Acta Materialia 240 (2022) 118314

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Chemical domain structure and its formation kinetics in CrCoNi

medium-entropy alloy
Jun-Ping Du a,∗, Peijun Yu a, Shuhei Shinzato a, Fan-Shun Meng a, Yuji Sato b, Yangen Li a,
Yiwen Fan a, Shigenobu Ogata a,∗
a
Department of Mechanical Science and Bioengineering, Osaka University, Osaka 560-8531, Japan
b
Department of Mechanical Engineering, The University of Tokyo, Tokyo 113-8656, Japan

a r t i c l e i n f o a b s t r a c t

Article history: The formation of local chemical order in medium-entropy alloys and high-entropy alloys (MEAs/HEAs)
Received 30 May 2022 has been strongly suggested in recent experimental observations. Since chemical order can lead to
Revised 19 August 2022
changes in mechanical and functional properties, tailoring of chemical order is a promising approach
Accepted 28 August 2022
for further improving those properties of MEAs and HEAs. However, details remain unclear regarding
Available online 30 August 2022
the atomic structure of the chemical order and the formation kinetics. Here, employing a large-scale
Keywords: Monte Carlo/molecular dynamics hybrid annealing simulation with a neural network potential, we find a
Atomic ordering chemical-domain structure (CDS) after annealing below 800 K in FCC CrCoNi MEA. In addition, the forma-
Kinetic Monte Carlo tion kinetics, such as the formation time and process and time–temperature–chemical-order diagrams of
Artificial neural networks the CDS, were successfully obtained using a kinetic Monte Carlo simulation with artificial neural network
Atomistic modeling acceleration. The findings provide key information for controlling chemical order via thermal processing.
Atomic structure
© 2022 The Author(s). Published by Elsevier Ltd on behalf of Acta Materialia Inc.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)

1. Introduction on atom probe tomography observations of CrCoNi MEA annealed

Medium-entropy alloys (MEAs) and high-entropy alloys (HEAs)
with multiple principal elements constitute a new category of po-
tential structural materials in engineering design that exhibit su-
perior combinations of strength, ductility, and fracture toughness
[1–12]. Compositional adjustments of these MEAs and HEAs have
produced other superior properties, such as strong corrosion resis-
tance [13,14], fatigue resistance [15,16], wear resistance [17], and
functional properties [12,18].
The existence of chemical short-range order (CSRO) in the an-
nealed equiatomic CrCoNi MEA system has been suggested by both
experimental [19,20] and theoretical approaches [21–24]. Zhang
et al. asserted that hardness enhancement in CrCoNi MEA was due
to nanometer-sized CSRO with a superlattice diffraction pattern
formed after aging at 1273 K for 120 h followed by slow furnace
cooling [19]. Meanwhile, Yin et al. argued that the CSRO formed
above 873 K in the alloy was negligible or had a negligible effect
on its strength and hardness [25]. Therefore, they speculated that
the chemical order found by Zhang et al. [19] was formed during
the furnace cooling when the system fell below 873 K [25]. Based
∗
Corresponding authors.
E-mail addresses: jpdu@tsme.me.es.osaka-u.ac.jp (J.-P. Du), ogata@me.es.osaka-
u.ac.jp (S. Ogata).
at 973 K for 384 h, Inoue et al. [26] recently argued that the struc-
tural unit of local chemical order is a 10-atomic-layer structure (∼
2 nm) with an alternating arrangement of Cr-rich {100} and Co/Ni-
rich {100} atomic layers. However, based on electron diffraction
observations of CrCoNi MEA annealed at 873 K and 1273 K for 1 h,
Zhou et al. [27] argued that the structural unit of local chemical
order is an alternating arrangement of Cr-rich {113} and Co/Ni-
rich {113} atomic layers with the size of 0.6 nm, similar to the
structural unit of local chemical order found in VCoNi MEA [28].
The differing conclusions among different experiments regarding
chemical order may be results of differences in experimental con-
ditions, such as sample preparation, heat treatment, and analytical
method.
As a complement to experimental research, atomic simulation
has been used to reproduce chemical order with the atomic-scale
resolution, for instance in annealing simulations by density func-
tional theory (DFT)-based atom-swap Monte Carlo (MC) methods
with molecular dynamics (MD) sampling (atom-swap-MC-based
MC/MD hybrid method). Although DFT is reliable in the descrip-
tion of complicated interatomic interactions in MEAs and HEAs,
the physical size of the simulation model is limited to, at most,
hundreds of atoms, i.e., ∼ 4 nm3 [21,22,24], due to the high com-
putational cost of the method. Therefore, although chemical order
in MEAs and HEAs has been determined using the DFT-based MC

