materials

Article
Effect of Heat Treatment on the Microstructure and Mechanical
Properties of the Al0.6CoCrFeNi High-Entropy Alloy
Pengyu Hou, Yue Yang, Leilei Zhang, Yi Meng, Yan Cui and Leigang Cao *

Department of Materials Science and Engineering, North China University of Technology, Beijing 100144, China;
pengyu5hpy@163.com (P.H.); yyue@ncut.edu.cn (Y.Y.); zhangleilei@ncut.edu.cn (L.Z.);
mengyi@ncut.edu.cn (Y.M.); cuiyan@ncut.edu.cn (Y.C.)
* Correspondence: caolg@ncut.edu.cn

Abstract: The effect of heat treatment on the microstructure and tensile properties of an as-cast
Al0.6 CoCrFeNi high-entropy alloy (HEA) was investigated in this paper. The results show that the
as-cast Al0.6 CoCrFeNi HEA presents a typical FCC dendrite morphology with the interdendritic
region consisting of BCC/B2 structure and heat treatment can strongly affect the microstructure and
mechanical properties of HEA. Microstructure analysis revealed the precipitation of a nano-sized L12
phase in the FCC dendrite and the formation of the FCC and σ phases in the interdendritic region
after annealing at 700 ◦ C. The coarse B2 phase was directly precipitated from the FCC dendrite in
the 900 ◦ C-annealed sample, with the coexistence of the B2, FCC, and σ phases in the interdendritic
region. Then, the interdendritic region converted to a B2 and FCC dual-phase structure caused by
the re-decomposition of the σ phase after annealing at 1100 ◦ C. The tensile test results show that
the 700 ◦ C-annealed HEA presents the most significant strengthening effect, with increments of
corresponding yield strength being about 107%, which can be attributed to the numerous nano-sized
L12 precipitates in the FCC dendrite. The mechanical properties of 1100 ◦ C-annealed alloy revert
to a level close to that of the as-cast alloy, which can be attributed to the coarsening mechanism of
B2 precipitates and the formation of a soft FCC phase in the interdendritic region. The observed
variation in mechanical properties during heat treatment follows the traditional trade-off relationship
between strength and plasticity.

Citation: Hou, P.; Yang, Y.; Zhang, L.; Keywords: high-entropy alloy; phase transition; strengthening; microstructure; mechanical property
Meng, Y.; Cui, Y.; Cao, L. Effect of
Heat Treatment on the Microstructure
and Mechanical Properties of the
Al0 .6 CoCrFeNi High-Entropy Alloy. 1. Introduction
Materials 2023, 16, 7161. https://
doi.org/10.3390/ma16227161
High-entropy alloys (HEAs), since being defined in 2004 [1,2], have been paid increas-
ingly intensive attention for their potential engineering applications due to their excellent
Academic Editor: Pan Gong mechanical properties. In many cases, multi-component HEAs with a key feature of high
Received: 10 October 2023
configurational entropy tend to form simple crystal structures such as FCC, BCC, HCP,
Revised: 8 November 2023 or a mixture of two or more phases [3,4]. Until now, many efforts have been carried out
Accepted: 9 November 2023 to optimize the elemental constitution and microstructure for advanced HEAs with high
Published: 14 November 2023 strength and high ductility. In this process, more and more investigations have revealed the
effectiveness of the classical strengthening mechanisms via the formation of solid solution,
the dispersive second phase, grain-refined microstructure and even deformation-induced
phase transition [5–7].
Copyright: © 2023 by the authors. In fact, a remarkable strengthening effect has been achieved on low-strength FCC-
Licensee MDPI, Basel, Switzerland.
structured HEAs using microstructure tailoring due to their good ductility [8]. For this
This article is an open access article
purpose, severe plastic deformation methods are usually chosen, such as cold rolling,
distributed under the terms and
high-pressure torsion, and equal channel angular pressing, which might also incorporate
conditions of the Creative Commons
subsequent annealing treatment [8]. For example, the remarkable reduction in grain
Attribution (CC BY) license (https://
diameter from 100 µm to about 50 nanometers in CoCrFeNiMn HEA by means of high-
creativecommons.org/licenses/by/
4.0/).
pressure torsion results in a significant increase in strength, being 1950 MPa [9].

Materials 2023, 16, 7161. https://doi.org/10.3390/ma16227161 https://www.mdpi.com/journal/materials

Materials 2023, 16, 7161 2 of 16

Actually, if there are phase transition behaviors in such thermal mechanical processes,
the mechanism of microstructure evolution and its effect on mechanical properties will
become more complex. An example is Alx CoCrFeNi HEAs [10], which are a promising
and important engineering material. The corresponding as-cast microstructures, as well as
the associated unstable phases, are very sensitive to Al content. Alx CoCrFeNi HEAs with
low Al content (x ≤ 0.45) are usually solidified into a simple FCC structure [11]. With the
increase in Al content, the BCC phase can solidify directly in the interdendritic (ID) region
of the as-cast Al0.5 CoCrFeNi HEA, with the fraction of the ID region being 10.6% [12].
Although the Al0.6 CoCrFeNi HEA also presents a dendrite morphology, the ID region
solidified into a BCC/B2 spinodal nano-structure, and its fraction increases to about 27.5%
according to the observations in the present paper. Furthermore, the Al0.7 CoCrFeNi HEA
solidifies into a eutectic-like morphology, comprising alternating structures of FCC single-
phase and spinodal BCC/B2 phases, giving it a promising strength–ductility balance [13].
When x exceeds 0.8, the spinodal structure will be predominant [14–16].
It has been proved that the thermal-mechanical processing is one of the most promising
routes to improve the mechanical properties of low-Al Alx CoCrFeNi HEAs with excellent
tensile strength and plasticity. Significant grain refinement (with grain size varying from
5.7 µm to 144 µm) has been successfully achieved in Al0.3 CoCrFeNi HEAs using cold rolling
(90%) and subsequent annealing, presenting a strong Hall–Petch relationship for both the
hardness and the tensile yield strength [5]. The enhanced strength can be attributed to
the refined FCC grains, B2 phase and even σ intermetallic phase. The latter two phases
precipitate from the FCC phase during the annealing process at intermediate temperatures
of 550–900 ◦ C. Similarly, Al0.7 CoCrFeNi HEA can also be strengthened due to the massive
FCC-BCC interfaces and the L12 precipitates in the FCC phase in the thermal-mechanical
processing [13]. Although the thermal-mechanical processing can also affect the mechanical
properties of high-Al Alx CoCrFeNi HEAs (x ≥ 0.8), the corresponding assessment is mainly
carried out on the basis of the hardness test and compressive test due to the related brittle
feature, the results of which are not stated in this paper [15,16].
The thermal stability analysis revealed that the supersaturated FCC phase, primar-
ily, solidified from the melt, and the disordered BCC phase was unstable, both of which
will undergo solid-state phase transitions at an elevated temperature and, thus, influence
the microstructure and mechanical properties [17,18]. It is worth noting that the defects
induced via pre-deformation in the thermal-mechanical processing could strongly facilitate
the nucleation and growth process during the phase transition [19]. This indicates that the
microstructure evolution caused by solid-state phase transition might be different in an
individual annealing process, which might be obscured by the accelerating effect caused
by the thermal-mechanical process. Therefore, in the present paper, phase transformation
behaviors of as-cast Al0.6 CoCrFeNi HEA under different treatment conditions and their
effects on phase constitution, microstructure evolution, and resulting mechanical proper-
ties were investigated. Based on a similar experimental design, the Al0.5 CoCrFeNi HEA
was significantly strengthened after annealing at 850 ◦ C, which was mainly attributed
to the precipitation behavior in the FCC dendrite, while the strengthening effect with a
slight increase of 3.8% in the BCC phase caused by potential BCC-FCC phase transition,
pending direct observations, should be relatively minor. That is to say, the phase tran-
sition characteristics corresponding to FCC dendrite and BCC interdendritic regions are
inadequate [18]. Instead, for the Al0.6 CoCrFeNi HEA, the fraction of the interdendritic
region with a BCC/B2 spinodal structure reaches to approximately 27.5%, which provides
a proper opportunity to investigate the coupling effect of different phase transitions that
occurred in the DR and ID regions on the microstructure and mechanical properties of the
Al0.6 CoCrFeNi HEA. Additionally, the research has potential application prospects for the
heat-treatable HEAs with modified microstructure assisted via directional temperature
field [20], electromagnetic field [21] and so on.
Materials 2023, 16, 7161 3 of 16

