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mater.scichina.com link.springer.com . . . . . . . . . . . . . . . . . . . . . . . . . Published online xx 0 2017 | https://doi.org/10.1007/s40843-017-9195-8

Science and technology in high-entropy alloys

Weiran Zhang1, Peter K. Liaw2 and Yong Zhang1,3*

ABSTRACT ABSTRACT As human improve their ability to transportation, food, machinery, and defense industries.
fabricate materials, alloys have evolved from simple to com- As illustrated in Fig. 1, in the early stage of alloy, one
plex compositions, and accordingly with improving functions principal element was fused with other elements in trace
and performances, promoting the advancements of human amount to improve the specific properties. Today, the
civilization. In recent years, high-entropy alloys (HEAs) have design concept of many essential alloys is considered as
attracted tremendous attention in various fields. With mul- the traditional alloy-design strategy, such as Fe alloys
tiple principal components, they inherently possess unique [4,5], Cu alloys [6,7], Al alloys [8], Mg alloys [9,10], Ti
microstructures and many impressive properties, such as high alloys [11], and Ni alloys [12]. However, the chemical
strength and hardness, excellent corrosion resistance, thermal composition of modern alloys is greatly expanded, for
stability, fatigue, fracture, and irradiation resistance, in terms example, Inconel 718 superalloy, which is a representative
of which they overwhelm the traditional alloys. All these of Ni alloy, contains a variety of other elements [13] in
properties have endowed HEAs with many promising poten- addition to Ni. One of the three basic principles of bulk
tial applications. An in-depth understanding of the essence of amorphous formation gives a description that an alloy
HEAs is important to further developing numerous HEAs contains at least three elements [14,15]. Through careful
with better properties and performance in the future. In this analysis, it is found that the alloys in Fig. 1 are still deeply
paper, we review the recent development of HEAs, and sum- influenced by the traditional alloy-design concept. While
marize their preparation methods, composition design, phase for further improving the properties, the traditional de-
formation and microstructures, various properties, and sign paradigm meets with the bottleneck. Fortunately, the
modeling and simulation calculations. In addition, the future complexity of the elemental composition in alloys has
trends and prospects of HEAs are put forward. been increasing steadily with time as illustrated in Fig. 1.
Crystalline multi-principal element alloys and high-
Keywords: Keywords: high-entropy alloys, multiple principal
entropy alloys (HEAs) were first independently reported
components, microstructures and properties, phase formation,
in 2004 by Cantor et al. [16] and Yeh et al., [17] which
modeling and simulation calculations
refer to the same concept. Different from the traditional
alloy-design concept, HEAs are not based on only one or
INTRODUCTION two elements but contain at least five principal elements
Metals and alloys have a long history, and they have been in an equal or near-equal atomic percentage (at.%) with
playing an irreplaceable role in the process of human no obvious difference between the solute and solvent [17].
civilization. As shown in Fig. 1, the Bronze appeared as According to the existing physical-metallurgy and phase
early as in Shang Dynasty, lasting over 1,000 years, and diagrams, such multi-element alloys may produce many
the Iron Age lasted about 3,000 years starting from the phases and intermetallic compounds, resulting in com-
Spring and Autumn Warring States period [1]. The ap- plex and brittle microstructures that are difficult to ana-
plication of Al alloys has also been developed for one lyze and engineer, but probably have finite practical
century [2], even Ti alloys for more than sixty years [3]. values [18]. Beyond expectations, experimental results
Till now, metals and alloys have been closely involved in indicate that the higher mixing entropy in these alloys
all aspects of our lives, including agriculture, housing, enhances the formation of random solid-solution phases

1
State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China
2
Department of Materials Science and Engineering, University of Tennessee, Knoxville, TN 37996, USA
3
Beijing Key Laboratory for Magneto-Photoelectrical Composite and Interface Science, University of Science and Technology Beijing, Beijing 100083,
China
*
Corresponding author (email: [email protected])

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High-entropy alloys
Bronze age Iron age Industrial revolution were born in 2004

CoCrFeNiMn (Cantor alloy)

AlCrFeNiCoCu
Al0.3CrFeNiCo
Al20(TiVCrMnFeCoNiCu)80
HEAs
Sconf (J mol−1 K−1)

s
se
ea
cr
in
i on
sit
1.5 R po Superalloys

s s
m

oy u
co

all rpho
l
Medium-entropy ica

o
m

Am
e
alloys zone Ch
Stainless steel
1R
IMs
Low-entropy Al alloys
alloys zone Mg
Iron Ti
alloys
alloys
Bronze

3000 2500 2000 1900 1950 2000

BC BC BC
Year

Figure 1 Rising trend of alloy chemical complexity versus time (IMs: intermetallics or metallic compounds, HEA: high-entropy alloy). Reproduced
with the permission from Ref. [1]. Copyright 2017, Springer.

with simple structures, such as face-centered-cubic progress of HEAs, provides a supplement to the research
(FCC), body-centered-cubic (BCC) structures, or hex- content of HEAs, and forecasts the future development of
agonal close packing (HCP) structures, and thus reduces HEAs.
the number of phases [19–29]. Since then, the new alloy-
design strategy opens a huge, unexplored field of multi- DEFINITIONS
component alloys. The strategy of alloy design has ob- There are two definitions of HEAs by composition and
tained unimaginable successes and great efforts have been entropy, which lead to some confusion and controversy
devoted to the development and application of many that whether the multi-component alloy could be re-
HEAs [30,31] in various fields due to their excellent garded as HEAs [30].
performance, such as the unique wear resistance [32],
excellent strength and thermal stability at elevated tem- Composition-based definition
peratures [33,34], superior high elongation [35,36], great The earliest composition-based definition was published
fatigue and fracture resistance [37–39], etc. in 2004 [17]. HEAs were preferentially defined as alloys
Up to now, thousands of reports on HEAs have been containing at least 5 principal elements, each with an
published, including the excellent book “High-entropy atomic percentage (at.%) between 5% and 35%. It is
Alloys: Fundamentals and Applications” [40], and several worth mentioning that the atomic percentage of each
review papers [19,20,41–45] covering almost every as- minor element, if any, is even smaller than 5 %. The
pects of current research on HEAs. However, our un- definition is expressed as follows [18,20,40]:
derstanding and research on HEAs is just the tip of the n major 5, 5 at . % ci 35 at.%
iceberg, and more unexplored secrets of HEAs are dis- (1)
closed continuously. Due to their remarkable properties and n minor 0, cj5 at.%,
and promising research prospects, many new findings in where nmajor and nminor are the numbers of major elements
HEAs are emerging beyond the existing review papers and minor elements, respectively. ci and cj are the atomic
and books [40,41]. This paper summarizes the recent percentages of the major element, i, and the minor ele-