https://doi.org/10.1016/j.actamat.2022.118314
1359-6454/© 2022 The Author(s). Published by Elsevier Ltd on behalf of Acta Materialia Inc. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/)
J.-P. Du, P. Yu, S. Shinzato et al.
method, the atomic structures of the nanometer-sized chemical or-
der found in experiments [19,26–28] may not be fully captured
in the physically small simulation model. More importantly, atom-
swap-MC-based MC/MD hybrid simulations can only reproduce
equilibrium chemical order at each temperature and thus do not
supply any kinematic information, such as the chemical order for-
mation time or formation process. To expand the size of the sim-
ulation model, the embedded atom method (EAM) [29] has been
used in place of DFT. However, the accuracy of the EAM is ques-
tionable for studying the details of chemical order in general. For
example, a strong attractive interaction in Ni–Cr pairs in CrCoNi
MEA has been found in DFT and experimental studies [20–22] but
has not been reproduced by the EAM. Recently, machine learning
interatomic potentials [30] based on a DFT training dataset, such
as a neural network potential (NNP) [31] or a Gaussian approxima-
tion potential [32], have rapidly developed and been successfully
applied to atomic simulations for various materials [33,34]. In our
prior work, we have trained an NNP (Version 1) on the CrCoNi
MEA system that describes well the bulk and defect properties
of the MEA including local chemical interactions [35]. Generally,
an NNP has a flexible architecture, so it can be used to describe
the complex potential surface of a multicomponent alloy system
given a well-prepared DFT-based training dataset. In addition, NNP
computation is much faster than that of DFT, and thus simulation
model of a physical size sufficient to contain the nanometer-sized
chemical order can be employed. In the present work, we further
trained the NNP (Version 1) for CrCoNi MEA [35] with n2p2 code
[36] to improve its performance, and then constructed an NNP
(Version 2) having a crucial advantage to the EAM (see Section 1 in
Supplementary Information). In this training, we included not only
the total potential energy of the system but also the atomic force
acting on each atom in the DFT training dataset. Then, based
on the NNP (Version 2), we applied the atom-swap-MC-based
MC/MD hybrid method to obtain the temperature-dependent equi-
librium chemical order for a simulated annealing of hundreds of
swaps per atom in a large CrCoNi MEA model: 32 nm3 (2916
atoms). This method newly revealed a chemical-domain structure
(CDS) in the MEA, which could be corresponding to the conven-
tional domains in alloys. This architecture was found to consist of
many few-nanometer-sized superlattice-chemical-ordered-domains
(SLCOD) with various orientations of order in single-phase FCC Cr-
CoNi MEA at annealing temperatures below 800 K. Especially, a
CDS with larger-sized SLCOD was found at annealing temperatures
below 700 K. The SLCOD has an intermetallic-compounds-type su-
perlattice chemical order, which consists of an alternating arrange-
ment of Cr-rich and Co/Ni-rich layers in {100} and {110} orienta-
tions. On the other hand, local CSROs within mostly the second-
nearest-neighbor range of FCC was found at annealing tempera-
tures above 800 K. The obtained results are consistent with re-
cent experimental results [19,20,26–28]. In addition to the chem-
ical order analysis at thermal equilibrium, we performed a ki-
netic Monte Carlo (kMC) vacancy diffusion simulation employing a
newly developed very fast neural network scheme of vacancy jump
rate prediction. The method successfully estimated the chemical
order formation time and the formation process at various tem-
peratures. With these predictions as a basis, time–temperature–
chemical-order diagrams were drawn, providing key information
for controlling chemical order via thermal processing.
2. Methodology
2.1. Neural network potential for CrCoNi MEA
The NNP (Version 2) for CrCoNi MEA was trained via n2p2 code
[36] based on a DFT training dataset (see Ref. [37]) using collinear
spin-polarized DFT calculations on VASP [38–40]. However, the ef-
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Acta Materialia 240 (2022) 118314
fect of non-collinear spin configurations on energy does not qual-
itatively alter the chemical ordering tendency [35]. The validation
of the NNP (Version 2) and the performance comparison with the
NNP (Version 1) [35] are presented in Section 1 in Supplemen-
tary Information. The NNP files used in simulations by LAMMPS
through the LAMMPS interface implemented in n2p2 can be down-
loaded from Ref. [37].
2.2. Monte Carlo/molecular dynamics hybrid simulations
To reveal the temperature-dependent equilibrium chemical or-
der in CrCoNi MEA, we performed atom-swap-MC-based MC/MD
hybrid simulations using LAMMPS code [41] at constant temper-
ature and zero pressure with a 2916-atom (N = 2916) Cr–Co–
Ni equiatomic cubic-shaped FCC supercell model and using the
newly trained NNP. Initially, we randomly assigned Cr, Co, and
Ni atoms to the FCC sites with keeping equiatomic concentration,
and applied the atom-swap-MC-based MC/MD hybrid method. One
MC/MD hybrid simulation step consists of three atom-swap MC tri-
als between atoms of different elements followed by a 10-fs MD
sampling under NPT (i.e., constant number of atoms, pressure, and
pm
temperature). Warren–Cowley order parameters [42], αimj = 1 − ij
cj ,
were used to characterize the degree of ordering of element i and
element j in the mth-neighbor coordinate shell, where pm ij
is the
probability of finding an atom of element j in the mth-neighbor
coordinate shell of an atom of element i, and c j is the atomic con-
centration of element j. When calculating the αimj value, each atom
was re-positioned on the FCC lattice site to extract “on-lattice”
chemical order. A positive αimj denotes a repulsive tendency be-
tween element j and element i, and vice versa.
2.3. Kinetic Monte Carlo simulations
As noted in Section 2.2, the atom-swap-MC-based MC/MD hy-
brid method can study only the thermal equilibrium state. There-
fore, we here performed kMC vacancy diffusion simulation in or-
der to estimate the chemical order formation time and forma-
tion process at various temperatures. The basic concept of the
kMC simulation is the same as in our prior work [43], in which
a time–temperature–CSRO relation was derived. The time incre-