2. Materials and Methods

The Al0.6 CoCrFeNi ingots were prepared using an electric arc-melting furnace with a
water-cooled copper hearth (MTDH-600; Shanghai Mengting Instrument Equipment Co.,
Ltd., Shanghai, China). The purity of the constituent metals was higher than 99.99%. The
furnace was evacuated to a pressure of 3 × 10−3 Pa using a rotary pump and a molecular
pump and then back-filled with argon (repeated five times) to obtain an Ar (3 × 103 Pa)
protective condition before the melting process. The ingots were turned over and melted
five times to ensure chemical homogeneity with a maximum heating current of 300 A.
Finally, the ingots were placed onto the casting mold and solidified into rods measuring
10 mm × 10 mm × 60 mm using the drop-casting method [7].
The casting rods were annealed at temperatures of 700 ◦ C, 900 ◦ C, and 1100 ◦ C,
respectively, for 3 h and cooled in air. The annealed samples for microstructure analysis
were mounted (160 ◦ C) using conductive resin and then ground progressively using a
series of abrasive SiC papers down to 2000 grit and polished using 5 µm, 2.5 µm, 1 µm,
and 0.25 µm diamond paste and, lastly, colloidal silica. Ultrasonic cleaning was used to
remove the potential residue and optical microscopy was used to check the surface quality
at each grinding and polishing stage. The samples were washed using dilute detergent and
absolute ethyl alcohol and then dried using hot air between each polishing step. The alloy
samples for phase identification were only ground down to 2000 grit, without mounting
and polishing procedures.
The microstructure and fracture morphology of the samples were studied by using a
scanning electron microscope equipped with a backscattered electron detector (SEM; Zeiss
Sigma-300, Carl Zeiss, Cambridge, UK). The elemental composition of the polished samples
was also measured with a Bruker Quantax spectrometer system (XFlash detector, Bruker,
Berlin, Germany) inside the SEM. A FEI Tecnai G2 F30 transmission electron microscope
(TEM, FEI company, Hillsboro, OR, USA) was also used for further detailed microstructure
investigation. TEM specimens were fabricated using a Gatan 691 (Gatan, Pleasanton,
CA, USA) ion polishing system (as-cast and 1100 ◦ C-annealed specimens) and by using
a focused ion beam technology (alloys were annealed at 700 ◦ C and 900 ◦ C) based on the
corresponding microstructural complexity.
In situ XRD was conducted to identify the phase constitution of the sample related to
the potential thermal phase transformations of the metastable phases (Cu-Kα radiation,
SmartLab, Rigaku, Tokyo, Japan). In situ heating was carried out in a sealed chamber under
a protective argon atmosphere, in which the sample could be heated to a maximum of
1150 ◦ C. The sample was scanned via X-ray at 25 ◦ C, 700 ◦ C, 900 ◦ C, 1000 ◦ C, and 1100 ◦ C
in the heating stage and at 700 ◦ C and 25 ◦ C again in the cooling stage. The sample was
kept for 10 min at each set temperature before scanning.
In most cases, the specimens used for tensile tests related to HEAs are usually small
due to the limitation of sample size. The thickness of the tensile specimens is usually
1~1.5 mm, according to the literature. However, the corresponding gauge length and
width vary greatly, such as 15 mm and 5 mm [6], 14 mm and 2 mm [12], 12.5 mm and
3.2 mm [22], 10 mm and 4 mm [23], 5 mm and 2.5 mm [24], and so on. In the present
paper, the standard used for the tensile test is GB/T 228.1-2010 [25], which was released
by the National Standard of the PRC. The specimen geometry refers to the equation of
L = L0 + 2b0 , where L0 is the gauge length, and L and b0 are the length and width of the
parallel section, respectively. Therefore, tensile samples with an 18 mm long parallel section
that has a width of 4 mm and an approximate thickness of 1.1 mm were prepared using an
electrical discharge machine. The surfaces of the specimens were ground using SiC paper
down to 2000 grit to remove the surface damage. Tensile tests were carried out on an MTS
Exceed E44 electronic universal test system (MTS Systems Corporation, Eden Prairie, MN,
USA) with a strain rate of 1 × 10−3 s−1 at room temperature. At least three independent
tensile tests were performed on the four different alloys studied to ensure consistency.
The deformation of the samples under loading was recorded using an EAG-010M-1000-S
s 2023, 16, x FOR PEER REVIEW 4 of 16

Materials 2023, 16, 7161 4 of 16

tests were performed on the four different alloys studied to ensure consistency. The de-
formation of the samples under loading was recorded using an EAG-010M-1000-S exten-
someter (Reliant Technology LLC., Colorado Springs, CO, USA) with a gauge length of 10
extensometer
mm and the maximum (Reliant Technology
measurement LLC., Colorado Springs, CO, USA) with a gauge length
range of 100%.
of 10 mm and the maximum measurement range of 100%.
3. Results
3. Results
3.1. Microstructures of as-Cast Al0.6CoCrFeNi
3.1. Microstructures of as-CastAlloy
Al CoCrFeNi Alloy
0.6
Figure 1 showsFigure
the microstructure
1 shows theofmicrostructure
as-cast Al0.6CoCrFeNi
of as-castalloy observed
Al0.6 CoCrFeNi using SEM
alloy observed using
and TEM instruments. It can be seen that the as-cast microstructure presents
SEM and TEM instruments. It can be seen that the as-cast microstructure presents a a typical
dendrite structure (DR),
typical with the
dendrite interdendritic
structure (DR), with region (ID) presenting
the interdendritic a dual-phase
region mor- a dual-phase
(ID) presenting
phology (Figure 1b). The BSE image of Figure 1a reveals the contrast difference between
morphology (Figure 1b). The BSE image of Figure 1a reveals the contrast difference between
the three areas,the
which
threewere
areas,labeled
whichaswere
Area-1, Area-2,
labeled and Area-3.
as Area-1, Area-2, The
andEDX measurement
Area-3. The EDX measurement
was carried outwasto analyze
carried out the to
average
analyze elemental compositions
the average elementalof these three areas
compositions based
of these three areas based
on the data obtained from five different positions of the sample, the results of which
on the data obtained from five different positions of the sample, the results of which are are
provided in Table 1. It isinclear
provided Tablethat theis composition
1. It clear that theofcomposition
the prepared ofalloy is equal to
the prepared the is equal to the
alloy
nominal values. Meanwhile, the measured elemental compositions of the dendrite
nominal values. Meanwhile, the measured elemental compositions of the dendrite and and
interdendritic regions from Areas
interdendritic regions1–3from
shown in Figure
Areas 1a areingiven
1–3 shown Figure in1aTable 2. Thein
are given results
Table 2. The results
show that the elemental
show that compositions
the elementalof the ID region
compositions ofof
theAreas 1–3 are
ID region of very
Areasclose, while
1–3 are very close, while
the elemental compositions
the elementalof the DR region
compositions of of
theAreas 1–3 fluctuate,
DR region of Areasespecially for Co
1–3 fluctuate, and
especially for Co and
Cr elements. Overall, the AlOverall,
Cr elements. elementthe is enriched
Al element in the ID region,
is enriched in as
theitID
is region,
a BCC stabilizer.
as it is a BCC stabilizer.