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ment, j, respectively. From this definition, HEAs need not of alloys, both definitions overlap for the most part. De-
to be equimolar or near-equimolar, and even contain spite these definitions, the compositions in non-over-
minor elements to balance various materials properties, lapping regions are also regarded as HEAs. For example,
such as the ductility, toughness, strength, creep, oxida- the maximum configurational entropy of a 5-component
tion, etc. [32,46,47]. HEA is 1.61R (ΔSconf=Rln5=1.61R) for the equimolar al-
loy, and the minimum value of the configurational en-
Entropy-based definition tropy is 1.36R for an alloy with 35% A, 35% B, 20% C, 5%
Entropy is a thermodynamic state function, and the es- D, and 5% E (atomic percentage, ΔSconf=−R(2×0.35×
sence of entropy is the system of “inherent chaos” [20]. ln0.35+0.2×ln0.2+2×0.05×ln0.05)=1.36R). The latter alloy
According to the Boltzmann’s thermodynamic statistics is also considered as an HEA by the composition-based
principle, the quantitative relationship between the en- definition but cannot fit into the entropy-based defini-
tropy and randomness of the system is given by: tion. Another example is an equimolar alloy containing
Sconf = k lnw , (2) 25 elements, with a concentration of 4 at.% for each
where k is the Boltzmann s constant, and w is the element. This alloy is still considered as an HEA since the
number of distinguishable ways of arranging the atoms in value of the configurational entropy is 3.219R (ΔSconf=−R
the solution. The total mixing entropy has four con- (25×0.04×ln0.04)=3.219R). An alloy with a certain com-
tributions: configurational entropy, S mixconf position fitting only one of the two definitions is regarded
, vibrational
vib mag
as an HEA. In addition, sometimes the quaternary equi-
entropy, S mix , magnetic dipole entropy, S mix , and molar alloy also considered to be an HEA in literature
elec
electronic randomness entropy, S mix , the relationship because its composition and configurational entropy are
among the various is given by: close to the lower limits of both definitions. Thus, the
conf
S mix = Smix vib
+ S mix elec
+ Smix mag
+ S mix . (3) definitions of HEAs are simply approximate guidelines,
The configurational entropy is dominant over the other not strictly laws [19,40] .
three contributions. Hence, the configurational entropy From the two definitions and the description of non-
often represents the mixing entropy in order to avoid overlapping regions of HEAs, it implies that the basic
complex calculations to determine the other three con- principle behind HEAs with multiple principal elements
tributions [40]. For an ideal random n-component solid is to achieve the high mixing entropy in order to enhance
solution, its ideal configurational entropy per mole is the formation of solid-solution phases. As 1.5R is a lower
approximately [19]: limit for HEAs, we further define medium-entropy alloys
Sconf = R[c1lnc1 + … + cnlncn]
(MEAs) and low-entropy alloys (LEAs) to differentiate
n the power of the mixing entropy effect for all alloys in the
= R ci lnci , nature. Herein, 1R is the boundary between MEAs and
i =1 (4) LEAs since the mixing entropy less than 1R is expected to
where R is the gas constant, and ci is the mole fraction of
be noncompetitive with a larger mixing enthalpy [40].
the ith element, and n is the number of the components.
Thus, the alloys are divided into the following three
According to the extreme theorem, when
categories and illustrated in Fig. 2 [48]:
c1 = c 2 = … = cn, the entropy of the system reaches its
1. LEAs: ΔSconf< 1R, including traditional alloys based
maximum value.
on one or two elements;
Consider an equi-atomic alloy in its liquid state or
2. MEAs: 1R ≤ΔSconf≤ 1.5R, including alloys based on
regular solid-solution state. Its configurational entropy
two to four elements;
per mole could be calculated as [30]:
3. HEAs: 1.5R <ΔSconf , including alloys based on five
Sconf = Rlnn . (5) elements at least or some quaternary equimolar alloys.
It defines that HEAs have a configurational entropy in a It should be noted that among various thermodynamic
random state larger than 1.5R, no matter they are single factors, such as the mixing enthalpy, mixing entropy,
phases or multiphases at room temperature. This defini- atomic-size difference, valence-electron concentration,
tion could be expressed as [48]: and electronegativity, the mixing entropy is the sole fac-
Sconf > 1.5R. (6) tor, which rises with increasing the number of principal
elements. The name “high-entropy alloys” is pertinent for
Developing definitions MPEAs (multiple principal elements alloys) [32,49–51].
Although each definition of HEAs contains a wide range Various names have appeared with the development of

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Solid
mixing Mechanical alloying

Arc melting
Component Liquid Inductive melting High-entropy
mixing Laser melting
∆Sconf>1.5 R elements alloys
Laser cladding
High-entropy alloys

Sputter deposition
Gas
1R≤∆Sconf ≤1.5 R mixing Pulse-laser deposition
Atomic-layer deposition
Medium-entropy alloys

Figure 3 Fabrication routes of HEAs.

∆Sconf<1 R
Low-entropy alloys

Figure 2 Alloys world based on the configurational entropy. B C D

E
A

HEAs, such as complex concentrated alloys (CCAs) Selected

composition
[19,52], complex multicomponent alloys (CMAs) [46,53], Bulk
Film
compositionally complex alloys (CCAs) [40], baseless al-
loys (BAs) [19], metal buffets (MBs) [45], etc. Substrate

PREPARATION OF HEAs Figure 4 Schematic of multi-target co-deposition for HEAs.

The discovery of HEAs is related to the study of bulk
amorphous alloys [20]. Therefore, the preparation
method of HEAs has inherited from the preparation [59]. Thus, compared to conventional alloys, the as-cast
technique of amorphous alloys, which can be divided into samples of HEAs may have obvious casting defects, such
three major routes [40], as shown in Fig. 3. The main as cracks, pores, and residual stresses along with com-
route is liquid mixing, including arc melting, electric- positional gradients and abnormal grain-size distribu-
resistance melting, inductive melting, laser melting, laser tions. In order to obtain organized and well-behaved
cladding, and laser engineered net shaping (LENS) [52]. HEAs, subsequent processing is essential [60–63].
The second route is solid mixing, which mainly contains As the development of HEAs, the elements with FCC or
the mechanical alloying and subsequent consolidation BCC crystalline structures were generally considered as
process. Another route is gas mixing, including sputter the matrix elements. Thereafter, appropriate modification
deposition, pulse-laser deposition (PLD) [20], atomic- elements were added to improve the required perfor-
layer deposition (ALD) [40], molecular-beam epitaxy mances. The “trial and error” traditional alloying method
(MBE) [54], and vapor-phase deposition. leads to the consumption of a large number of human
The aforementioned methods could fabricate three-di- and material resources, research-cycle extension, low ef-
mensional bulk, two-dimensional film-like, and one-di- ficiency, etc. These shortcomings are more conspicuous
mensional fibrous HEAs, and the three-dimensional for multi-element HEAs [64]. The development of high-
sample block-body-study is the most widely used throughput experiments can well solve these problems
[36,39,55,56]. Among the reported preparation methods, [65]. High-throughput experiments have been developed
arc melting is the dominant fabrication route to produce in the preparation of thin films and bulk alloys, especially
bulk HEAs [20,53,57,58]. More recently, gradient bulk for the fabrication of thin films. In addition, the multi-
samples of HEAs were produced by elemental power target co-deposition method is suitable for the prepara-
mixes with LENS apparatus [52]. Due to the inherent tion of HEA films with various constituent elements [66].
compositional complexity and the huge difference in the As shown in Fig. 4, co-deposition uses a different distance
melting points between the constituent elements, the between the substrate and the target, and different targets
preparation of HEAs is challenging. Significant elemental provide a certain concentration gradient on the substrate
segregation occurs during melt solidification and cooling during deposition to produce a HEA film with a con-

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tinuous concentration gradient [66]. Subsequently, com- Table 1 Mixing enthalpy data (KJ mol−1) between the elements of Fe,
Ni, Cr, Cu, and Zr
bining with high-throughput characterization techniques,
we can achieve rapid screening of HEAs, and then the Fe Ni Cr Cu Zr
bulk-like selected components are prepared. According to Fe ‒ −2 −1 13 −25
the composition design of HEAs, many single-element or Ni ‒ ‒ −7 4 −49
alloy targets can be prepared, with the atomic percentages Cr ‒ ‒ ‒ 12 −12
of elements controlled by adjusting the target sputtering Cu ‒ ‒ ‒ ‒ −23
power. The HEA films with a continuous composition Zr ‒ ‒ - ‒ ‒
gradient is obtained and then the bulk-like selected alloy
can be manufactured. Nowadays, the high-throughput
highway to the computational HEAs design is a great was BCC phase. In addition, Qiao et al. [23] found that
opportunity and challenge for the development of HEAs the as-cast alloy GdHoLaTbY (in atomic proportion)
[67]. formed a HCP phase.

