Corrosion Science 209 (2022) 110761

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Enhanced corrosion resistance of CoCrFeMnNi high entropy alloy using

heterogeneous structure design
Jiapan Wang a, Zhe Zhang a, b, c, *, Hailong Dai a, Hiroshi Fujiwara d, Xu Chen a, b, c, Kei Ameyama d
a
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
b
Tianjin Key Laboratory of Chemical Process Safety and Equipment Technology, Tianjin 300350, China
c
Zhejiang Institute of Tianjin University, Ningbo, Zhejiang 315201, China
d
Department of Mechanical Engineering, Faculty of Science and Engineering, Ritsumeikan University, Shiga 525-8577, Japan

A R T I C L E I N F O A B S T R A C T

Keywords: High entropy alloys (HEAs) with heterogeneous grain structure exhibit an unprecedented combination of high
High entropy alloy strength and high ductility. Therefore, it is imperative to clarify corrosion behavior for various applications. In
Heterogeneous grain structure the present work, the corrosion behavior of harmonic structured (HS) CoCrFeMnNi HEAs with different shell
Electrochemical testing
fractions was investigated. The inhomogeneity of corrosion in the HS CoCrFeMnNi HEAs was revealed. The
Corrosion
Passive film
peculiar core-shell network structure is beneficial to the corrosion resistance compared with the conventional
coarse-grained (CG) or ultrafine-grained (UFG) structure. The shell fraction of approximately 30% is the opti­
mized design for corrosion resistance.

1. Introduction In recent years, improving the synergy of strength-ductility in

High entropy alloys (HEAs) exhibit unprecedented mechanical
properties and have great potential to be used as structural materials [1,
2]. Therefore, it is of great important to clarify the corrosion behavior of
HEAs. Extensive researches have been carried out on the corrosion
behavior of HEAs. It was found that the pitting resistance of HEAs in
aqueous solution containing chlorine was better than that of traditional
alloys [3]. CoCrFeMnNi HEAs showed excellent fracture toughness and
good low temperature mechanical properties [4]. Meanwhile, they
possessed a higher passive current density than 316 L stainless steel,
4130 alloy and 800 H high-nickel alloys [5,6]. It is known that the
corrosion resistance depends on alloying element, processing method,
microstructure and so on. The pitting resistance and passivation ability
of CoCrFeMnNi HEA improved with increasing addition of chromium
content, which was related to the enrichment of chromium in passive
film [7–9]. Moreover, the CoCrFeMnNi HEA strengthened by carbon
solution also showed excellent pitting resistance [10,11]. Al0.1CoCrFeNi
HEA demonstrated a better resistance to general and pitting corrosion
than 304 stainless steel [12]. However, the high content of manganese
oxide in passive film was harmful to the corrosion resistance of HEAs.
The manganese inhibited the passivation process and increased the
chemical dissolution rate of passive film [13].
various structural materials using heterogeneous grain structure design
has attracted great attention [14,15]. In order to prevent rapid deteri­
oration of ductility in grain-refined materials, several heterogeneous
structure topologies have been proposed, such as gradient structure
[16], heterogeneous lamellar structure [17], laminate structure [18]
and harmonic structure (HS) [19], etc. The heterogeneous structure
topology can effectively overcome the strength-ductility trade-off in
HEAs [20,21]. Compared with the conventional coarse-grained (CG) or
ultrafine-grained (UFG) materials, the heterogeneous structured mate­
rials usually have inhomogeneous grain distribution. Therefore, it is
necessary to reveal the inhomogeneity of corrosion performance in the
heterogeneous structured HEAs.
The effects of grain size on corrosion behavior have been investi­
gated in the past decades. The high energy of grain boundary and the
segregation of alloying elements can promote the chemical activity,
which increases the dissolution rate of UFG materials. It was shown that
the UFG CoCrFeMnNi HEA (0.689 µm) had worse corrosion resistance
than CG CoCrFeMnNi HEA (48 µm). The abundant UFG boundaries
promoted the occurrence of the galvanically induced intergranular
corrosion [22,23]. However, the refined grain structure can provide
more nucleation sites and enhance diffusion rate of charged species
across the passive film, resulting in the superior passivation ability.