Figure 1. Images (a,b) show SEM-BSE and TEM dark-field micrographs of as-cast Al0.6CoCrFeNi
Figure 1. Images (a,b) show SEM-BSE and TEM dark-field micrographs of as-cast Al0.6 CoCrFeNi
HEA, respectively, showing the typical dendrite morphology. (c) SADP of the dendrite, indicating
HEA, respectively, showing the typical dendrite morphology. (c) SADP of the dendrite, indicating
the primary solidification of the FCC phase. (d) SADP of the interdendritic region, showing the
disordered BCCtheandprimary
orderedsolidification
B2 structure,ofrespectively.
the FCC phase. (d)dark
(e) The SADP of the
field TEM interdendritic region, showing the
image was taken
disordered
from the additional spot of BCC and ordered
the BCC/B2 B2 structure,
reflections (yellowrespectively.
circle in (d)).(e) The dark field TEM image was taken from
the additional spot of the BCC/B2 reflections (yellow circle in (d)).
Figure 1b was taken from Area-3, indicating the difference in contrast between the
Table 1. The measured average composition of Areas 1–3 in the as-cast Al0.6 CoCrFeNi HEA.
ID-1 and ID-2 areas. TEM analysis revealed that the microstructures of ID-1 and ID-2 are
the same, with the results of ID-1 shown Al/at.%
in Figure 1c–e. TEM-selected
Co/at.% area diffraction
Cr/at.% Fe/at.% Ni/at.%
patterns (SADPs)Nominal
confirmComposition
that the dendrite is a
13.0 disordered FCC
21.7 phase and
21.7 the interden-
21.7 21.7
drite consists of disordered BCC and ordered BCC (B2) phases. Figure 1e shows the dark
Area-1 Average 13.1 ± 0.1 22.3 ± 0.1 21.6 ± 0.4 21.8 ± 0.2 21.1 ± 0.4
field TEM image taken
Area-2
from the additional12.9
Average
spot± of
0.3
the BCC/B2 reflections
22.5 ± 0.1
(yellow21.7
21.7 ± 0.3
circle in
± 0.2 21.2 ± 0.2
Area-3 Average 12.9 ± 0.3 22.4 ± 0.2 21.7 ± 0.3 21.8 ± 0.2 21.1 ± 0.2
Materials 2023, 16, 7161 5 of 16

Table 2. The measured average composition of the FCC and ID region corresponding to Areas 1–3 in
Figure 1a.

Al/at.% Co/at.% Cr/at.% Fe/at.% Ni/at.%

Area-1 FCC phase (DR) 10.6 ± 0.2 19.0 ± 0.1 24.9 ± 0.5 24.7 ± 0.7 20.7 ± 0.9
ID region 15.5 ± 0.5 20.8 ± 0.2 23.4 ± 0.2 20.8 ± 0.3 19.6 ± 0.2
Area-2 FCC phase (DR) 11.1 ± 0.1 23.0 ± 0.2 21.4 ± 0.3 22.3 ± 0.2 22.3 ± 0.3
ID region 15.5 ± 0.3 20.9 ± 0.2 23.5 ± 0.4 20.9 ± 0.5 19.2 ± 0.5
Area-3 FCC phase (DR) 10.8 ± 0.3 23.0 ± 0.6 21.5 ± 0.3 23.2 ± 0.4 21.3 ± 0.3
Materials 2023, 16, x FOR PEER REVIEW ID region 15.7 ± 0.3 20.7 ± 0.3 23.0 ± 0.5 20.8 ± 0.3 19.8 ±6 0.3
of 16

Figure 1b was taken from Area-3, indicating the difference in contrast between the
takenand
ID-1 from theareas.
ID-2 additional spot of the
TEM analysis BCC/B2
revealed thatreflections (yellow circle
the microstructures in Figure
of ID-1 2g),are
and ID-2 as
shown
the same, in Figure
with the 2f.results
It can beof seen
ID-1 that
shownthese
in additional
Figure 1c–e. spots were attributed
TEM-selected area to the rela-
diffraction
tively bright
patterns (SADPs) areas, corresponding
confirm to the isordered
that the dendrite B2 phase,
a disordered and the
FCC phase andother constituent
the interdendrite
phase ofof
consists this area should
disordered BCC be and
the disordered
ordered BCC BCC phase.
(B2) Figure
phases. 2h presents
Figure 1e showsthe themicrostruc-
dark field
TEM
ture ofimage
the ID taken from
region of the additional
Figure spot of thethe
2c. Interestingly, BCC/B2 reflections
corresponding (yellow
SADPs circle2i,j)
(Figure in
Figure 2d). It can
only identify be seen that
the existence of these additional
B2 (ordered BCCspots were
phase) andattributed
σ phases.to the relatively bright
areas,Incorresponding
addition, the to the ordered B2ofphase,
microstructure the FCCanddendrite
the otherregion
constituent phaseinshould
presented Figurebe2a–c
the
disordered
also revealed BCC thephase. A similarofmicrostructure
precipitation a large number with
of the same phase
nano-sized constitution
phases in the 700has been
°C-an-
reported
nealed Alin0.6the Al-Co-Cr-Fe-Ni
CoCrFeNi HEA. Figurealloy 2l
systems
shows[14,26]. Thezone
the [-112] addition
axis of thethe
from Al element in the
FCC dendrite
FCC-structured
region, with the additional spots of extra {110} super-lattice reflections in comparison with
CoCrFeNi high-entropy alloy facilitates the formation of the phases
the
thatbody-centered
of the as-cast cubicalloy crystal
(Figurestructure. Here, the
1c), confirming thesolidification
presence ofpath of the
the L1 Al0.6 CoCrFeNi
2 phase. Figure 2k
alloy
showsis the
for the
dark primary
field TEMgrowth of the
image FCC phase,
obtained fromwith the interdendritic
the {110} superlattice region converting
reflection, clearly
to the BCCthat
revealing andthese
B2 phases via a spinodal
nano-phases decomposition.
within the FCC dendrite are L12 precipitates.

Figure 2.
Figure 2. Images
Images(a–c)(a–c)show
showSEM-BSE
SEM-BSE micrographs
micrographs of of
700700 °C-annealed
◦ C-annealed AlCoCrFeNi
Al0.6 0.6CoCrFeNi HEA, pre-
HEA, present-
senting the three typical morphologies of microstructure evolution in the ID region; (d) TEM bright-
ing the three typical morphologies of microstructure evolution in the ID region; (d) TEM bright-field
field image of the ID region labeled by yellow rectangle in (b); (e) SADP from the [011] zone indi-
image of the ID region labeled by yellow rectangle in (b); (e) SADP from the [011] zone indicating
cating the bright phase in (b) is the decomposed FCC phase; (f) the dark field TEM image taken
the
frombright phase in (b)
the additional is the
spot decomposed
of the FCC phase;
BCC/B2 reflections (f) thecircle
(yellow dark in field TEM
(g)); (g) image
SADP taken
of thefrom
B2/BCCthe
additional spot of the BCC/B2 reflections (yellow circle in (g)); (g) SADP of
phases, showing the diffraction of super-lattice spots; (h) TEM bright-field image of the ID region the B2/BCC phases,
showing
shown in the (c); diffraction
(i,j) SADP of ofthe
super-lattice spots;respectively;
σ and B2 phase, (h) TEM bright-field
(k) the dark image
fieldof
TEMthe image
ID region shown
taken from
the(c);
in additional
(i,j) SADP spotof of
thethe FCC/L1
σ and 2 reflections
B2 phase, (yellow (k)
respectively; circle
theindark
(l)), field
showing
TEMthe precipitation
image taken from of the
L12 phase; (l)
additional SADP
spot of theofFCC/L1
the dendrite region,(yellow
2 reflections showing the diffraction
circle of super-lattice
in (l)), showing spots. of the L12
the precipitation
phase; (l) SADP of the dendrite region, showing the diffraction of super-lattice spots.
Figure 3 shows the microstructure of the 900 °C-annealed Al0.6CoCrFeNi HEA, pre-
senting a more obvious microstructure evolution. As can be seen in Figure 3a,b, a large
fraction of the rod-like phase precipitated from the dendrite. Moreover, the enhanced con-
trast of the constituent phases in the interdendritic region clearly indicates the existence
Materials 2023, 16, 7161 6 of 16

Materials 2023, 16, x FOR PEER REVIEW 7 of 16

3.2. Microstructure of Annealed Al0.6 CoCrFeNi Alloy

In order
confirmed as to revealB2
ordered thephase
microstructure
precipitates,evolution
rather than viathe
solid-state
disordered phase
BCCtransitions
phase or the at
elevated temperatures, the microstructures of the Al CoCrFeNi alloys annealed at 700 ◦ C,
0.6
L12 precipitates in the 700 °C-annealed sample. The width of the B2 nano-precipitates can
900 ◦ C, and 1100 ◦ C for 3 h were analyzed via SEM and TEM, the results of which are
reach 100 nm, which is much larger than that of the L12 nano-precipitates in the 700 °C-
shown in Figures
annealed 2–4, respectively.
alloy (Figure 2k). Figure 3eIn orderthe
shows to microstructure
confirm the originof theofID
the microstructural
region, where the
evolution,
constituting phases are successfully identified as the B2, FCC, and σ phases,regions
FIB was used to prepare TEM specimens from interdendritic of the
respectively,
alloys heat-treated at 700 ◦ C and 900 ◦ C. Although the annealed Al CoCrFeNi HEA
according to the corresponding SADPs (Figure 3f–h). This result is consistent 0.6 with the
maintains the that
observations samethedendrite morphology,
disordered BCC phase these
willdata present
convert to B2two
andimportant
FCC phasesobservations
when the
corresponding
temperature isto the dendrite
above region and the interdendritic region, respectively.
650 °C [15].