PHASE FORMATION Mesophase and other complex phases in HEAs

Although there are more than four or five elements in The high entropy of HEAs hinders the formation of in-
HEAs [20], they tend to form a relatively-simple phase termetallic compounds and the occurrence of phase se-
after solidification, such as FCC [21], BCC, or HCP paration, therfore the formation of solid-solution phases
[23,68] structures. However, with the extensive and deep is promoted [52]. However, there are many factors that
research on HEAs, it is found that the alloys also contain affect the formation of HEAs, including the mixed en-
ordered intermetallics, amorphous and nanocrystalline thalpy, atomic-size difference, valence-electron con-
precipitates [19,47,69]. centration, and so on [50]. The mesophase or complex
multi-phase coexistence forms in HEAs due to the ex-
Simple solid-solution structure in an HEA istences of some chemically-compatible elements. Li et al.
HEAs are easy to form phase structures with simple FCC, [73] studied the HEA of FeNiCrCuZr. They found that
BCC and HCP solid-solution structures [9,20,23]. One apart from the BCC phase, intermetallic compounds also
famous HEA is the Cantor alloy [20], containing Fe precipitated in the alloy; and the formation of inter-
(BCC), Co (HCP), Cr (BCC), Mn (BCC), and Ni (FCC) in metallic compounds was due to the strong compound-
an equimolar ratio, with only an FCC solid-solution formation tendency of Zr with other metals, consistent
phase when solidified dendritically in the as-cast sample. with measurements that the mixing enthalpies between
Then the 5-component alloy was expanded to a 6- Zr and other metals are too negative (Table 1). Thus, the
component alloy by adding Cu (FCC), Nb (FCC), or V mixing enthalpy became another dominant factor to fa-
(BCC), showing the simple FCC solid-solution structure cilitate the formation of intermetallic compounds in Fe-
in the as-cast alloy with different lattice parameters. NiCrCuZr. In some systems the high mixing entropy
When the HCP-type Ti was added, a BCC structure cannot completely overcome the contribution of the high
formed within the FCC solid-solution phase [16]. An- enthalpy mixing to the free energy.
other typical example is the AlxCoCrFeNi (molar per-
centage, 2≥ x ≥0) system prepared by arc melting [70]. Nanocrystalline and amorphous phases in HEAs
The as-cast CoCrFeNi alloy has a pure FCC solid-solution Conventional alloys or bulk amorphous alloys can only
phase. As increasing the Al molar percentage from 0 to 2, precipitate nanocrystals under special heat-treatment
the AlxCoCrFeNi system changes the crystal structure conditions. The lattice-distortion effect and the slow-
from FCC to FCC+BCC phases, and finally to a single diffusion effect in HEAs seriously hinder the nucleation
BCC phase [55]. A typical alloy TaNbHfZr has a solely and growth of the grains. Hence, some HEAs precipitate
BCC structure [71]. nanometer phase and even amorphous phase during the
Although the HCP phase is often referred to as a typical as-cast or complete-tempering condition [20,40,47]. As
simple solid-solution structure of HEAs, there is few illustrated in Fig. 5, a series of heat-treatment conditions
discovery for this phase. Tsau [72] found the HCP solid- were performed on Al0.5CoCrFeNi alloy [74], and the
solution phase in the alloy of TiCrZrNb (in atomic pro- bright-field image of the acicular precipitate and the
portion), but the HCP phase did not exist independently, corresponding diffraction patterns are present, indicating
and it was in the interdendritic region, and the matrix that such precipitates have the same BCC (B2) phase as

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Al0.5 Tungsten bar

Metals

Dendrite
(FCC) Button-shaped
sample

Precipitate
(B2, BCC)

011 Rod-shaped
sample
002
−
011
0.5 µm
Z=[100]

Figure 5 The bright-field image and corresponding diffraction pattern Figure 6 Schematic of arc melting.
of the acicular precipitate in the Al0.5CoCrFeNi alloy (the precipitate
possesses an ordered BCC crystal structure). Reproduced with the per-
mission from Ref. [74]. Copyright 2014, Elsevier.

The microstructure of the alloy can also be changed by

controlling the growth direction and the growth rate of
the interdendritic structure. Zhao et al. [75] developed an crystal during the solidification process of the alloy.
amorphous alloy, which can be uniformly deformed Zhang et al. [79] successfully prepared Al0.3CrFeNiCo
without generating shear at room temperature. Mean- columnar crystals by Bridgman primary and secondary
while, its critical size is greater than 3 mm, and the directional solidification. The effects of directional soli-
amorphous transition temperature of the alloy is close to dification on the microstructure, crystal orientation, and
room temperature, with low density, high specific mechanical properties of the Al0.3CrFeNiCu2 alloy were
strength, and low elastic modulus. studied. In addition, eutectic and peritectic structures can
be observed in HEAs of different systems. For example,
MICROSTRUCTURES AlxCrCeFeNi2 HEAs exhibit eutectic clusters similar to
In the case of multicomponent alloys, there are more sunflower shapes [80], while AlCoCrFeNb0.5Ni [81] and
chances of segregation of elements due to the difference CoFeNi2V0.5Nb0.75 [58] alloys exhibit lamellar eutectic
between the constituent elements in melting points, structures.
densities, and other physical properties. Depending on
the growth conditions, grains may grow into planar, PROPERTIES
cellular, or dendritic morphologies [76]. For HEAs, arc
melting limits the fabrication of HEA ingots, compared to Hardness
induction melting. The melting furnace with non-con- The HEA is widely studied not only because it forms a
sumable tungsten electrode is only useful for making unique multi-component solid-solution phase but also
ingots with a limited size and shape (button shaped or because it possesses high hardness and strength. Fig. 7
slender-rod shaped as shown in Fig. 6). After the arc shows the hardness of a variety of alloys in the as-cast and
melting or induction melting, the alloy exhibits as-cast fully-annealed states. Compared with other traditional
dendrites. The dendrites and inter-dendrites have sig- alloys, such as the 316 stainless steel, Hastelloy c, HEAs
nificant component segregations [40]. Solidification/ have higher hardness and better anti-annealing softening
cooling rates have a significant influence on the micro- performance [17].
structural evolution of as-cast HEAs [77]. The AlCoCr-
CuFeNi HEA fabricated by splat quenching with rapid Compressive property
solidification rate (106–107 K s−1) possessed a single BCC The mechanical properties of HEAs are evaluated by
phase with fine polycrystalline structures, whereas the as- compressive loading on the cylindrical samples [82,83],
cast alloy had multi-phases with serious inter-dendritic which could be prepared easily by arc melting. The HEA
segregation [78]. systems generally possess an FCC phase and have great

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1000 ture alloys. The compression yield stress reduces with

As-cast
increasing temperature, and the inflection point is around
Annealed
800 1,000 K for almost all alloys. NbMoTaW and NbMo-
TaWV exhibit outstanding behaviour and remain useful
strengths up to 2,000 K (Fig. 8b).
600
Hardness(HV)