ment tkMC corresponding to the average incubation time for a
ln(1/r )
vacancy jump in the kMC simulation is given by tkMC = 12 ,
i=1 νi
where r is a random number uniformly distributed between 0
and 1 such that ln(1/r ) = 1. νi is the jump frequency of any one
of the 12 vacancy jump directions to the nearest-neighbor FCC
sites. νi = ν0 exp(−E i /kB T ), where ν0 = 1012 s−1 , is an attempt
frequency and is set as the typical atomic vibration frequency. It
should be noted that we approximate the attempt frequency by the
constant value for simplicity, while it should have a local chemical
environment dependency which can be explicitly computed using,
for example, minimum energy pathway analysis [44,45]. kB is the
Boltzmann constant, and T is the temperature. E i is the activa-
tion energy for the vacancy jump given by the minimum energy
path computations using the nudged elastic band (NEB) method
[46,47] with an interatomic potential. However, here the high com-
putational cost of NNP makes it inefficient to compute E i with
the NEB method. Therefore, we newly developed a fast computa-
tional technique of vacancy jump activation energy estimation us-
ing an artificial neural network (ANN), which can avoid the time-
consuming minimum energy path computations at each kMC step
(see Fig. 1) and significantly accelerate the kMC simulation. The
ANN predicts the vacancy jump activation energy E as the out-
put from two inputs: on-lattice (unrelaxed) atomic configuration
J.-P. Du, P. Yu, S. Shinzato et al.
Fig. 1. Illustration of the relaxed structure energy estimator based on artificial neural network predicting vacancy jump activation energy (E) from two inputs: unrelaxed
configuration before the vacancy jump (RI ) and unrelaxed near-saddle atomic configuration (RS ).
before the vacancy jump RI and unrelaxed near-saddle atomic con-
figuration RS = 12 (RI + RF ), where RF is the on-lattice atomic con-
figuration after the vacancy jump (see Fig. 1). The same descriptors
of atomic structure in the ANN as in the NNP (Version 2), such
as symmetry functions, were used. The training dataset was con-
structed using the NEB method [46,47] and the NNP (Version 2) for
72,490 different vacancy configurations in a 107-atom cubic FCC
supercell (see Section 2 in Supplementary Information). In the NEB
calculation, the initial and saddle atomic configurations were fully
relaxed for computation of the energies in these configurations,
E relax (RI ) and E relax (RS ), respectively. The activation energy was
computed as the difference between the ANN outputs of these en-
ergies: E = E relax (RS ) − E relax (RI ). The constructed ANN’s activa-
tion energy prediction showed an average error of only 0.05 eV, as
confirmed using a test dataset containing 20,0 0 0 different vacancy
configurations that are not included in the training dataset (see
Supplementary Fig. S8). The calculated 20,0 0 0 activation energies
for vacancy migration show a large variation, i.e. the range with
the three standard deviations of the mean is 0.31 eV ∼ 1.38 eV and
0.34 eV ∼ 1.36 eV for the NNP and the ANN, respectively, which
are in good agreement with that for DFT, 0.35 eV ∼ 1.24 eV [48].
The ANN prediction scheme can accelerate the kMC simulation
speed 500 times in the case of the 2916-atom Cr–Co–Ni equiatomic
cubic-shaped FCC supercell model with one vacancy (see Supple-
mentary Fig. S9) because 200 ∼ 300 times of energy/force eval-
uations are necessary for one activation energy evaluation while
only twice ANN evaluations for initial and saddle atomic configura-
tions are needed in ANN prediction strategy. The advantage of the
ANN scheme becomes more significant for larger models requiring
a larger number of energy/force evaluations in one activation en-
ergy evaluation.
The ANN training dataset for activation energy estimation was
constructed from the vacancy jump activation energy estimated at
0 K using the NNP with the NEB method [46,47]. The effect of vi-
brational entropy was neglected in the kMC simulation, while it
was considered in the atom-swap-MC-based MC/MD hybrid sim-
ulations in the Section 2.2. The effect of the vibrational entropy
on the activation energy is roughly a few kB T [49], where kB
is the Boltzmann constant, and T is the temperature. Thus, ex-
pected error in time in log-scale is not significant, such as ∼
log[exp(akB T /kB T )] < 1 (a ∼ 2 [50]).
3. Results
3.1. Temperature-dependent chemical order in CrCoNi MEA
The values of Warren–Cowley order parameters, αimj , up to m
= 22 are shown in Fig. 2 for models annealed using the atom-
swap-MC-based MC/MD hybrid method at various temperatures:
700 K and 800 ∼ 1200 K after 600N and 100N atom-swap MC
trials, respectively, where N = 2916 atoms. To avoid the artificial
effects of the initial structure selection on the annealed structure,
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Acta Materialia 240 (2022) 118314
we performed two simulations for each temperature starting from
different random initial structures. In the following discussion, we
present averaged data of the two simulations except for atomic
structure visualization. It should be worth noting that we annealed
also at 500 K and 600 K, and found that at these temperatures the
αimj values are still gradually developing even after 600N MC tri-
als while maintaining the essential chemical order trend described
in the following discussion (see Section 3 in Supplementary Infor-
mation). Figure 2 shows that the αimj value of the first- and second-
neighbor coordinate shells, αi1j and αi2j , are well developed at lower
temperatures and gradually decrease with increasing temperature.
The first-neighbor coordinate shell demonstrates a repulsive Cr–Cr
interaction (positive αCrCr
1 ) and attractive Cr–Co and Cr–Ni inter-
actions (negative αCrCo and αCrNi
1 1 ), in agreement with the results
of DFT-based MC simulations [21,22] and experiments using X-ray
absorption fine structure techniques [20]. In contrast, Cr–Cr, Cr–Co,
and Cr–Ni pair interactions of the second-neighbor coordinate shell
show a completely opposite tendency. Notably, above 800 K the
range of chemical order is limited to mostly the second-nearest-
neighbor, that is, only so-called CSRO is formed at such high tem-
peratures. In contrast, at 700 K non-negligible finite αimj s can be
observed over a longer range more than m = 22 (r = 12 Å) show-
ing that not only CSRO but also a long-range chemical order be-
yond CSRO is formed.