* Corresponding author at: School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China.
E-mail address: zhe.zhang@tju.edu.cn (Z. Zhang).

https://doi.org/10.1016/j.corsci.2022.110761
Received 30 July 2022; Received in revised form 4 October 2022; Accepted 18 October 2022
Available online 21 October 2022
0010-938X/© 2022 Elsevier Ltd. All rights reserved.
J. Wang et al.
Thus, the passivation behavior of 316 L austenitic stainless steels with
nanograins and nano-twins was improved [24]. Additionally, the
re-passive ability and pitting resistance of UFG 316 L steels (0.75 µm)
were also better than those of CG 316 L steels (10 µm) [25].
In recent years, the researches gradually shift from corrosion
behavior of CG or UFG materials to that of heterogeneous structured
materials. Since UFG structure has faster passivation kinetics than CG
structure, the corrosion degree of heterogeneous materials is highly
affected by the grain size distribution [26]. Bimodal structure refers to a
heterogeneous structure with bimodal grain size distribution. The
bimodal structured 316 L steel showed much higher pitting resistance
than CG 316 L steel. The UFG structure can restrain the stable propa­
gation of pits in CG structure, resulting in the enhanced pitting resis­
tance [27,28]. The intergranular corrosion depth in aluminum alloy
decreased with increasing fraction of ultrafine grains [29]. Moreover,
the bimodal structured Al6063 alloy containing 15 vol% CG structure
had the best corrosion resistance, which was attributed to an optimal
cathode-anode surface area ratio and an effective self-anodic protection
mechanism [30]. In the gradient nanostructured 316 L steel, grain size
gradient distribution and the rapid diffusion of elements increased the
thickness and density of passive film [31,32].
Harmonic structure (HS) is a typical heterogeneous structure topol­
ogy. Compared with bimodal structure with irregular CG and UFG dis­
tribution, HS is composed of coarse grains (“core”) and a periodic three-
dimensional network of ultrafine grains (“shell”). The previous results
showed that the harmonic structure can improve the synergy of strength
and ductility in various materials [19,33,34]. The HS CoCrFeMnNi HEAs
were prepared and showed not only good strength-ductility synergy but
also good fatigue resistance [35]. Until now, the preliminary in­
vestigations on the corrosion resistance of the HS materials have been
carried out. Prabhat et al. [36,37] investigated the effect of harmonic
structure design on corrosion resistance of stainless steels. The results
showed that the pitting resistance of the HS 304 L steels and 316 L steels
was better than that of the conventional CG steels. The network struc­
tured ultrafine grains and high grain boundary fraction promoted the
excellent passivation performance. In addition, due to the unstable
passive film in UFG structure, the shell region of the HS steels was
corroded more severely than the core region.
As mentioned above, compared with mechanical properties and
deformation mechanism of the heterogeneous structured materials, less
attention has been paid to corrosion behavior. Although preliminary
achievements have been made in corrosion performance of the hetero­
geneous structured steels and aluminum alloys, the understanding of
inhomogeneity of corrosion performance in the heterogeneous struc­
tured HEAs is still inadequate. It is necessary to clarify the corrosion
behavior of the heterogeneous structured material for various applica­
tions. Therefore, in this study, a series of HS CoCrFeMnNi HEAs with
different shell fractions are prepared. The corrosion behavior is studied
by cyclic polarization (CP) technique and electrochemical impedance
spectroscopy (EIS). Moreover, the passive film characteristics are also
investigated. Finally, the effects of the peculiar UFG network structure
and its volume fraction on electrochemical corrosion behavior of the HS
CoCrFeMnNi HEAs are clarified.
2. Experimental procedures
2.1. Materials preparation
Commercial gas-atomized CoCrFeMnNi HEA powders with a diam­
eter of 45–105 µm were used, and the chemical composition is shown in
Table 1
Chemical composition of CoCrFeMnNi HEA powders.
Element Co Cr Mn Fe Ni N O
Content (at%) 20.60 19.00 20.47 19.53 20.40 0.0074 0.0359
2