For the AlxCoCrFeNi and AlxCoCrCuFeNi systems

[17,70], increasing the amount of Al results in the for-
400 mation of a BCC phase in the FCC matrix, which yields
an increase in the compressive strength at the expense of
ductility. The HEAs with an FCC phase, such as Al0.1
200 CoCrFeNi [84], CoCrFeNi, and CoCrFeNiMn [85], ex-
hibits excellent plasticity and work-hardening behaviour
0 with low yield strength under compressive loading. The
Al0.75CoCrFeNi alloy with FCC + BCC dual phases ex-
o
Cu TiVF iZrCo
NiZ rCo

l
el

V
r
iZr
Zr

r
Cr

r
tee

Ste y
llite
AlT eNiZ

oC

oC
rC

l-4
Ste

llo
TiV FeNi

o
eN

AlT eNiZ

iZ

Sta ss S
rC

C
rC

ste

6A
hibits an excellent yield and ultimate strengths of
iZr
eN
TiV eN
F
iVF

ss
6 S NiZ

Ti-
TiV

TiV

Ha
eN

nle
inle
F
iVF

1,938 MPa and 2,221 MPa, respectively, and a limited

Fe

e
Cu

Mo

iVF

F
tai
TiV
Cu

Mo

ductility of 7.6% [86].

AlT
Mo

PH
31
-4
17

Tensile property
Figure 7 Comparison of hardness between HEAs and conventional Few studies were focused on the tensile properties of
alloys before and after annealing. (a) Ni-2.15Cr-2.5Co-13.5Mo-4W HEAs. The crystal structure of the HEAs has a large in-
-5.5Fe-1Mn-0.1Si-0.3V-0.1C (wt.%); (b) Co-29Cr-4.5W-1.2C (wt.%).
The data are from Ref. [17]. fluence on the tensile properties [36].
He et al. [87] conducted systematic study on the in-
fluence of the progressive addition of Al on the me-
combination of strength and ductility in compression, chanical behaviour of the FCC-phase CoCrFeNiMn HEA,
when compared to those with a BCC phase, in Fig. 8a. illustrated in Fig. 9. The FCC alloy of AlxCoCrFeNiMn
However, the yield strength of HEAs with a BCC phase is system exhibits excellent plasticity and low strength,
very high and comparable to bulk metallic glasses [46]. whereas the dual phase alloys exhibit a better combina-
Increasing in the number of principal elements, the tion of strength and ductility. The AlCoCrFeNi2.1 alloy
strength of the HEAs system increases due to solid-so- with dual phases also presents promising tensile proper-
lution hardening, with reduced ductility [20]. Miracle and ties with an elongation and fracture strength of 23% and
Senkov [19] reviewed the compression yield stresses be- 1,200 MPa, respectively [88].
tween the refractory HEAs and other elevated-tempera- In the range of low-temperature to room-temperature,

a b
2500 CoCrFeNiMn
CoCrFeNiMnV0.25 Al0.4Hf0.6NbTaTiZr
Al0.3CoCrFeNi
Al0.6CoCrFeNi
2000 AlMo0.5NbTa0.5TiZr
Al0.75CrFeNi AlNbTiV
2000 Al0.75CoCrFeNi
Al0.75CoCrFeNiTi0.25 CrMo0.5NbTa0.5TiZr
Compressive yield (MPa)

Al0.85CoCrFeNi CrNbTiVZr
AlCoCrFeNi
Compressive σy (MPa)

AlCoCrCuFeNi 1500 CrNbTiZr

BCC+FCC AlCoCrFeNiTi0.5 HfNbTaTiZr
1500 AlCoCrFeNiV0.2 MoNbTaVW
AlCoCrFeNiV0.8
BCC MoNbTaW
NbTiVZr
1000
1000

FCC
500 500

0 0
0 20 40 60 80 100 200 400 600 800 1000 1200 1400 1600 1800
Ductility (%) Temperature (K)

Figure 8 (a) Compressive behaviour of various HEAs; (b) compressive yield strength versus temperature. Reproduced with the permission from Ref.
[19]. Copyright 2017, Elsevier.

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1800
1200 Al0.3CoCrFeNi
FCC FCC+BCC

1000 Tensile strength 1600

77 K 2×10−4s−1
Yield strength

Tensile strength (MPa)

Elongation
Strength (MPa)

800
1400
I
II 298 K 5×10−5s−1
600 298 K 2×10−4s−1
1200
400

298 K 1×10−3s−1
1000
200 1.00 1.60 3.15
−2 0 2 4 6 8 10 12 Diameter (mm)
Al at.%
20
Al0.3CoCrFeNi
Figure 9 Tensile strength, yield strength, and elongation of the as-cast
AlxCoCrFeNiMn alloys. Reproduced with the permission from Ref. [87].
16 77 K 2×10−4s−1
Copyright 2014, Elsevier.
Elongation (%)
12 298 K 2×10−4s−1
the yield strength and the deformation of the alloy de-
crease as the temperature drops. However, Li et al. [36]
8 298 K 5×10−5s−1
found that the Al0.3CoCrFeNi alloy tensile strength and
elongation in the liquid nitrogen temperature reached the
maximum. The curves of the quasi-static tensile en- 4 298 K 1×10−3s−1

gineering of the alloy in the range of 77–298 K are shown

in Fig. 10. The Al0.3CoCrFeNi HEA at low temperature 0
has good plastic-deformation behavior for the formation 1.00 1.60 3.15
Diameter (mm)
of deformation twins, which is similar to the alloy of
CoCrFeMnNi studied by Otto et al. [62]. The yield Figure 10 Tensile strength (a) and elongation (b) as a function of fiber
strength and shaping deformation were measured in the diameter, respectively. Reproduced with the permission from Ref. [36].
Copyright 2017, Elsevier.
range of 77–1,073 K. At the liquid-nitrogen temperature,
the yield strength reaches the maximum, indicating that
the alloy with a fine grain structure has very good me-
chanical properties over the entire testing temperatures, HEA system shows that the CoCrFeNi alloy has good
similar to conventional alloys, and exhibits serrated flows pitting corrosion resistance, similar to 304 stainless steel
at intermediate temperatures. Diao et al. [45] summarized [43,91–93]. The polarization curves of the Al0.5
the yield strength of HEAs and conventional alloys from CoCrCuFeNi alloy and 304 stainless steel in 1 mol L−1
room temperature to 1,900 K. The excellent mechanical H2SO4 solution showed that the corrosion potential of
properties of HEAs over a wide range of temperatures HEAs is higher, with better corrosion resistance [43,91–
under tensile loading is evident, promising them ideal 94].
candidates for structural applications, compared to con- The relationship between Ep and Icorr of HEAs (Alx
ventional superalloys and stainless steels [45,62,89,90]. CoCrFeNi in which x = 0.3, 0.5, and 0.7) and conven-
tional alloys (such as stainless steels, Al-, Ti-, Cu-, and Ni-
Corrosion resistance based alloys) [91] are displayed in Fig. 11. The data were
Under high concentrations of sulfuric acid, hydrochloric measured in the environment of 3.5 wt% NaCl solution at
acid, nitric acid and other corrosive solution condition, room temperature. It suggests that HEAs have higher
HEAs show excellent corrosion resistance, especially the pitting potential and lower corrosion current densities
one with Cu, Ti, Cr, Ni, or Co [43,91,92]. Some HEAs than Al-, Cu-, and some of Ti-based alloys. Therefore, the
presents outstanding corrosion resistance even better HEAs show excellent localized and general corrosion
than the traditional stainless steel. The CoCrFeNiCux resistance.