Figure3.3.Images
Figure Images(a,b)
(a,b)show
show low-
low- and
and high-magnified
high-magnified SEM-BSE
SEM-BSE micrographs
micrographs of of the
the 900
900 °C-annealed
◦ C-annealed
Al0.6CoCrFeNi HEA, showing the rod-like precipitation in the dendrite region and a ternary-phase
Al0.6 CoCrFeNi HEA, showing the rod-like precipitation in the dendrite region and a ternary-phase
morphology in the interdendritic region. (c) High-resolution TEM micrograph of the rod-like pre-
morphology in the interdendritic region. (c) High-resolution TEM micrograph of the rod-like precipi-
cipitation. (d) Fourier transform image indicating the rod-like precipitation is B2 phase. The diffrac-
tation. (d) Fourier
tion spots of {110}transform image
crystal plane are indicating
labeled by the rod-like
yellow precipitation
circles. is B2image
(e) Bright-field phase.ofThe
thediffraction
interden-
spots of {110} crystal plane are labeled by yellow circles. (e) Bright-field image of
dritic region with corresponding SADP patterns (f–h) showing the existence of the B2 phase, σthe interdendritic
region
phase,with
and corresponding
FCC phase. SADP patterns (f–h) showing the existence of the B2 phase, σ phase, and
FCC phase.
Figure 4 shows the microstructure of the 1100 °C-annealed Al0.6CoCrFeNi ΗΕΑ ana-
lyzedThe viaSEM
SEMandandTEM TEM,micrographs
wherein the from the 700 ◦region
interdendritic C-annealed
furtherAlconverts
0.6 CoCrFeNi HEA,
to a dual-
presented in Figure 2, show three typical morphologies of microstructure
phase structure (Figure 4a,b). TEM analysis confirmed that the dark phase and gray phase evolution in the
interdendritic
are the B2 phase region
andaccording to the
FCC phase, enhanced
as shown contrast
in Figure 4c.ofThis
the result
constituent phases observed
is consistent with the
using a backscatter
fact that the σ phaseSEM detector.
is also unstableComparing Figures
and will convert to 1b
B2 and
and 2a,
FCCitphases
seems forthattempera-
in some
regions
tures inthe phase
excess of transition has not
950 °C [15,26]. yet begun,
Therefore, while°C-annealed
the 1100 the brightnessAl0.6variation
CoCrFeNi presented
alloy onlyin
Figure
consists2b,c
of indicates
the B2 and the occurrence
FCC of theresult
phases. This phaseis transition and the
also consistent withformation of additional
the density variation
phases. This resultBSE
in the greyscale is reasonable
image whichsince the annealing
presents only two temperature is slightly
distinct phases (Figure higher
4a,b).than
Mean-the
initial decomposition temperature of the BCC phase (about 650 ◦ C). In order to confirm the
while, the B2 precipitates in the FCC dendrite are coarsened, with the width being about
origin
1 μm of the observed
(Figure 4d). microstructure, FIB was used to prepare TEM specimens from the
dendrite and interdendritic boundary of the structure shown in Figure 2b,c, respectively.
Materials 2023, 16, 7161 7 of 16

Figure 2d,f show the bright field and dark field TEM images of the ID region shown in
Figure 2b, respectively. The SADP from the [011] zone presented in Figure 2e confirms
that the bright phase in Figure 2b is the FCC phase, which is one of the products
Materials 2023, 16, x FOR PEER REVIEW 8 of 16of
BCC decomposition. The SADP from the area next to the FCC phase of the ID region
displays super-lattice spots (Figure 2g) from the ordered B2 phase, which cannot be used to
distinguish the existence of the disordered BCC phase from the identical lattice parameters
The FCC phase in the dendrite region and the B2 phase in the interdendritic region
of the BCC and B2 phases. Therefore, the dark field TEM image was obtained, taken from
of the 1100 °C-annealed HEA were measured by point-scanning of five random positions,
the additional spot of the BCC/B2 reflections (yellow circle in Figure 2g), as shown in
the results of which are provided in Table 3. EDX results show that, after the decomposi-
Figure 2f. It can be seen that these additional spots were attributed to the relatively bright
tion reaction, Al and Ni elements of the FCC phase in the dendrite region decreases to 7.9
areas, corresponding to the ordered B2 phase, and the other constituent phase of this area
at.% and 17.1 at.%, respectively. Co, Cr and Fe elements mainly accumulate in the FCC
should be the disordered BCC phase. Figure 2h presents the microstructure of the ID region
phase, especially for Cr elements, which increases from 21.6 at.% to 26.6 at.%. Conversely,
of Figure 2c. Interestingly, the corresponding SADPs (Figure 2i,j) only identify the existence
Al and Ni elements mainly accumulate in the B2 phase, being about 31.7 at.% and 30.1
of B2 (ordered BCC phase) and σ phases.
at.%, respectively.

Figure4.4. Images
Figure Images (a,b)
(a,b) show
show low-
low- and
and high-magnification
high-magnification SEM-BSE
SEM-BSEmicrographs
micrographsofofthe
the1100
1100°C-
◦ C-
annealed Al0.6CoCrFeNi HEA, respectively, showing the coarse B2 precipitation in the dendrite re-
annealed Al0.6 CoCrFeNi HEA, respectively, showing the coarse B2 precipitation in the dendrite region
gion and a new dual-phase structure in the interdendritic region. (c) TEM image of the interdendritic
and a new
region, withdual-phase structure
SADP patterns in the
showing theinterdendritic
B2 phase (darkregion.
phase in(c) TEM
(b)) and image
the FCCofphase
the interdendritic
(gray phase
region, with SADP patterns showing the B2 phase (dark phase in (b)) and the
in (b)). (d) TEM image of the dendrite region, with corresponding SADP patterns showing FCC phase (gray
the dis-
phase in (b)).
tribution (d)precipitates
of B2 TEM imageinofthe theFCC
dendrite region, with corresponding SADP patterns showing the
dendrite.
distribution of B2 precipitates in the FCC dendrite.
Table 3. EDX results of the 1100 °C-annealed Al0.6CoCrFeNi HEA.
In addition, the microstructure of the FCC dendrite region presented in Figure 2a–c
Al/at.%of a large
also revealed the precipitation Co/at.%
number Cr/at.%
of nano-sized Fe/at.%
phases in Ni/at.%
the 700 ◦ C-
FCC phase (DR) 7.9 ± 0.3 24.3 ± 0.4 26.6 ± 0.2 24.6 ± 0.4
annealed Al0.6 CoCrFeNi HEA. Figure 2l shows the [-112] zone axis from the FCC dendrite 17.1 ± 0.4
region,B2with
phasethe(ID) 31.7
additional ± 0.5of extra
spots 16.9{110}
± 0.5super-lattice
9.5 ± 0.2reflections
12.0 ± 0.4 30.1 ± 0.4with
in comparison
that of the as-cast alloy (Figure 1c), confirming the presence of the L12 phase. Figure 2k
3.3. In the
shows Situdark
XRDfield
Analysis
TEM of image
Al0.6CoCrFeNi
obtained Alloy
from the {110} superlattice reflection, clearly
revealing that
Figure these nano-phases
5 shows the results of within theXRD
the in situ FCCheating
dendrite are L12 precipitates.
experiment of the Al0.6CoCrFeNi
HEA. Comparing the XRD patterns of the alloys before and after heat treatment at room
temperature (25 °C) and referring to the results of microstructure analysis, the results in-
dicate that the disordered BCC phase is unstable and converted fully to an ordered B2 and
FCC phase. Meanwhile, the decreasing diffraction peaks of the BCC phase (labeled 2 in
Materials 2023, 16, 7161 8 of 16