By sampling local chemical arrangements within the range of
r = 12 Å at different FCC atom sites in the annealed models, such
as the fully annealed models at 700 K and partially annealed mod-
els at 600 K and 500 K (see Section 3 in Supplementary Informa-
tion), and by carefully observing these chemical arrangements, we
found that two types of superlattice chemical order were forming,
differing in orientation depending on the sampling (see Fig. 3). One
is a Cr/CoNi {100} superlattice (Fig. 4(a)) with an alternating ar-
rangement of {100} Cr-rich and Co/Ni-rich layers, as has been sug-
gested in prior experiments [26] and DFT computations [23] (see
Section 4 in Supplementary Information). The other is a Cr/CoNi
{110} superlattice (Fig. 4(b)) with an alternating arrangement of
{110} Cr-rich and Co/Ni-rich layers. The latter is newly found in
the present study and shows the same stacking pattern of Cr-rich
layers as the intermetallic compound oI6-Ni2 Cr [51] with Immm
symmetry. The formed superlattice structures provide the possi-
ble atomic pictures of the ordered structures in the order–disorder
transition found in the CrCoNi MEA [52]. For each of these two su-
perlattices, we can define a unit chemical structure consisting of
Cr-rich and Co/Ni-rich layers (see Fig. 4). Since there are six equiv-
alent {110} planes and three equivalent {100} planes in the FCC
lattice, six and three equivalent superlattices with different ori-
entations can exist, respectively. To study their energetic stabili-
ties, we used DFT to compute the energies of these unit chem-
ical structures. For the structures with the alternative arrange-
ment of Cr-rich and Co/Ni-rich layers in CrCoNi MEA, 108-atom
supercells were used for DFT computations. For each case, we pre-
J.-P. Du, P. Yu, S. Shinzato et al.
Fig. 2. Range of chemical order at various temperatures in CrCoNi medium-entropy alloy. Stacked Warren–Cowley order parameters (αimj ) between element i and element
j in the mth-neighbor coordinate shell from the element i are shown as functions of the coordinate shell radius (r) in structures annealed at various temperatures ranging
from 700 K to 1200 K and in random structure. 600N and 100N atom-swap Monte Carlo trials were performed for 700 K and 800 ∼ 1200 K simulations, respectively, where
N = 2916 atoms.
pared ten structure samples with different random atomic arrange-
ments of Co and Ni in the Co/Ni-rich layers of the superlattice
structure while the Cr-rich layers of the superlattice structures are
fully occupied by Cr. We then took the average of the energies of
the ten structure samples. The DFT computations were also per-
formed using collinear spin-polarized DFT calculations on VASP
[38–40]. The exchange correlation between electrons was treated
with the generalized gradient approximation in the Perdew-Burke-
Ernzerhof (PBE) form Perdew et al. [53]. An energy cutoff of 350 eV
was used for the plane wave basis set. A Monkhorst-Pack mesh
(4 × 4 × 4 ) was used for the Brillouin-zone integration. The ge-
ometry optimizations were performed until atomic forces were
smaller than 0.01 eV/Å. A total energy convergence criterion of
10−6 eV was used for the electronic structure optimization. Thus,
the average enthalpy difference between the two superlattices is
only 0.027 eV/atom, suggesting that the two types of superlattices
can co-exist.
3.2. Three-dimensional chemical domain formation in CrCoNi MEA
To more objectively confirm whether the Cr/CoNi {100} and
{110} superlattices were formed at the lower temperatures, we
applied a chemical structure matching analysis to the annealed
models. Thus, to determine which superlattice-chemical-order each
atom in a model more likely belongs to, we defined and used
a matching degree D for an atom site i in the model. The
matching degree D for site i in the model was defined as Di =
N
1 
Is
max{Is ,TI }
s N
δα (K )β (k) . Here Is represents the Cr/CoNi {100} or
Is K=1
{110} superlattice, TIs represents the space group operation of su-
perlattice Is , NIs represents the number of atom sites in the unit
chemical structure (Fig. 4) of superlattice Is : NCr/Ni{100} = 14 or
NCr/Ni{110} = 19. α (K ) represents element type at site K (Kth site)
4
Acta Materialia 240 (2022) 118314
in the unit chemical structure of the superlattice, and β (k ) repre-
sents element type at site k in the model, where site k is located
around the site i. Site k is the corresponding site of site K in the
unit chemical structure when the unit chemical structure superim-
poses on the model local structure centered on site i after space
group operation TIs . δ is Kronecker delta: if the element type at
site k is the same as that at site K, then δα (K )β (k ) = 1; otherwise
δα (K )β (k) = 0. If Di > 0.85, we define site i as belonging to super-
lattice Is = argmax{Is ,TI } Di , while if Di ≤ 0.85, then site i does not
s
belong to either of the superlattices. The space-group operation TIs
giving the maximum D value provides the orientation of the su-
perlattice chemical order. Performing the analysis of the matching
degree D across all atoms in each annealed model at each tem-
perature, we determined the type of superlattice by D > 0.85 and
its orientation at each atom site, and then we assigned a color to
each atom depending on the type of superlattice and orientation
(see Fig. 5(a)). At temperatures of 700 K and below, we found a
CDS consisting of many nanometer-sized SLCOD of various super-
lattice orientations, i.e., a kind of “chemical” polycrystal. The size of
1
each SLCOD was estimated by d = (n) 3 , where n is the number
of atoms in a SLCOD and  is the averaged atomic volume in the
MEA. Fig. 5(b) and (c) show the temperature dependence for the
maximum size and average size of SLCOD. The maximum size of
SLCOD at 500 ∼ 700 K was larger than 2 nm, with SLCOD still con-
tinuing to grow after 600N atom-swaps in 500 K and 600 K. The
size of SLCOD at each equilibrium state decreased with increasing
annealing temperature and eventually became CSRO at tempera-
tures above 800 K. Notably, the structures obtained by the two in-
dependent simulations at 700 K were almost fully covered by the
two chemical order superlattices. Since the recent experiment by
Zhou et al. [27] suggests a Cr/CoNi {113} chemical structure with
an alternating arrangement of {113} Cr-rich and Co/Ni-rich layers
(see Fig. 6), which is similar to the Cr/CoNi {110} but not the same,
J.-P. Du, P. Yu, S. Shinzato et al. Acta Materialia 240 (2022) 118314