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Thermal stability
AlxCoCrFeNi HEAs
Oxide
0.4 Stainless steels 1,173 25
Ni-alloys Ti-alloys
Carbide

Fractional decrease in
Temperature (K)
Ep (V) vs. SEC

hardness (%)
0.0

FCC 1,073 9.5

Cu-alloys

−0.4 AlxCoCrFeNi HEAs

Al-alloys Stainless steels FCC
Al-alloys Carbide
Ti-alloys
−0.8 Cu-alloys 973 2.6
Ni-alloys
Schematic of composite
0.0 0.4 0.8 1.2 1.6 2.0 2.4 microstructure 600 h
Icorr (µA cm ) −2
Figure 12 Diagram of composite microstructures observed in the as-
sintered condition. Reproduced with the permission from Ref. [96].
Figure 11 Comparison of Ep and Icorr between HEAs of AlxCoCrFeNi (x
Copyright 2017, Elsevier.
= 0.3, 0.5, and 0.7) and other conventional alloys in 3.5 wt% NaCl
solution at room temperature. Reproduced with the permission from
Ref. [91]. Copyright 2017, Elsevier. studied the in situ electron irradiation of ZrHfNb with an
amorphous structure, and Jin et al. [100] studied the
CoCrFeNiMn with an FCC structure. It was found that
Thermal stability the CoCrFeNiMn HEA did not change significantly after
Refractory HEAs [27] are a category of emerging multi- 773 K high-temperature and 3 meV Ni ions irradiation,
component alloys, showing superior mechanical proper- and the grains did not coarsen. High performance of
ties at elevated temperatures and being important for HEA radiation-resistant materials provides a new idea for
application [33,95]. The NbMoTaW alloy has better nuclear materials, and it has been used as catalyst in the
performance retention than the refractory metal tungsten nuclear energy [97,101–103]. Waseem et al. [68] con-
after a heat exposure at 1,373 K for 3 days [33]. Mean- sidered that the WxTaTiVCr as low/reduced-activation
while, the HEAs with these excellent properties drive a alloys have a promising future for fusion power plants.
new class of materials in nanoscale devices potentially in
high-stress and elevated-temperature applications. Sa- Thermoelectric property
thiyamoorthi et al. [96] found that ultrafine-grained Thermoelectric materials capable of the direct conversion
CoCrFeNi HEAs show the exceptional thermal stability between heat and electricity have attracted tremendous
upon the exposure of sintered compacts to high tem- attention in the past several decades for the engine-waste
perature (973 to 1,173 K) and prolonged duration of heat recovery to improve the fuel efficiency. HEAs have a
600 h, as illustrated in Fig. 12. Samples exposed to 973 K high degree of chaos in its atomic arrangement, resulting
for 600 h show negligible change in hardness. Meanwhile, in the enhanced scattering of phonon and effectively re-
the fractional decrease in hardness after 600 h at 1,073 K ducing its lattice thermal conductivity. The PbSnTeSe
and 1,173 K is 9.5%, and 25%, respectively. [104] HEA was discovered, possessing quite a low lattice
thermal conductivity of 0.6 W m−1 K−1 at room tem-
Irradiation property perature. By minor additions of La to substitute Pb, the
In general, the interaction between energetic ions and thermoelectric performance of PbSnTeSe could be further
atoms in the material causes lattice damage, resulting in a enhanced, as indicated in Fig. 13a. The series of
variety of defects, including point defects, dislocation Pb1−xSnTeSeLax alloys containing various miscellaneous
loops and holes [97], etc. The research shows that the contents of La, x = 0, 0.02, 0.04, 0.06, 0.08, and 0.10, are
HEA still has high phase stability, even the Au ion-irra- designated hence as base, 0.5La, 1.0La, 1.5La, 2.0La, and
diation dose exceeding 50 dpa (displacement per atom). 2.5La, respectively. The Pb1−xSnTeSeLax alloys show a
At the same irradiation dose (50–70 dpa), compared to lattice thermal conductivity below 1 W m−1 K−1 at room
other commonly-used irradiation-resistant materials, temperature, which is far lower than that of binary
such as M316 stainless steel and pure Zr, an HEA has a compounds with the same crystal structure, for example,
relatively-low volume swelling rate [98]. Nagase et al. [99] SnTe, PbTe, and PbSe, due to the strong phonon scat-

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a b 2.25

(200)
1.2
Base 1.5 La PbTe 1.1
2.00

κ-κe (W m−1 k−1)

(220)
0.5 La 2.0 La 1.0
SnTe 0.9
1.0 La 2.5 La
Intensity (a.u.)
1.75

κ-κe (W m−1 k−1)

0.8
PbSe 0.7

κb
(222)

(420)
1.50 0.6

(400)

(422)
0.5
(111)

(600)
(311)

(440)
0.4
1.25 3.3 3.0 2.7 2.4 2.1 1.8 1.5 1.2 0.9
Base 1.5 La 1000/T(K−1)
1.00 0.5 La 2.0 La
1.0 La 2.5 La
0.75
PDF#65-8374
0.50
20 30 40 50 60 70 80 90 100 300 400 500 600 700 800 900

27.2
27.6
28.0
38.0
38.5
2θ (°) T (K)

Figure 13 (a) XRD patterns of Pb1−xSnTeSeLax HEAs; (b) the combined lattice and bipolar thermal conductivity for all the samples. The lattice
thermal conductivity of PbTe, PbSe, and SnTe at room temperature is also shown in (b). The inset in (b) presents κ−κe as a function of 1,000/T.
Reproduced with the permission from Ref. [104]. Copyright 2017, Taylor & Francis Group.

tering resulted from the severe lattice-distortion of the multi-scale simulations to accelerate material-develop-
PbSnTeSe HEA. Unfortunately, the lattice thermal con- ment methods and approaches [109,110]. The material
ductivity of the base alloy starts to rise when the testing simulation is widely used to predict material properties. It
temperature exceeds 400 K due to the strong bipolar ef- can be used to simulate the material from different scales,
fect. For all the La-doped alloys, the bipolar effect is and qualitatively and/or quantitatively describe the
suppressed to a certain degree but still exists. The inset of characteristics of the material, and promote us to un-
Fig. 13b analyzes the lattice thermal conductivity without derstand the material from multiple angles. Fig. 14 dis-
bipolar contribution, κ−κe vs. 1,000/T (κ: thermal con- plays the relationship between the time and space.
ductivity, κe: electronic thermal conductivity). It is ob- Computational materials science involves all aspects of
vious that the lattice thermal conductivity at 873 K would the material, such as different levels of structures, various
be lower than 0.5 W m−1 K−1 for the base alloy, if the properties, etc. Thus, there are many corresponding cal-
bipolar effect was entirely eliminated. culation methods, the first-principles density functional
HEAs also have other excellent properties, such as ex- theory (DFT), molecular dynamics (MD), discrete dis-
cellent wear resistance [105], fracture toughness [36], as location dynamics (DDD), phase-field method (PFM),
well as very high resistivity [56,106]. At the same time, the thermodynamics model (TM), finite element method
HEA has good soft magnetic properties [20,107]. For the (FEM) [111], etc. For materials with different space scales,
FeCoNi(AlSi)0.2 HEA [106] prepared by arc-melting there are corresponding material calculation methods,
method, the saturated magnetic strength, coercivity, and including the calculation of phase diagram (CALPHAD)
electrical resistivity at room temperature reach 1.15 T, and high-throughput methods [26,65,69,112–117].
1,400 A m−1 and 69.5 mΩ cm−1, which are promising in There are many formation rules and empirical criteria
the high-frequency communication. for HEAs, which will not apply to all HEAs. Zhang et al.
[29] summarized the factors of the atomic-size difference,
HEAs AND “MATERIALS GENOME δ, and the enthalpy of mixing, ΔHmix, of the multi-com-
INITIATIVE” ponent alloys:
The purpose of the “Materials Genome Initiative” is to
N N 2
increase the speed of discovery, development, production, = x i (1 x i / xjrj) , (7)
i =1 j =1
and application of new materials by means of calcula-
N
tions, database and experimentation, which changes the Hmix = 4 Hijmixx ix j , (8)
experiment-oriented “trial and error” research and design i =1, i j

model [108]. Therefore, HEAs as a typical new material where N is the number of the elements in an alloy, xi or xj
can meet its opportunity to develop rapidly in the sub- is the atomic percentage of the ith or jth component, rj is
sequent days. The project emphasizes a change in the the atomic radius of the jth component, ΔHmix is the
research and design culture of materials through the in- mixing enthalpy for AB alloys. Subsequently, to further
tegration of the computational and experimental data, understand the relationship between ΔHmix and ΔSmix ,
and the integration of high-throughput computations and Zhang and Yang [51] proposed a new parameter, Ω, and