Figure 3 shows the microstructure of the 900 ◦ C-annealed Al0.6 CoCrFeNi HEA, pre-
senting a more obvious microstructure evolution. As can be seen in Figure 3a,b, a large
fraction of the rod-like phase precipitated from the dendrite. Moreover, the enhanced
contrast of the constituent phases in the interdendritic region clearly indicates the existence
of three different phases, namely, the dark matrix phase, the gray phase and the spherical
bright phase. FIB was also used to prepare TEM specimens from the dendrite and interden-
dritic boundary to confirm the origin of the observed microstructure. Figure 3c shows a
high-resolution TEM image of the rod-like precipitates within the FCC dendrite, with the
corresponding Fourier transform image shown in Figure 3d, indicating a body-centered
cubic structure. With a further consideration of the thermodynamic calculation [27] and
the subsequent results of 1100 ◦ C-annealed samples, these rod-like precipitates were con-
firmed as ordered B2 phase precipitates, rather than the disordered BCC phase or the L12
precipitates in the 700 ◦ C-annealed sample. The width of the B2 nano-precipitates can reach
100 nm, which is much larger than that of the L12 nano-precipitates in the 700 ◦ C-annealed
alloy (Figure 2k). Figure 3e shows the microstructure of the ID region, where the constitut-
ing phases are successfully identified as the B2, FCC, and σ phases, respectively, according
to the corresponding SADPs (Figure 3f–h). This result is consistent with the observations
that the disordered BCC phase will convert to B2 and FCC phases when the temperature is
above 650 ◦ C [15].
Figure 4 shows the microstructure of the 1100 ◦ C-annealed Al0.6 CoCrFeNi HEA ana-
lyzed via SEM and TEM, wherein the interdendritic region further converts to a dual-phase
structure (Figure 4a,b). TEM analysis confirmed that the dark phase and gray phase are
the B2 phase and FCC phase, as shown in Figure 4c. This result is consistent with the fact
that the σ phase is also unstable and will convert to B2 and FCC phases for temperatures in
excess of 950 ◦ C [15,26]. Therefore, the 1100 ◦ C-annealed Al0.6 CoCrFeNi alloy only consists
of the B2 and FCC phases. This result is also consistent with the density variation in the
greyscale BSE image which presents only two distinct phases (Figure 4a,b). Meanwhile,
the B2 precipitates in the FCC dendrite are coarsened, with the width being about 1 µm
(Figure 4d).
The FCC phase in the dendrite region and the B2 phase in the interdendritic region of
the 1100 ◦ C-annealed HEA were measured by point-scanning of five random positions, the
results of which are provided in Table 3. EDX results show that, after the decomposition
reaction, Al and Ni elements of the FCC phase in the dendrite region decreases to 7.9 at.%
and 17.1 at.%, respectively. Co, Cr and Fe elements mainly accumulate in the FCC phase,
especially for Cr elements, which increases from 21.6 at.% to 26.6 at.%. Conversely, Al
and Ni elements mainly accumulate in the B2 phase, being about 31.7 at.% and 30.1 at.%,
respectively.

Table 3. EDX results of the 1100 ◦ C-annealed Al0.6 CoCrFeNi HEA.

Al/at.% Co/at.% Cr/at.% Fe/at.% Ni/at.%

FCC phase (DR) 7.9 ± 0.3 24.3 ± 0.4 26.6 ± 0.2 24.6 ± 0.4 17.1 ± 0.4
B2 phase (ID) 31.7 ± 0.5 16.9 ± 0.5 9.5 ± 0.2 12.0 ± 0.4 30.1 ± 0.4

3.3. In Situ XRD Analysis of Al0.6 CoCrFeNi Alloy

Figure 5 shows the results of the in situ XRD heating experiment of the Al0.6 CoCrFeNi
HEA. Comparing the XRD patterns of the alloys before and after heat treatment at room
temperature (25 ◦ C) and referring to the results of microstructure analysis, the results
indicate that the disordered BCC phase is unstable and converted fully to an ordered B2
and FCC phase. Meanwhile, the decreasing diffraction peaks of the BCC phase (labeled 2
in Figure 5) as the temperature is increased from 900 ◦ C to 1100 ◦ C indicate the gradual
decomposition of the σ phase. Similar behaviors were also observed in the heat treatment
experiments of the AlCrFeNiMo0.2 HEA [28]. The relative intensity of the diffraction peak
for the B2 and BCC phases significantly decreased after annealing at 1100 ◦ C. The existence
 Figure 5) as the temperature is increased from 900 °C to 1100 °C indicate the gradual de-
composition of the σ phase. Similar behaviors were also observed in the heat treatment
Materials 2023, 16, 7161 9 of 16
experiments of the AlCrFeNiMo0.2 HEA [28]. The relative intensity of the diffraction peak
for the B2 and BCC phases significantly decreased after annealing at 1100 °C. The exist-
ence of the σ phase can also be proved by XRD patterns of the alloys heated at 700 °C and
of the
900 phase canto
°Cσaccording also
thebecorresponding
proved by XRD patterns
weak of the alloys
diffraction peaks.heated at 700 ◦ C and evolu-
The corresponding 900 ◦ C
according
tion of thetoσ the corresponding
phase is illustratedweak diffraction
in Figures peaks.
2–4. The Thediffraction
X-ray corresponding evolution
pattern can beof the
used
σ phase is illustrated in Figures 2–4. The X-ray diffraction pattern can be
effectively for phase identification as per Bragg’s law, nλ = 2dsinθ, where d is the distanceused effectively
for phasediffraction
between identification as per
planes, λ isBragg’s law, nλ = of
the wavelength 2dsinθ, where
the X-ray d is the
beam, θ isdistance between
the incident/dif-
diffraction planes, λ is the wavelength of the X-ray beam, θ is the incident/diffracted
fracted angle of the beam and n is an integer. Here, the predominant constituting phases angle
of the beam and n
(FCC, BCC, and B2 phases) are cubic crystal structures. The expected expansion of and
is an integer. Here, the predominant constituting phases (FCC, BCC, the
B2 phases)
crystal areduring
lattice cubic crystal structures.
the heating processThecan
expected expansion
give rise of the crystal
to an increase in the lattice during
distances be-
the heating process can give rise to an increase in the distances between
tween diffraction planes (d). Therefore, the corresponding diffraction peaks shifted to lowdiffraction planes
(d). Therefore,
diffraction the corresponding
angles during the heating diffraction peaks
process. By shifted
analogy,to the
low diffraction
diffraction angles during
peaks shifted
the heating process. By analogy, the diffraction peaks shifted back to the
back to the high diffraction angles due to the contraction of the crystal lattice during the high diffraction
angles due
cooling to the contraction of the crystal lattice during the cooling process.
process.

XRDresults
5. XRD
Figure 5. resultsofofininsitu
situ heating
heating of of
thethe as-cast
as-cast Al
Al0.6 0.6 CoCrFeNi
CoCrFeNi alloyalloy
fromfrom 25 °C25to◦1100
about
about C to
°C. ◦ C.heating
1100The temperature
The heating temperature coverscovers
the phase transition
the phase relating
transition to thetodecomposition
relating of theofBCC
the decomposition the
phase and the formation and re-decomposition of the
BCC phase and the formation and re-decomposition of the σ phase.σ phase.

3.4. Mechanical
3.4. Mechanical Properties
Properties of
of as-Cast
as-Cast and
and Annealed
Annealed Al Al0.6 CoCrFeNiAlloy
0.6CoCrFeNi Alloy
Figure 66 shows
Figure the engineering
shows the stress–strain curves
engineering stress–strain curves for
for the
the as-cast and annealed
as-cast and annealed
Al 0.6 CoCrFeNi HEAs. According to Figure 6, the yield strength and tensile
Al0.6CoCrFeNi HEAs. According to Figure 6, the yield strength and tensile strength of strength of the
the
as-cast Al
as-cast Al0.6 CoCrFeNi HEAs are 462 MPa and 994 MPa, respectively, which are higher than
0.6CoCrFeNi HEAs are 462 MPa and 994 MPa, respectively, which are higher

