.-%) are present in some HEAs, it is not surprising that they can in
principle outperform stainless steels.31 It would of course be interesting to identify the mechanism of cor-
rosion protection, for example whether it involves the spontaneous formation of a transparent chromium
oxide layer, and whether this layer is regenerative as in stainless steel.32,33 Some interesting results on chro-
mium free HEAs show that in some circumstances,34 the corrosion resistance can be greater than that of
stainless steel; the mechanism is not clear. Corrosion resistant HEAs may find application as claddings pro-
vided that an appropriate deposition technology can be achieved.35,36
Whether HEAs have mechanical properties that are unique is not obvious. For example, the lack of sensi-
tivity of the elastic modulus to strain rate37 is known for metals.38 A critical assessment of the data available
thus far, with the aim of comparing against conventional materials, would be useful. Mishra et al.39 argue that
the misfit strain between atoms is related to dislocation mobility in concentrated alloys; the concept needs
some justification because the meaning of atomic misfit becomes less clear when the distinction between
solvent and solute disappears, and when solute atoms are closely spaced.
H. K. D. H. Bhadeshia
Editor

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