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Atomic-scale Meso-scale Macro-scale the field of HEAs, and the gigantic development of ma-
days

terial computation, there are many calculations and pre-

TIME

FEM
dictions to study the structures, properties, dynamics, and
thermodynamics of HEAs [119–123].
sec

PFM
TM DFT computations
Among the available predictive computing techniques,
ms

MCMD the DFT method is probably the ideal technique for sol-
AcceleratedM
D DDD ving multi-composition alloy systems [40,112], such as
HEAs. Generally, the first-principle calculation and
µs

modeling are the solution of the Schrodinger equation,

MD which only requires structures and atomic numbers as the
input to predict physical properties; and no experiments
DFT
ps

SPACE needed. The following equation is the many-body

nm µm mm m Schrodinger s equation [124]:
Figure 14 A map of time and spatial scales in computational materials. H (r ) = E (r ), (11)
where the H is Hamiltonian operator, (r ) is the state-
wave function, and E is the energy. However, the
defined by:
Schrödinger equation is very difficult to describe a com-
Tm S mix
= , (9) plex system, and can only handle simple electronic sys-
Hmix
tems, such as hydrogen atoms [125]. Therefore, the
where Tm is the melting temperature of the N-component researchers use some methods to scientifically and ra-
alloy. Zhang et al. [40] summarized the published HEAs tionally approximate and simplify the Schrödinger
and suggested a phase-formation rule using the δ and Ω equation. The most classical method is the DFT [126].
with Ω ≥ 1.1 and δ ≤ 6.6%. However, the FCC-type The solution of the bulk ground state is accurately re-
phase-forming δ shows a large overlap with that of the duced to the solution of the ground density distribution,
BCC-type phase, which means new rules or parameters which is given by the Schrödinger equation of a single
need to be considered for the phase-formation. Guo et al. particle. Kohn and Sham [40] considered that the particle
[118] considered that the phase stability of FCC and BCC density function of a multi-particle system can be ob-
solid solutions could be well delineated by the valance tained by a simple single-particle wave equation, and the
electron concentration (VEC) and defined by: Kohn-Sham equation [127] is a self-consistent equation.
N
VEC = x iVECi , (10) The DFT mainly converts the problem of multi-elec-
i =1 trons into that of a single electron, and describes the
where xi and VECi is the atomic percentage and VEC of physical properties of the ground state through the
the ith component. The simplified rule to identify the ground state electron density. The DFT calculations
phases of HEAs is: VEC<6.87, BCC; VEC8, FCC. Al- usually only contain the basic physical constants, such as
though the understanding of the prediction from funda- the speed of light, Planck s constant, electronic charge,
mental properties of constituent elements to phase etc. as input parameters [128]. Based on the most accu-
stability benefits the alloy design greatly, and then could rate theory, the predicted results are in good agreement
be used to predict the mechanical or physical properties with the experimental results [112]. The first-principles
of the alloys, the accuracy of the previous parameters are approach referred here deals with the DFT. Although the
limited [118]. Thus, the computation modeling is an ex- DFT has many simplifications of the Schrodinger equa-
cellent opportunity and challenge. tion, the computational process is still challenging due to
The HEA is a new type of materials that exhibits a the HEAs containing multiple principal components.
disordered structure, and the alloy generally contains at Thus, hybrid Monte Carlo/molecular dynamics (MC/
least five composition elements, and the atomic ratio of MD) simulations, ab initio molecular dynamics (AIMD)
each element is above 5% [17,20]. Such a multi- simulations, special quasi-random structure (SQS) mod-
component alloy is a vast challenge for the computational eling, coherent potential approximation (CPA), even
modeling [50]. However, with the research and interest in small sets of ordered structures (SSOS) calculations are

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used for the DFT calculation of HEAs [24,40,59,116,129– amorphous phase when x≥30, respectively. This trend
135]. was consistent with the common neighbor analysis with
By the DFT calculations, the electron density near the lower Al contents [24].
Fermi surface is often used to reveal the stability of ma-
terials and some functional properties, especially the band CALPHAD modeling
gap, magnetic properties, etc. The element of the transi- The most important tools to design the HEAs are the
tional (3d) HEAs is usually magnetic [40,44,106,128, phase diagrams and thermodynamic properties depend-
129,136]. The model of the transitional HEAs can be ing on the thermodynamic databases. Gao et al. [40,44]
constructed by a supercell or SQS. Normally, only the summarized that the term, “thermodynamic database” ,
spin orbit is considered or the magnetic force is not taken means that the parameters for the Gibbs energies of a
into account. In the DFT calculations, we need to con- large number of binary and ternary systems are as-
sider the spin polarization. Zuo et al. [129] used the SQS sembled, which are important for the intended compo-
to construct the structures of CoFeMnNi and Co- sitional ranges. Gao also gave the schematic of the
FeMnNiCr, and CoFeMnNiAl, with the DFT calculations CALPHAD processing and suggested that the first step in
conducted at 0 K through the VASP (the Vienna ab initio developing a thermodynamic database of a HEAs system
simulation package). The electron density of the 3d HEAs is to collect the thermochemistry and phase-equilibrium
with spin polarization is considered and illustrated in Fig. data from the articles about the lower-order systems,
15. The DFT calculations on the electronic and magnetic generally the related binaries and/or ternaries. However,
structures reveal that the anti-ferromagnetism of Mn if such data are not available unfortunately, it becomes
atoms in CoFeMnNi is suppressed especially in the Co- necessary to design and carry out experiments. In this
FeMnNiAl HEA, because Al changes the Fermi level and regard, the thermodynamic data obtained from the DFT
itinerant electron-spin coupling that leads to ferro- calculations will be useful to fill up experimental data
magnetism. [31,116]. Thus, the reliable thermodynamic databases,
containing a series of functions related to the composi-
MD calculations tion and temperature, are assessed by the CALPHAD
The MD calculations are used for predicting the ther- method, based on the reliable experimental data and ac-
momechanical properties, which computes the materials curate DFT results [40,50,113–117,119–122].
from a molecular-scale and has a very extensive range of Previously, Zhang et al. [26] studied the phase stability
applications [137]. MD is well suited to reproduce the of Al-Co-Cr-Fe-Ni HEAs and found that the experi-
smart amplitude oscillations of atoms in the vicinity of mental results are consistent with the CALPHAD mod-
crystal lattice sites. The probability of an atom crossing eling (Fig. 17). As one of the new-generation low-density
the barrier from one lattice site to another is prohibitively structural materials for automobile and aerospace, the
low and will rarely occur on the MD time scale at low phase stability of Al-Co-Cr-Fe-Ni HEAs is a research
temperature [132]. The method mainly relies on New- focus, and the CALPHAD method proves a powerful tool
tonian mechanics to simulate the motion of the molecular to study the phase stability and transformation as well as
system. The samples are extracted from the whole system the alloy design.
consisting of different states of the molecular system, and
calculation is used to construct the configuration of the High-throughput methods
system. As the “Materials Genome Initiative ” focuses on calcu-
Sharma et al. [24] investigated phase transformations lations, database, and experimentation in a three-in-one
(PTs) in AlxCrCoFeNi using classical MD simulations. way, there are more examples of success in terms of
The influents of cooling rates, temperature, and Al con- computations and simulations as a way to speed up the
tents on PTs were investigated by the MD simulation and material design [69,128]. Troparevsky et al. [112] used the
experimental method in AlxCrCoFeNi (Fig. 16). The high-throughput DFT to calculate the formation enthalpy
cooling rates’ effect could be neglected. Two transfor- between binary alloys to predict the formation of single-
mations, molten/amorphous and amorphous/crystalline phase HEAs. The method correctly identifies all known
phases, were observed with the temperature decreased single-phase alloys while getting rid of the similar ele-
below the certain temperature. At last, the nucleation type mental combinations that are known to form an alloy
was determined by the contents of Al. The nucleation containing multiple phases. More importantly, they pre-
type was the Al phase when x=10 and 20, while the dicted plenty of potential single-phase alloy compositions