than those ofas-cast

those of the Al0.5 CoCrFeNi
the as-cast HEAs,
Al0.5CoCrFeNi being
HEAs, 402 MPa
being 402 MPaand 568
and MPa, respectively
568 MPa, [29].
respectively
This is because the addition of the Al element in the FCC-structured CoCrFeNi
[29]. This is because the addition of the Al element in the FCC-structured CoCrFeNi HEAs HEAs
facilitates the formation of the hard BCC phases, giving rise to continuous improvement
facilitates the formation of the hard BCC phases, giving rise to continuous improvement
in the mechanical properties. Meanwhile, the as-cast Al CoCrFeNi HEA processes good
in the mechanical properties. Meanwhile, the as-cast Al0.6 0.6CoCrFeNi HEA processes good
plasticity with the elongation being 20.3%, which is due to the matrix of the soft FCC phase
plasticity with the elongation being 20.3%, which is due to the matrix of the soft FCC phase
in the as-cast structure.
in the as-cast structure.
The strengthening effect of the annealed HEA is closely related to the characteristics
The strengthening effect of the annealed HEA is closely related to the characteristics
of the reinforcement, where small and hard precipitates with a high fraction and relatively
of the reinforcement, where small and hard precipitates with a high fraction and relatively
uniform distribution are preferred. As can be seen in Figure 2k, after annealing at 700 ◦ C, a
uniform distribution are preferred. As can be seen in Figure 2k, after annealing at 700 °C,
high fraction of the nano-sized L12 phase precipitates from the FCC dendrite region with
a high fraction of the nano-sized L12 phase precipitates from the FCC dendrite region with
uniform distribution. This should be the main reason for the significant increase in the
yield and tensile strength, being 961 MPa and 1179 MPa, respectively. In addition, it is
clear by comparing Figures 1 and 2 that the morphology of the interdendritic region of the
as-cast and 700 ◦ C-annealed HEA are basically the same. The formation of the σ phase,
which is harder than the other constituent phases, can also improve the strength to a certain
 uniform distribution. This should be the main reason for the significant increase in the
yield and tensile strength, being 961 MPa and 1179 MPa, respectively. In addition, it is
Materials 2023, 16, 7161 10 of 16
clear by comparing Figures 1 and 2 that the morphology of the interdendritic region of
the as-cast and 700 °C-annealed HEA are basically the same. The formation of the σ phase,
which is harder than the other constituent phases, can also improve the strength to a cer-
extent, although its fraction is low. ◦ C-annealed
tain extent, although its fraction is The
low.corresponding elongation
The corresponding of theof
elongation 700
the 700 °C-an-
Al0.6 CoCrFeNi
nealed HEA only
Al0.6CoCrFeNi HEA retains 2.9%, which
only retains 2.9%, follows the traditional
which follows trade-off
the traditional relationship
trade-off rela-
between between
tionship strength strength
and plasticity.
and plasticity.

Figure
Figure 6.
6. Room-temperature tensile
Room-temperature tensile stress–strain
stress–strain curves
curves for as-cast
for the the as-cast and annealed
and annealed Al0.6CoCrFeNi
Al0.6 CoCrFeNi HEA.
HEA.
As the annealing temperature is further increased, the B2 phase (thermodynamic
As the annealing
equilibrium phase [27])temperature
precipitates is furtherfrom
directly increased,
the FCCthe B2 phase
dendrite (thermodynamic
according to the cor-
equilibrium phase [27]) precipitates directly from the FCC
responding SADPs shown in Figures 3c and 4d. However, the effect of precipitation dendrite according to the cor-
responding
hardening isSADPs expected shown in Figures
to weaken 3c anddue
gradually 4d. However, the effect
to the increase ofand
in size precipitation hard-
will give rise to
the softening
ening of thetoalloy
is expected weaken compared
graduallywithdue
thattoofthe 700 ◦ C-annealed
the increase in size andalloy. Correspondingly,
will give rise to the
the yield strength andcompared
tensile strength of the ◦ C-annealed alloy drops to 670 MPa and
900 700
softening of the alloy with that of the °C-annealed alloy. Correspondingly,
1010yield
the MPa, respectively,
strength with the
and tensile corresponding
strength of the 900 elongation
°C-annealedreverting
alloy dropsbacktoto6706.2%.
MPaAfter
and
annealing
1010 MPa, at 1100 ◦ C, the
respectively, withσ phase fully disappeared
the corresponding and the
elongation interdendritic
reverting back to region was
6.2%. After
completelyatreplaced
annealing 1100 °C,by thethe σ FCC
phaseand B2disappeared
fully dual-phase microstructure (Figure region
and the interdendritic 4). Thewasmi-
crostructurereplaced
completely evolutionbycausedthe FCC by phase
and B2transition
dual-phase andmicrostructure
the coarsening (Figure
of the B24).precipitation
The micro-
further weakens
structure evolutionthecaused
strengthening
by phase effect of the alloy,
transition and the resulting in a decrease
coarsening of the B2inprecipitation
the strength.
Therefore, the mechanical properties effect
of the 1100 ◦
further weakens the strengthening of theC-annealed alloy return
alloy, resulting to a levelinclose
in a decrease the
to that of the as-cast alloy, with the yield strength, tensile strength,
strength. Therefore, the mechanical properties of the 1100 °C-annealed alloy return to a and elongation being
492 MPa,
level close1007 MPa,
to that andas-cast
of the 19.6%,alloy,
respectively.
with the yield strength, tensile strength, and elonga-
Figure 7 shows the morphology
tion being 492 MPa, 1007 MPa, and 19.6%, of the fracture surface of the as-cast and annealed
respectively.
Al0.6 CoCrFeNi
Figure 7 shows the morphology of the fracture surface
HEAs after tensile tests. The fracture surface of ofthe
theas-cast
as-castAl 0.6 CoCrFeNi
and annealed
HEA exhibits many dimples, indicating a ductile fracture (Figure
Al0.6CoCrFeNi HEAs after tensile tests. The fracture surface of the as-cast Al0.6CoCrFeNi 6a). The observed large
dimension
HEA exhibitsof dimples corresponds
many dimples, to theacoarse
indicating ductile and soft FCC
fracture dendrite
(Figure 6a). structure.
The observed However,
large
the 700 ◦ C-annealed Al CoCrFeNi HEA exhibits typical river patterns and indicates the
0.6
dimension of dimples corresponds to the coarse and soft FCC dendrite structure. How-
cleavage
ever, fracture,
the 700 which isAl
°C-annealed because the precipitation hardening of the nano-sized L12 phase
0.6CoCrFeNi HEA exhibits typical river patterns and indicates
in the FCC dendrite and the
the cleavage fracture, which is because the dislocation movement
precipitation is severely
hardening hindered. Although L1
of the nano-sized the2
precipitation formed from the FCC dendrite of the 900 ◦ C-annealed Al CoCrFeNi HEA
phase in the FCC dendrite and the dislocation movement is severely hindered. 0.6 Although
converted to the B2 phase, its size is much larger than the L1 phase in the 700 ◦ C-annealed
the precipitation formed from the FCC dendrite of the 900 °C-annealed Al0.6CoCrFeNi 2
alloy (Figure 2k), and thus the effect of precipitation hardening is weakened. Therefore,
HEA converted to the B2 phase, its size is much larger than the L12 phase in the 700 °C-
the 900 ◦ C-annealed Al0.6 CoCrFeNi HEA exhibits mixed-mode fracture mechanism of
annealed alloy (Figure 2k), and thus the effect of precipitation hardening is weakened.
ductile and cleavage fractures, with the presence of fine dimples. The 1100 ◦ C-annealed
Al0.6 CoCrFeNi HEA also exhibits a mixed fracture mechanism, but is also different in
its details. First, the dimension of the dimples is larger than that of the 900 ◦ C-annealed
Al0.6 CoCrFeNi HEA, which could be attributed to the increasing size of B2 precipitates
in the 1100 ◦ C-annealed sample. Moreover, the fracture of the 1100 ◦ C-annealed sample
 Therefore, the 900 °C-annealed Al0.6CoCrFeNi HEA exhibits mixed-mode fracture mech-
anism of ductile and cleavage fractures, with the presence of fine dimples. The 1100 °C-
annealed Al0.6CoCrFeNi HEA also exhibits a mixed fracture mechanism, but is also differ-
Materials 2023, 16, 7161 11 of 16
ent in its details. First, the dimension of the dimples is larger than that of the 900 °C-an-
nealed Al0.6CoCrFeNi HEA, which could be attributed to the increasing size of B2 precip-
itates in the 1100 °C-annealed sample. Moreover, the fracture of the 1100 °C-annealed
is than
sample is flatter flatter than
that of that of the and
the as-cast as-cast
900and 900 ◦ C-annealed
°C-annealed samples.samples. This
This result result is consistent
is con-
◦
sistent with thewith the corresponding
corresponding FCC and FCC
B2 and B2 dual-phase
dual-phase microstructure
microstructure (Figure(Figure
4a,b) of4a,b)
the of the 1100 C-
1100 °C-annealedannealed Al0.6 CoCrFeNi
Al0.6CoCrFeNi HEA consisting
HEA consisting of thedendrite
of the FCC FCC dendrite
regionregion
with B2with
pre-B2 precipitation
and the interdendritic region with the FCC phase in the
cipitation and the interdendritic region with the FCC phase in the B2 matrix. B2 matrix.