Fig. 3. Observed long-range superlattice chemical order in the CrCoNi medium-entropy alloy. Local chemical structures exhibiting superlattice chemical order were sampled
from various locations within the CrCoNi medium-entropy alloy models fully annealed at 700 K and partially annealed at 600 K and 500 K.

Fig. 4. (a) Cr/CoNi {100} and (b) Cr/CoNi {110} superlattice atomic arrangements.

5
J.-P. Du, P. Yu, S. Shinzato et al. Acta Materialia 240 (2022) 118314

Fig. 5. Nanometer-sized chemical-domain structure (CDS) of superlattice-chemical-ordered domains (SLCOD) in CrCoNi medium-entropy alloy. (a) Representative distribu-
tions and (b) maximum size (dmax ) and (c) mean size (d) of Cr/CoNi {100} and Cr/CoNi {110} SLCOD in structures annealed at various temperatures ranging from 700 K to
1200 K and in random structure. 600N and 100N atom-swap Monte Carlo trials were performed for 700 K and 800 ∼ 1200 K simulations, respectively, where N = 2916
atoms. Above 800 K, the CDS was almost at equilibrium.

we applied the chemical structure matching analysis for Cr/CoNi
{113} to the equilibrium structures at different temperatures. We
found that the CSRO structures formed in the equilibrium struc-
tures at 800 K and above have subnanometer-sized Cr/CrNi {113}
chemical domain in addition to the subnanometer-sized Cr/CoNi
{100} and Cr/CoNi {110}, while the volume fraction of the Cr/CoNi
{113} domain is smaller than that of the Cr/CoNi {100} and Cr/CoNi
{110} domains (see Fig. 6 and Supplementary Fig. S13). The Cr/CoNi
{113} structure is closely related to the Cr/CoNi {110} structure, be-
cause the Cr/CoNi {110} superlattice can equivalently be viewed
as Cr/2CoNi {113}, such as an alternative arrangement of one Cr-
rich and two Co/Ni-rich {113} layers as shown in Supplementary
Fig. S14; nevertheless the Cr/CoNi {113} structure has a higher av-
erage enthalpy than Cr/CoNi {110} and Cr/CoNi {100} structures
by 0.081 and 0.054 eV/atom, respectively (see Section 5 in Sup-
plementary Information), and thus can appear only at the higher
temperatures, 800 K and above. Moreover, the Cr/CoNi {113} can
have a higher energy penalty for its further growth beyond the
CSRO size (∼ 1 nm) because the number of the unfavored Cr–Cr
nearest-neighbor pairs density rapidly increases with the increase
of domain size as seen in Supplementary Fig. S14, while Cr/CoNi
{110} and Cr/CoNi {100} do not as seen in Fig. 4. Formation kinet-
ics and size distribution of the Cr/CoNi {113} structure at the 873 K
and above is discussed in the Discussion section with a comparison
with experiments.
The above results of CDS formation at the lower temperatures
suggests that by controlling thermal processing, such as quenching
rate and annealing time and temperature, we can control the for-