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 a b c
1
0.2 0.2

0 0.0 0.0

−0.2 −0.2
−1

1
0.2 0.2

0 0.0 0.0

−0.2 −0.2
−1

1
0.2 0.2

PDOS of Co (statives (eV atom))

Total DOS (statives (eV atom))

PDOS of Fe (statives (eV atom))
0 0.0

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0.0
−0.2
−1 −0.2

. . . . . China
−5 0 5 10 15 20 −5 0 5 10 15 20 −5 0 5 10 15 20

. . . . . Press
Energy (eV) Energy (eV) Energy (eV)

. . . . .and
d e f g
0.2 0.2 0.01 0.1

0.0 0.0 0.00 0.0

−0.2 −0.2 −0.01 −0.1

. . . Springer-Verlag
0.04

. . . . . . . . . . . . Berlin
0.2 0.2 0.1
0.02
0.0 0.0 0.00 0.0

−0.2 −0.2 −0.02 −0.1

. . . . . Heidelberg
−0.04

. . . . . . . . .2017
0.2 0.2 0.2 0.1

PDOS of Mn (statives (eV atom))

PDOS of Al and Cr (statives (eV atom))

PDOS of Ni (statives (eV atom))

0.0 0.0 0.0 0.0
Decomposed PDOS of Mn (statives (eV atom))

−0.2 −0.2 −0.2 −0.1

−5 0 5 10 15 20 −5 0 5 10 15 20 −5 0 5 10 15 20 0 5 10 15 20
Energy (eV) Energy (eV) Energy (eV) Energy (eV)

Figure 15 (a) Spin-polarized total DOS (density of states); (b) Co d partial DOS; (c) Fe d partial DOS; (d) Mn d partial DOS; (e) Ni d partial DOS; and (f) Al s, p and Cr d partial DOS for the FCC
CoFeMnNi, FCC CoFeMnNiCr, and BCC CoFeMnNiAl from DFT calculations at 0 K; (g) Mn d-orbital-decomposed partial DOS. The vertical-dotted lines present the Fermi level. Reproduced with
the permission from Ref. [129]. Copyright 2017, Elsevier.
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a 0 b 30
AlxCrCoFeNi Al20CrCoFeNi
−0.5 Cooling 25
T=300 K

−1.0 20
T=1083 K
Etot (kJ mol−1)

−1.5 15 T=1866 K

g (r)
Al-0%
Al-10% T=2650 K
−2.0 10
Al-20%
T=3433 K
−2.5 Al-30% 5
T=4216 K
Al-40%
−3.0 0
0 1000 2000 3000 4000 5000 6000 0 2 4 6 8 10
T (K) Radius (Å)

Figure 16 (a) The influence of Al content on phase transition via Etot-T (total energy per atom-temperature); (b) the phase type of nucleation via
radial distribution at different temperature below 2,650 K. Reproduced with the permission from Ref. [24]. Copyright 2017, Elsevier.

c
Al
Co
Cr
Fe
20 nm
Ni

a 1.0
1250°C b
0.9
0.8 Fcc_A1
0.7
Phase fraction

Liquid
0.6 Bcc_B2
0.5 Bcc_A2
0.4 Fcc_A1
σ Bcc_B2
0.3
0.2
0.1
500 µm
0
700 800 900 1000 1100 1200 1300 1400 1500
Temperature (°C) d

20 nm

Figure 17 Comparison of the CALPHAD calculations and experimental observation of Al0·7CoCrFeNi HEA. (a) Equilibrium calculation; (b) optical-
microscope image of the specimen aged at 1,523 K for 1,000 h; (c) APT result: FCC_A1; (d) APT result: BCC_A2 + BCC_B2. Reproduced with the
permission from Ref. [26]. Copyright 2016, Elsevier.

and guided experimental studies. In Fig. 18, the high- diagrams for the material design and formation predic-
throughput DFT calculation method demonstrates the tion. Miracle and Senkov [19] used the CALPHAD cal-
higher accuracy in predicting new materials. culations to predict the phase formation of the alloy and
HEAs generally contain at least five alloying elements found that phase prediction is far from the experimental
and every element with high content [20,40,45]. Such results, as shown in Fig. 19. Chen et al. [138] used
multi-component alloys are difficult to rely on the ex- CALPHAD calculations combined with DFT to establish
isting binary-alloy phase diagrams or ternary-alloy phase a thermodynamic database especially for HEAs within a

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existing HEAs and materials-science literature, as fol-

FeCoNi: Cr Pd Mn Mo Ti V lowing.
Cr 1. Among HEAs, CoCrFeMnNi [16], HfNbTaTiZr
Pd [139] and DyGdHoTbY [23] are classical representatives
Mn
of the equimolar single-phase HEAs in FCC, BCC, and
Mo
HCP lattice structures, respectively. The two definitions
Ti
of HEAs have been described, respectively. There are two
V
restrictions for the former one, single-phase and equal
NbMoTa: W V Ti Zr Hf molar. Therefore, searching for the HEAs with single-
W phase solid-solution structure and more than five prin-
V cipal elements is a research focus for decades. With the
Ti in-depth understanding of HEAs, these two restrictions
Zr have been broken. Now, the non-equimolar complex
Hf phases (the matrix is a solid solution) HEAs have been an
Multiple phases Single solid-solution phase Experimental verification important part of HEAs. Therefore, the HEA can be di-
Figure 18 The predicted phase composition after one- or two- com-
vided into the first and the second generations, as illu-
ponents added to FeCoNi and NbMoTa. Reproduced with the permis- strated in Fig. 20 and Table 2. The research scope of
sion from Ref. [112]. Copyright 2015, the American Physical Society. HEAs expands from the central region to the surround-
ings, which means the development from the equimolar
single-phase solid-solution alloys to the non-equimolar
12
multi-phase solid-solution alloys, which affects the defi-
Gibbs phase rule
nition of HEAs and the research scope. In other words,
10
the evolution of HEAs conception facilitates the material
CALPHAD calculations
design and development, meanwhile extends this idea to
8 Experiments
Number of phases