Figure 7. Fracture morphologies of the as-cast and annealed Al0.6CoCrFeNi HEAs. (a) as-cast; (b)
Figure 7. Fracture morphologies of the as-cast and annealed Al0.6 CoCrFeNi HEAs. (a) as-cast;
700 °C; (c) 900 °C; and (d) 1100 °C.
(b) 700 ◦ C; (c) 900 ◦ C; and (d) 1100 ◦ C.
4. Discussion 4. Discussion
The pseudobinary isopleth diagram
The pseudobinary of the
isopleth AlxCoCrFeNi
diagram of the Al alloy systemalloy
x CoCrFeNi with system
varyingwith varying Al
Al content, reproduced from reference
content, reproduced from [27,30], is illustrated
reference [27,30], isin Figure 8. in
illustrated The composition
Figure 8. The composition of
of the studied the
Al0.6studied
CoCrFeNi Al0.6HEA is marked
CoCrFeNi HEAwith a red vertical
is marked with a red dotted linedotted
vertical on theline
dia-on the diagram.
gram. The points
The1,points
2, and1,32,correspond to the Al
and 3 correspond CoCrFeNi
to0.6the HEAs annealed
Al0.6 CoCrFeNi at 700 ◦ C, 900 ◦ C,
at 700 °C,
HEAs annealed
900 °C, and 1100
and 1100 ◦
°C, respectively.
C, respectively.However,
However, thetheconstituent
constituentphases phases of the as-cast
of the as-castAl0.6 CoCrFeNi
Al0.6CoCrFeNi HEA
HEA (FCC(FCC++BCC BCC++B2, B2,Figure
Figure2)2)dodo not seem
not seem to to
fit fit
thethethermodynamic
thermodynamic prediction at low
temperatures (Figure 8) due to the absence of the L1
prediction at low temperatures (Figure 8) due to the absence of the 2L12 and σ phases. In- and σ phases. Instead, the experi-
mental observation is consistent with the phase prediction
stead, the experimental observation is consistent with the phase prediction at high tem- at high temperatures (above
1300 ◦ C).°C).
For For
the multi-component high-entropy alloys, the diffusion-dependent processes
peratures (above 1300 the multi-component high-entropy alloys, the diffusion-
like crystallization,
dependent processes grain growth,
like crystallization, and precipitation
grain growth, and precipitationare expected to be to
are expected slow, due to the
be slow, due tosluggish
the sluggishlong-range diffusion
long-range [31]. [31].
diffusion Therefore, the solidification
Therefore, pathpath
the solidification of the
ofAl0.6 CoCrFeNi
melt would be for the growth of the FCC dendrite
the Al0.6CoCrFeNi melt would be for the growth of the FCC dendrite with chemical su- with chemical supersaturation and the
residual liquid in the interdendritic region solidifies to
persaturation and the residual liquid in the interdendritic region solidifies to the BCC the BCC phase, which subsequently
decomposes decomposes
phase, which subsequently to BCC and B2 phases.
to BCC and The rest of The
B2 phases. the phase
rest of transitions below 1300 ◦ C are
the phase tran-
suppressed,
sitions below 1300 resulting in
°C are suppressed, the retention
resulting of the supersaturated
in the retention FCC phase
of the supersaturated FCCand disordered
BCC phase
phase and disordered BCCinphasethe as-cast
in thealloy.
as-cast alloy.
The thermodynamic equilibrium phases are expected to be obtained in the annealed
alloys via the decomposition of the unstable phases. Therefore, the thermodynamic
stable phases for this composition at 700 ◦ C and 900 ◦ C should be the same, namely,
FCC + B2 + σ. The corresponding phase fractions vary as the annealing temperature is
increased, which will not be discussed here. Since the σ phase can be obtained via the
decomposition of the BCC phase in the ID region, the precipitation within the FCC dendrite
is expected to be of the B2 phase. This result is consistent with the observation in the
900 ◦ C-annealed sample, with the formation of a nano-sized rod-like B2 phase. However,
Materials 2023, 16, 7161 12 of 16

the L12 phase, rather than the predicted B2 phase, is formed directly from the FCC dendrite
at 700 ◦ C. The onset nucleation kinetics of precipitates (L12 , B2, σ, and BCC) were first
analyzed in Al0.3 CoCrFeNi HEA by Gwalani et al. [27]. The predicted results show that,
although the B2 phase has the maximum driving force over the entire temperature range
according to the calculated extended line, the nucleation barrier of the L12 phase is the
minimum and is lower than that of the B2 phase at temperatures below about 760 ◦ C. These
results are in line with the observations in the present paper. Despite being a metastable
phase, the nano-sized L12 phase is precipitated directly from the FCC phase due to the
low interfacial energy between these two phases as they have the same lattice parameters
(Figure 2k). The coherent characteristics of the L12 precipitates and the FCC matrix have
also been reported in Al0.3 CoCrFeNi [5]. However, the nucleation barrier of the L12 phase
is higher than that of the B2 phase at temperatures above 760 ◦ C. Instead, the B2 phase,
possessing the maximum driving force, directly precipitated from the FCC dendrite at
900 ◦ C. The size of the B2 precipitates, with a width of 100 nm, is larger than that of the
L12 phase observed at 700 ◦ C, due to the coarsening mechanism of the precipitates with
increasing annealing temperature [32]. Here, the interface of the B2 phase and the FCC
matrix is not coherent due to the difference in the crystal orientation according to the
high-resolution TEM analysis and lattice parameters, and the semi-coherent or incoherent
characteristics are also reported in the Al0.3 CoCrFeNi. It is clear that the constituent phases
of the 900 ◦ C-annealed Al0.6 CoCrFeNi are consistent with the thermodynamic prediction.
The FCC dendrites contain the B2 precipitates and the interdendritic region contains the
B2, FCC, and σ phases. As the annealing temperature is increased to 1100 ◦ C, the σ phase
decomposes to the FCC and B2 phases and the interdendritic region also converts to an
FCC-BCC dual-phase structure (Figure 4b). This result is also consistent with the thermo-
dynamic prediction that the stable phases of the Al0.6 CoCrFeNi at 1100 ◦ C are FCC and
Materials 2023, 16, x FOR PEER REVIEW 12 ofB216
phases (point 3 in Figure 8).

Figure8.8.Calculated
Figure Calculatedisopleth
isoplethofofthe
theAl
Al xCoCrFeNiwith
x CoCrFeNi withxx==0–1
0–1[27,30].
[27,30].The
Thered
reddotted
dottedline
lineshows
showsthe
the
composition of the Al 0.6CoCrFeNi alloy. Points 1, 2, and 3 correspond to the samples annealed at 700
composition of the Al0.6 CoCrFeNi alloy. Points 1, 2, and 3 correspond to the samples annealed at
°C,◦900
700 °C,◦and
C, 900 1100
C, and °C.◦ C.
1100

InThe thermodynamic
general, equilibrium
the FCC phase phases
is soft and are expected to alloys
the FCC-structured be obtained
alwaysinpresent
the annealed
good
alloys viayet
plasticity thelow
decomposition
strength. TheofBCC
the unstable phases.than
phase is harder Therefore,
the FCCthe thermodynamic
phase stable
due to the lack of
slip direction, which can be used to strengthen the alloys with increasing fractions. The σ+
phases for this composition at 700 °C and 900 °C should be the same, namely, FCC + B2
σ. The
phase corresponding
with phase fractions
a tetragonal structure vary asslip
lacks multiple thesystems,
annealing
and temperature
thus is harderisand
increased,
brittle,
which will not be discussed here. Since the σ phase can be obtained via the decomposition
of the BCC phase in the ID region, the precipitation within the FCC dendrite is expected
to be of the B2 phase. This result is consistent with the observation in the 900 °C-annealed
sample, with the formation of a nano-sized rod-like B2 phase. However, the L12 phase,
Materials 2023, 16, 7161 13 of 16