6
J.-P. Du, P. Yu, S. Shinzato et al.
Fig. 6. Representative distributions of Cr/CoNi {113} chemical structure at 800 K and above in structures shown in Fig. 5. Chemical structure of Cr/CoNi {113} are shown in
the dashed frame and two equivalent {113} planes are shown as a guide to the eye.
mation of nano-structured CDS while managing the size of SLCOD,
and thus we can tailor the mechanical and functional properties of
CrCoNi MEA.
3.3. Time–Temperature–Chemical-order diagram
Concrete kinematic information regarding chemical order for-
mation is essential for tailoring the CDS via thermal process-
ing. Such information can also provide a comprehensive under-
standing of recent experiments conducted under different con-
ditions. Therefore, the vacancy jump kMC simulations based on
the ANN’s activation energy prediction scheme were performed to
give the time–temperature–αimj (T–T–αimj ) diagrams and the time–
temperature–maximum-domain-size dmax (T–T–dmax ) diagram by
applying LAMMPS [41] to a 2916-atom Cr–Co–Ni equiatomic cubic-
shaped FCC supercell model with one vacancy. For the initial
chemical structure for the T–T–αimj and the T–T–dmax computa-
tions, an annealed structure (αCrCr
1 =0.15) given by the atom-swap-
MC method at a CrCoNi melting temperature of 1530 K estimated
by the NNP was used. To avoid artificial effects of the initial struc-
ture selection, we performed three simulations at each tempera-
ture, starting from different snapshots of the atom-swap MC sim-
ulation results after well-annealing at 1530 K. The αimj and the
dmax values were then computed by taking the average of each
over the three simulations to give the averaged T–T–αimj diagrams
and T–T–dmax diagram. To draw the diagrams, the αimj –tkMC and
the dmax –tkMC relationships at various temperatures
 (T ) were fitted
to the function, Y = A(T ) − (A(T ) − B ) exp(− C (T )tkMC ), where Y
is αimj or dmax , tkMC is the time given by the kMC simulations,
both A(T ) and ln(C (T )) are quadratic or exponential functions
of T , and B is a constant. For instance, A(T ) = a0 + a1 T + a2 T 2
and A(T ) = a0 exp(−T /a1 ) + a2 for αimj and dmax , respectively, and
ln(C (T )) = c0 + c1 T + c2 T 2 for both αimj and dmax , where a0 , a1 , a2 ,
c0 , c1 , and c2 are fitting parameters as listed in Supplementary Ta-
7
Acta Materialia 240 (2022) 118314
ble S6. Next, we correlated the tkMC under the fixed vacancy con-
1
centration (cv0 = 2916 ) in kMC simulations to an annealing time (ta )
under an average vacancy concentration (cv ) in a realistic MEA sys-
tem by cv0 dtkMC = cv dta , according to the assumption that the evo-
lution time is inversely proportional to the average vacancy con-
centration. The obtained annealing time (ta ) is strongly dependent
on the cv as shown in Section 6 in Supplementary Information.
For instance, in isotherm annealing at 673 K it may require a very
long annealing time, perhaps months or years, to form an equi-
librium state under an equilibrium vacancy concentration (∼ 10−7
appm) at the annealing temperature. However, if an equilibrium
vacancy concentration at 10 0 0 K (∼ 10−3 appm) can be maintained
at the annealing temperature of 673 K, the annealing time to the
equilibrium state becomes hours, which leads to an acceleration of
the chemical order formation by ∼ 104 . The equilibrium vacancy
Eq
concentration (cv (T )) [54] in the CrCoNi MEA was estimated by
exp(n − 1 − kEvT )
Eq
cv ( T ) = B
, where n is 3 for the ternary sys-
n + exp(n − 1 − kEvT )
B
tem, and Ev = 1.78 eV is the averaged vacancy formation energy
computed using the NNP, which is in excellent agreement with
that computed using DFT, 1.82 eV [55]. It should be noted that
for simplicity we employed the average vacancy formation energy
as an approximation to estimate the vacancy concentration, while
the vacancy concentration should have a chemical order depen-
dency because the distribution of vacancy sites and vacancy en-
ergies varies with the chemical order and can somewhat affect the
vacancy concentration [56,57]. When we anneal the MEA samples
at lower temperatures immediately after cooling down from a near
melting temperature, it is reasonable to assume a higher vacancy
concentration at the beginning of the isotherm annealing than the
equilibrium vacancy concentration at the annealing temperature
because it takes longer time at such lower temperatures to release
the excess vacancies gained at the solidification process near melt-
ing temperature to approach the equilibrium concentration.
J.-P. Du, P. Yu, S. Shinzato et al. Acta Materialia 240 (2022) 118314

Fig. 7. Time evolution of chemical ordering in CrCoNi medium-entropy alloy. (a) Time–temperature–αCrCr
1
and (b) time–temperature–maximum-domain-size (T–T–dmax )
diagrams for chemical domain evolution induced by vacancy diffusion in isotherm annealing immediately after cooling down from 1500 K to each isotherm annealing
temperature in CrCoNi medium-entropy alloy.