meet the specific needs, rather than rigidly adheres to the

6
classical high-entropy definition. The non-equimolar
complex-phases HEAs can be modified in the future to
Max improve their performance by changing the component
4
ratio and adding minor components to maintain a certain
2 phase in special condition, or forming a second phase for
Min precipitation strengthening or composite strengthening,
0 such as the TRIP (transformation-induced plasticity)
2 3 4 5 6 7 8 9 10
Number of elements (N)
HEA Fe50Mn30Cr10Co10 [140], the precipitation-hardening
HEA [74], and eutectic HEA [90].
Figure 19 The number of formed phases for experiments and CAL- 2. At present, the common preparation methods of
PHAD calculations. Reproduced with the permission from Ref. [19].
Copyright 2017, Elsevier.
HEAs are traditional arc melting and induction melting.
In order to shorten the development cycle and collect
numerous data via a few experiments, new preparation
15-element framework applied in many groups well. methods, such as 3D printing, magnetron sputtering and
FUTURE TRENDS AND PROSPECTS directional solidification, etc. are applied to the study of
The HEAs have excellent properties, such as excellent HEAs. And with the application of high-throughput ex-
mechanical properties, high-temperature performance, as perimental method in HEAs research [141], a series of
well as corrosion and irradiation resistance, which are the small samples with different composition or one sample
potential materials under extreme conditions. Although containing composition gradient were fabricated.
many studies focus on HEAs, our understanding of HEAs Combing with the highly developing technology of mi-
fundamental is rare. The HEAs contain a variety of sys- croscopy, material properties testing and computer, a lot
tems with more than five different elements in approxi- of data and reliable relationship between composition and
mately equal-molar, which make it unlimited possibilities properties were got in a short time.
for discovery and development of new alloys. Several 3. As shown in the definition of HEAs, component,
future trends and prospects are proposed, based on the phase and thermodynamic properties (entropy) play the

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Component: based on at least 4

principal elements
Feature: dual or complex phases,
non-equimolar
Component: based on at
least 5 principal elements The 2 nd generation HEAs
Feature: single phase
Component: based on equimolar
1~2 principal elements
Feature: tougher than The 1 st generation HEAs
the elementary
substance

The traditional alloys

Figure 20 The evolution of alloys.

Table 2 Characteristics for the two generations of HEAs

Classification Component Feature Composition Atoms arrangement Typical alloys

A B
1~2 principal ele- Tougher than the Fe-Ni, Fe-C,
The traditional alloys ments elementary substance Cu-Al, Al-Mg

A B
C D E
At least 5 principal Single phase, CoCrFeNiMn,
The 1st generation HEAs
elements equimolar AlCoCrFeNi

A B
C D NbMoTaW,
At least 4 principal Dual or complex
The 2nd generation HEAs phases, non-equimo- Al0.3CoCrFeNi,
elements lar Fe50Mn30Cr10Co10

critical role on the properties of HEAs. Therefore, com- certain critical environment. For example, HEAs show
pared with experimental methods to design the HEAs, the great fatigue and fracture resistance [37–39], and superior
alloy designing, based on the properties calculated by the high tensile strengths at cryogenic temperatures [36,39].
DFT or MD method and the multi-component phase These outstanding properties make it possible for the
diagrams assessed by CALPHAD, is an effective method HEAs to use in turbine blades of aircraft [79], and
to save time and reduce the cost. However, the multiple cryogenic environments [36] as engineering alloys. HEAs
elements (more than 5) and microstructures (solid-solu- possess low swelling after ion irradiation and some self-
tion) of HEAs make the computational process much healing effects that has good application prospect in the
more complex and time-consuming than that in con- field of nuclear materials [142].
ventional alloys. In addition, there is a certain gap be- 5. The studies of HEAs are mainly focused on the bulk
tween the phase composition of HEAs measured by the alloys, but less on the high-entropy films properties of
experimental method and the prediction by the CAL- corrosion resistance, wear resistance, irradiation proper-
PHAD method [69]. Therefore, it is crucial to develop ties, mechanical properties, and elevated temperatures
reliable and robust databases for HEAs through the stability. High-entropy nitride films have been applied in
“Materials Genome Initiative”. There is no doubt that cutting [143]. Another significant potential application of
advanced computing methodologies that can simulate the high-entropy films is used as diffusion barriers [144].
dislocation-related properties in HEAs are highly desir- Sheng et al. [145] proposed huge application potentials of
able nowadays. high entropy films in the fields of solar thermal conver-
4. There is a great opportunity for HEAs to overcome sion systems.
the bottlenecks of conventional alloys and to be applied in 6. Although massive articles focus on the mechanical

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elevated-temperature mechanical properties. More me-
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Received 20 November 2017; accepted 22 December 2017;
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SCIENCE CHINA Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . REVIEWS

Weiran Zhang is a PhD student at the State Key Laboratory for Advanced Metals and Materials, University of Science &
Technology Beijing (USTB), under Prof. Zhang s supervision. Her interest focuses on the low-activation of high-entropy
alloys and DFT.

Peter K. Liaw obtained his BSc degree in physics from Tsing Hua University, Taiwan, and his PhD in materials science
and engineering from the Northwestern University. After working at Westinghouse Research and Development (R&D)
Center for thirteen years, he joined the faculty and became an Endowed Ivan Racheff Chair of Excellence in the
Department of Materials Science and Engineering at the University of Tennessee (UT), Knoxville. He has been working in
the areas of fatigue, fracture, nondestructive evaluation, and life-prediction methodologies of structural alloys and
composites. Since joining UT, his research interests include mechanical behavior, nondestructive evaluation, biomaterials,
high-temperature alloys, bulk metallic glasses, high-entropy alloys, ceramic-matrix composites and coatings. He has
published 890 peer-reviewed papers, edited more than 30 books.

Yong Zhang has been a full professor of the USTB & State Key Laboratory for Advanced Metals and Materials since 2004.
He attained his Bachelor degree at Yanshan University in 1991, majored in materials science. He obtained Master degree
majored in nuclear materials in 1993, and PhD in composite materials in 1998 at the USTB. Then he worked as a
postdoctoral fellow in the Institute of Physics, Chinese Academy of Science, and Singapore-Massachusettes Institute of
Technology (MIT) Alliance (SMA). His interest focuses on high-entropy materials and serration behaviors.

高熵合金材料研究进展
张蔚冉1, Peter K. Liaw2, 张勇1,3*
摘要 根据人类开发材料的能力来看, 合金成分经历了从简单到复杂的发展过程. 通过改善合金的功能和性能, 促进了人类文明进步. 具有
多组分的高熵合金(HEAs)可以有效地改善合金的微观结构和性质. 高熵合金具有诸如高强度和高硬度、优异的耐腐蚀性和热稳定性、良
好的抗疲劳强度及断裂强度、强耐辐射性等优异的性能, 这是传统的合金无法比拟的. 这些优异的性能也说明高熵合金未来具有非常高
的应用前景. 近年来, 高熵合金在各个领域也呈现出快速发展的趋势. 为了更好地了解高熵合金的基础, 未来快速开发出具有更加优异性
能的高熵合金, 本文综述了近年来关于高熵合金的发展. 高熵合金的发展已经经历了两个阶段, 第一个阶段为等摩尔-单相固溶体机构的
高熵合金, 第二阶段为非等摩尔比的多相固溶体高熵合金. 本文主要讨论了高熵合金的制备方法、组分设计、相形成和微观结构、优异
的性能和高熵合金在计算模拟方面的应用, 同时提出了高熵合金的未来发展趋势和前景.

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