which can also act as a reinforcement [33]. In addition, the disordered–ordered transition
can also improve the strength of the alloy due to the reduced number of slip planes in
ordered phases [34]. For the Al0.6 CoCrFeNi HEA annealed at 700 ◦ C, the decomposition
of the disordered BCC phase begins with the formation of the softer FCC phase and the
harder σ phase (Figure 2b,c). In some regions, the phase transition has not yet occurred.
Therefore, it is assumed that the phase transition of the interdendritic region at 700 ◦ C does
not affect the mechanical properties, due to the opposite effect of the decomposed FCC
and σ phases. Therefore, the formation of the nano-sized L12 phase with a large fraction
gives rise to the most significant improvement in the strength for the 700 ◦ C-annealed
Al0.6 CoCrFeNi HEA. The corresponding fracture model converts to the cleavage fracture.
The precipitation of the coarse B2 phase from the FCC dendrite, with semi-coherent or
incoherent interfaces, results in the strength reduction in the alloys after annealing at 900 ◦ C
and 1100 ◦ C. Although the formation of the hard σ phase in the interdendritic region would
have a weak effect on improving the strength of the 700 ◦ C-annealed and 900 ◦ C-annealed
Al0.6 CoCrFeNi HEAs, the decomposition of the σ phase could have a considerable impact
on softening of the 1100 ◦ C-annealed Al0.6 CoCrFeNi HEA. This is because the BCC + B2
structure in the interdendritic region completely converts to the soft and coarse FCC + B2
structure, wherein the fraction of the FCC phase is more than 50% in the interdendritic
region (Figure 4b).
Different from the co-existence of the FCC, B2, and σ phase obtained in the Al0.3 CoCrFeNi
HEA by means of 90% cold rolling and directly annealed at 620 ◦ C, the disordered BCC phase
in the present paper, as well as the decomposed σ phase at 700 ◦ C and 900 ◦ C, was confined
to the interdendritic region. Here, there is still one problem that cannot be explained with
solid evidence, namely that the co-existence of the FCC and σ phases, formed from the
decomposition of the BCC phase, are not detected at the same time, as shown in Figure 2b,c.
Even so, TEM-EDS analysis was also carried out on the interdendritic region shown in
Figures 1 and 2b,c, the results of which are shown in Figure 9. It is clear that, for the as-cast
and 700 ◦ C-annealed Al0.6 CoCrFeNi HEAs, the B2 phase is rich in Al and Ni and lean in Cr
and Fe. The decomposed FCC phase (Figure 9b) is rich in Cr, Fe and Co, and lean in Al and
Ni, which is slightly different from that of the BCC and σ phases. As can be seen in Figure 9c,
the decomposed σ phase is rich in Cr and Fe and lean in Al and Ni. According to the Cr
element distribution image in Figure 9b, the remaining disordered BCC phase contains a
higher composition of Cr than that of the decomposed FCC phase. Therefore, the σ phase
might be obtained via the decomposition of the remaining BCC phase. This raises the question
of whether the σ phase is first formed via the decomposition of the BCC phase, which might
be due to the local elemental segregation during solidification (Figure 1a and Table 2) and
constitutes part of future studies.
Except for the size variation in the precipitation, the potential coarsening behavior of
the grain or structure originally solidified from the Al0.6 CoCrFeNi should be considered as
well, especially for the FCC dendrite. According to the SEM investigation of the as-cast and
annealed Al0.6 CoCrFeNi HEAs, it can be concluded that no obvious dendrite coarsening
was found. The difference in the dendrite structure presented in Figures 1–4 is caused by
the solidification in the arc-melted casting rod, wherein the grain might present a certain
orientation [4]. This is also the reason for the reflected difference in the (111)/(200) peak
ratio, as shown in Figure 5.
The results also indicate the element segregation of the as-cast Al0.6 CoCrFeNi HEA
with the formation of coarse FCC dendrite, which will reduce the strengthening effect
caused by the decomposition of the supersaturated FCC phase. As mentioned above,
the microstructure and mechanical properties of the Al0.6 CoCrFeNi HEA could also be
tuned by deformation and subsequent recrystallization mechanisms. Recent studies also
revealed that the microstructure of the as-cast HEAs can be strongly adjusted during the
fabrication process with the assistance of advanced technologies, such as 3D printing [35,36],
solidification assisted by directional temperature field [20], electromagnetic field [21], and
high cooling rate and/or high undercooling [34,37]. The favorable microstructures could be
 with the formation of coarse FCC dendrite, which will reduce the strengthening effect
caused by the decomposition of the supersaturated FCC phase. As mentioned above, the
microstructure and mechanical properties of the Al0.6CoCrFeNi HEA could also be tuned
by deformation and subsequent recrystallization mechanisms. Recent studies also re-
vealed that the microstructure of the as-cast HEAs can be strongly adjusted during the
Materials 2023, 16, 7161 14 of 16
fabrication process with the assistance of advanced technologies, such as 3D printing
[35,36], solidification assisted by directional temperature field [20], electromagnetic field
[21], and high cooling rate and/or high undercooling [34,37]. The favorable microstruc-
grain
tures refinement and refinement
could be grain weakened element segregation.
and weakened Therefore,
element it is also
segregation. an effective
Therefore, it isroute
also
to improve the mechanical properties of the HEAs related to unstable phases
an effective route to improve the mechanical properties of the HEAs related to unstable by means
of theseby
phases advanced
means of solidification technologies
these advanced combining
solidification subsequent
technologies simplesubsequent
combining annealing
processes, thus avoiding the severe plastic deformation operations.
simple annealing processes, thus avoiding the severe plastic deformation operations.

Figure 9. Images (a–c) show TEM micrographs corresponding to the ID-2 in Figure 1b and the ID
Figure 9. Images (a–c) show TEM micrographs corresponding to the ID-2 in Figure 1b and the ID region
region in Figure 2b,c, respectively. The measured elemental composition is listed on the same line
in Figure 2b,c, respectively. The measured elemental composition is listed on the same line in order.
in order.
5. Conclusions
5. Conclusions
In conclusion, the mechanical properties of Al0.6 CoCrFeNi HEA can be enhanced via
In conclusion,
the phase transitionstheofmechanical properties
the as-solidified of Al0.6
unstable CoCrFeNi
phases usingHEA can be
a simple enhanced
heat via
treatment
the phase transitions of the as-solidified unstable phases using a
process. The maximum increase in yield strength can be achieved after annealing at simple heat treatment
700 ◦ C, with
process. The the
maximum
increment increase in yield
being about strength
107%, which can be achieved
is mainly after annealing
attributed to the numerousat 700
°C, with the increment being about 107%, which is mainly attributed
L12 nano-precipitates in the FCC dendrite region. The disordered BCC phase in the to the numerous L12
nano-precipitates
interdendritic in the
region can FCC dendriteinto
decomposes region.
FCC The
and disordered
σ phases at BCC
700–900 ◦
phase in the
C and theinterden-
σ phase
dritic
will region can decomposes
subsequently convert to B2into andFCCFCCand σ phases
phases at 1100at ◦700–900 °C and the
C. The softening of σthephase ◦ C-
1100will
subsequently
annealed alloyconvert
can be to B2 and FCC
attributed phases
to the at 1100B2°C.
coarsening The softening
precipitates in theof dendrite
the 1100 region
°C-an-
nealed
and thealloy
soft can
FCCbephase
attributed
formed to the coarsening
in the B2 precipitates
interdendritic in the dendrite
region. Finally, region and
the corresponding
the soft FCC
mechanical phase formed
properties in values
revert to the interdendritic
very close to region.
those ofFinally, theAl
the as-cast corresponding
0.6 CoCrFeNi HEA. me-
chanical properties revert to values very close to those of the as-cast Al0.6CoCrFeNi HEA.
Author Contributions: P.H.: conceptualization, methodology, data curation, writing—original draft; Y.Y.:
methodology; L.Z.: methodology,
Author Contributions: investigation; Y.M.:methodology,
P.H.: conceptualization, investigation, methodology,
data curation,writing—review and
writing—original
editing; Y.C.:methodology;
draft; Y.Y.: conceptualization,
L.Z.:investigation;
methodology, L.C.: conceptualization,
investigation; data curation,methodology,
Y.M.: investigation, funding acquisition,
writ-
writing—review and editing, supervision. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China (No.
52001006), the Beijing Natural Science Foundation (No. 2194074), the Science and Technology Project
of Beijing Municipal Education Commission (No. KM201910009005) and the Young Yuyou Talent
Project (No. 20XN212/001) of North China University of Technology.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are contained within the article.
Materials 2023, 16, 7161 15 of 16

Conflicts of Interest: The authors declare no conflict of interest.

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