Therefore, to take the advantage of the high vacancy concen- extremely low. While the slow furnace cooling from high temper-
tration for promoting the chemical order formation, we adopted ature as adopted by Zhang et al. [19] is an alternative heat treat-
a heat treatment process of isotherm annealing immediately af- ment process that takes advantage of the high vacancy concentra-
ter rapid cooling from the near melting temperature of 1500 K to tion formed at high temperature to promote the chemical order
the annealing temperature, so that the vacancy concentration at formation.
Eq
the beginning of the isotherm annealing is cv (T , t = 0 ) = cv (T =
1500 K ). Then, the evolution of cv (T , t ) was obtained by solving
4. Discussion
the diffusion equation for vacancies in a spherical crystalline grain
with a typical radius of 100 μm (see Section 6 in Supplementary
As discussed above, the Cr/CoNi {100} superlattice structure
Information). The time given by the kMC simulations can be re-
 ta suggested by Inoue et al. [26] and the Cr/CoNi {113} superlattice
cv ( T , t )
lated to the annealing time ta by tkMC = dt. Obtained structure suggested by Zhou et al. [27] were both found in the
0 cv0
equilibrium structures as well at different temperatures. These su-
T–T–αCrCr and T–T–dmax diagrams are shown in Fig. 7(a) and (b),
1
perlattice structures were also found in the present study as shown
respectively. The other Warren–Cowley order parameters, such as
above. Moreover, to directly compare our kMC simulation to recent
T–T–αi1j and T–T–αi2j , can be found in Supplementary Fig. S17. No-
experiments for the Cr/CoNi {113} chemical-domain size distribu-
tably these results confirm that there is a one-to-one correspon-
tion, we computed the Cr/CoNi {113} chemical-domain size distri-
dence between changes in these parameters, and thus the degree
bution by annealing at 873 K and 1273 K using the kMC method as
of chemical order can be representatively described by αCrCr 1 . The
displayed in Fig. 9. The chemical ordering at 873 K and 1273 K can
obtained diagrams are insensitive to the value of the radius of
reach an equilibrium state within 1 h (see Supplementary Fig. S20).
the spherical crystalline grain as shown in Supplementary Fig. S18.
From Fig. 9, we can find that the distribution of chemical-domain
Considering the high-temperature isotherm annealing at 1173 K
size given by the kMC simulation shows a peak at around 5 Å and
and 1273 K [19,25], the diagrams indicate that both αCrCr 1 and
average sizes of 5.3 Å and 5.4 Å at 873 K and 1273 K, receptively.
dmax can quickly reach to an equilibrium state within seconds.
The size distribution detected in our isothermal annealing sim-
In isotherm annealing at low temperatures, such as 673 K and
ulation reasonably agrees with the experiment samples prepared
573 K, a CDS with SLCOD can be formed requiring a longer an-
by the isothermal annealing and the subsequent water-quenching
nealing time, about hours. The representative evolution evident in
[27]. Here, it should be noted that the ordering kinetics around
the kMC simulations of the CDS at 1073 K and 673 K is shown
1273 K is quite rapid (see Fig. 7). Thus, the difference in anneal-
in Fig. 8. From Fig. 8, we can see that the formed CDSs have the
ing time at such high temperatures should not lead to a meaning-
same superlattice-chemical-order as obtained in the atom-swap-
fully distinct degree of chemical order. Moreover, since the degree
MC-based MC/MD hybrid simulations. At 1073 K, the maximum
of chemical order formed at such a high temperature is quite lim-
domain size dmax reaches to equilibrium within one second, while
ited (see Fig. 7), further chemical order can be expected to develop
at 673 K, dmax continues to grow to about 19 Å within 20 s.
in the subsequent quenching process. The final degree of chemi-
The choice of the heat treatment process is crucial for the de-
cal order at room temperature strongly depends on the history of
gree of the formed chemical order, since the evolution of the va-
cooling rate in the quenching process.
cancy concentration depends only on time and temperature and
The effects of chemical order on the dislocation plasticity of
cannot be controlled arbitrarily. If a MEA sample has been placed
MEAs and HEAs manifest mainly in the impedance of disloca-
at room temperature for a long enough time (∼ hours), even if it
tion nucleation and slip, leading to sluggish dislocation dynam-
has an equilibrium vacancy concentration of 400 K at the begin-
ics [9,19,28,29]. Moreover, a CDS with SLCOD may offer an addi-
ning of isotherm annealing, the annealing time for the formation
tional contribution to alloy strengthening, since the 12 110 dislo-
of CDS with SLCOD at 673 K requires years (see Supplementary
cation on the {111} plane needs to cut the {100} or {110} Cr-rich
Fig. S19), because the vacancy concentration at 673 K and below is
layers when the dislocation glides. To study these effects, we per-

8
J.-P. Du, P. Yu, S. Shinzato et al. Acta Materialia 240 (2022) 118314

Fig. 8. Representative evolution of chemical-domain structure at 1073 K and 673 K as induced by vacancy diffusion in isotherm annealing immediately after cooling down
from 1500 K to the isotherm annealing temperature of 1073 K and 673 K, respectively.

Fig. 9. Cr/CoNi {113} unit chemical structure given by the kinetic Monte Carlo (kMC) simulation. (a) and (b) show probability distribution of the chemical-domain size of
the Cr/CoNi {113} unit at 873 K and 1273 K, respectively, given by the present kMC simulation and those given by the inverse Fast Fourier transform image (IFFT) and the
dark-field (DF) images in experiment [27]. The inset tables in (a) and (b) list the averaged domain sizes (d). (c) Representative chemical-domain structure obtained by kMC
at 873 K and 1273 K in those equilibrium states after 1 h annealing (see Supplementary Fig. S20). The atoms in each CSRO Cr/CoNi {113} unit are only shown and colored
according to the orientations of the two {113} planes in the unit chemical structure.

9
J.-P. Du, P. Yu, S. Shinzato et al.
formed nanoindentation simulation and observed the delay in the
first pop-in due to the existence of CDS with chemical domain
boundary [19] (see Section 7 in Supplementary Information).
Meanwhile, It has been questioned whether the effect of chemi-
cal order on mechanical properties is negligible. We speculate that
the effect could strongly depend on the heat treatment protocol.
The CrCoNi MEA samples prepared by water quenching to room
temperature from annealed temperatures above 873 K do not show
a measurable yield strength variant [25,26]. In contrast, the sam-
ples prepared by furnace cooling from annealed temperature above
873 K to room temperature show both yield strength and hard-
ness enhancement [19]. From our T−T−chemical-order diagrams,
we can deduce that the chemical order in the samples preserved
by quick water quenching was not well-developed and thus shows
little effect on the mechanical properties. While in the samples
preserved by furnace cooling more strong chemical order should
be developed during the relatively slow furnace cooling process,
especially at temperatures below 873 K, and thus may enhance
the yield strength and the hardness. Note that a very recent ex-
periment [58] found the degree of chemical order in the furnace-
cooled CrCoNi MEA is indeed promoted compared to that in the
water-quenched one. In addition, a wavy dislocation slip motion
was found in the water-quenched one, while the planar dislocation
slip motion was found in the furnace-cooled one. However, a clear
difference in the yield strengths could not be found [58]. Possibly,
the degree of chemical order has not yet been higher enough to
cause an increase in yield strength. Another possible reason is that
planar slip implies the presence of a diffuse antiphase boundary;
although the dislocation slip through the CSRO structure generates
resistance to the dislocation due to breaking the favorable solute-
solute bonds [59], the diffuse antiphase boundary reduces the re-
sistance to the dislocation in it due to the solute–dislocation inter-
action [60,61], and these two effects on the yield strength cancel
each other out.
The T−T−chemical-order diagrams in the present study provide
the information to design heat treatment protocols for promoting
the chemical order in the CrCoNi MEA. For example, we can per-
form rapid cooling from higher temperature (like 1500 K) to 673 K
with a high cooling rate to maintain the high vacancy concentra-
tion, followed by an isothermal annealing at 673 K for like a couple
of hours, and then a furnace cooling to room temperature. Such
heat treatment protocol may lead to a higher degree of chemical
order and more apparent effects on the strength.
5. Conclusion
In summary, we used a newly developed neural network po-
tential based on DFT to find novel CDS structure at temperatures
below 800 K in CrCoNi MEA. The CDS consists of two types of su-
perlattices, such as Cr/CoNi {100} and Cr/CoNi {110}, with different
orientations, while at temperatures 800 K and above CSRO with
different local structures, such as Cr/CoNi {100}, Cr/CoNi {110}, and
Cr/CoNi {113}, appeared. Moreover, we used a newly developed
fast kMC computation technique based on an ANN and success-
fully drew time–temperature–chemical-order diagrams that predict
the annealing-temperature-dependent time necessary for chemical
order formation. Such non-empirical prediction of CDS and its for-
mation kinetics opens new doors for the rigorous management of
chemical order and thus mechanical and functional properties of
multicomponent alloys.
Data Availability
The data used in this work are available from the authors upon
request.
10
Acta Materialia 240 (2022) 118314
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
CRediT authorship contribution statement
Jun-Ping Du: Conceptualization, Formal analysis, Methodology,
Writing – original draft, Writing – review & editing. Peijun Yu:
Methodology. Shuhei Shinzato: Methodology, Writing – review
& editing. Fan-Shun Meng: Methodology. Yuji Sato: Methodol-
ogy. Yangen Li: Methodology. Yiwen Fan: Methodology. Shigenobu
Ogata: Conceptualization, Formal analysis, Writing – original draft,
Writing – review & editing.
Acknowledgments
This work was supported by the Element Strategy Initia-
tive for Structural Materials (ESISM) of MEXT, Grant Number JP-
MXP01121010 0 0. P.Y. and S.O. acknowledge the support by JSPS
KAKENHI Grant No. JP18H05453. S.O. acknowledges the support by
JSPS KAKENHI Grant Nos. JP17H01238 and JP17K18827. The calcula-
tions were performed on the large-scale computer systems at the
Cybermedia Center, Osaka University, and the Large-scale parallel
computing server at the Center for Computational Materials Sci-
ence, Institute for Materials Research, Tohoku University.
Supplementary material
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.actamat.2022.118314.
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