Corrosion Science 209 (2022) 110761
Table 1. The initial powders were milled by a planetary ball milling for
50, 75 and 100 h respectively to prepare samples with different shell
fractions. The mass ratio of ball to powder was 10:1, and the milling
speed was 200 rpm. The mechanical milling (MM) process was filled
with argon atmosphere to prevent oxidation. After mechanical milling,
the initial powders and milled powders were sintered by spark plasma
sintering (SPS) at 950 ℃ and 50 MPa for 10 min. Due to the low density
at the edge of the sintered compacts, the corrosion property was studied
in the center of the sintered compacts in this paper. The samples with the
dimensions of φ15 × 2 mm were machined from the center of the sin­
tered compacts. Before the tests, the samples were ground sequentially
by 400–2000 grit SiC papers and finally polished by 0.1 µm diamond
polishing paste. Then, the samples were cleaned by deionizer water and
alcohol.
2.2. Electrochemical test
Electrochemical tests were carried out on an electrochemical work­
station (CS 350 H, CorrTest) using a conventional three-electrode sys­
tem, wherein a platinum plate was used as the counter electrode, a
saturated Ag/AgCl electrode was used as the reference electrode, and
the sample was used as the working electrode. The tested area of the
sample was approximately 1.0 × 1.0 cm2. 3.5 wt% NaCl solution was
used as the corrosion medium. Open circuit potential (OCP) was main­
tained for 4 h to obtain a stable value. Electrochemical impedance
spectroscopy (EIS) was recorded over a scan frequency ranging from 105
Hz to 10− 2 Hz with an amplitude of 10 mV at OCP. The EIS data were
fitted using ZsimpWin software and equivalent circuit model. Cyclic
polarization test was carried out with a scanning rate of 0.1667 mV/s
from − 0.7 VAg/AgCl to 0.7 VAg/AgCl relative to the OCP. Then, the voltage
was reversed back to the starting potential. All tests were performed at
room temperature. Each condition was repeated three times to ensure
repeatability of the results. To study the morphology of pitting corro­
sion, 72-hour immersion test in 0.5 M hydrochloric acid was also
conducted.
2.3. Characterization of the passive film
To investigate the passive films on the surface of samples with
different microstructures, the samples were passivated at − 0.05 VAg/
AgCl for 0.5 h in 3.5 wt% NaCl solution. The potential was selected ac­
cording to the cyclic polarization curves. Mott-Schottky curves were
scanned from − 0.85 VAg/AgCl to 0.35 VAg/AgCl with 20 mV/step at a
frequency of 1000 Hz, and the change of potential in the capacitance
measurement process would not affect the defect structure and thickness
of the passive film. In order to analyze the chemical compositions of
passive films, the samples were immersed in 3.5 wt% NaCl solution for 4
h, and then analyzed by X-ray photoelectron spectroscopy (XPS, Thermo
Scientific Escalab 250Xi). Avantage software was used to analyze the
XPS data, and all peaks were calibrated using standard C1 s peak at
284.8 eV.
2.4. Microstructure and pitting morphology observations
The microstructures of the samples were observed using an optical
microscope (OM, Keyence VHX-900) and a scanning electron micro­
scope (SEM, FEI Apreo S Lo Vac) equipped with an electron backscat­
tering diffraction (EBSD, EDAX) system. The UFG area fraction was
defined as shell fraction, which was calculated from OM images. The
samples for EBSD analysis were prepared by electro-polishing using a
mixture solution of 10 vol% perchloric acid and ethanol solution at 20 V.
SEM was used to investigate the surface morphology of samples.
Moreover, the samples were encapsulated with epoxy resin and the
characteristics of pitting corrosion in the cross section of the samples
were observed by OM. The Volta potential distribution of the samples
was mapped with scanning Kelvin probe force microscopy (SKPFM,
J. Wang et al. Corrosion Science 209 (2022) 110761

Bruker Dimension icon) and the scanning range was 20.0 × 20.0 µm.

3. Results

3.1. Microstructure characterization

Fig. 1 shows the microstructure of the sintered CoCrFeMnNi HEA

samples. As shown in Fig. 1(a1,2), the sample sintered from initial
powders has an equiaxed CG structure with an average grain size of
10.98 µm. By contrast, Fig. 1(b1-d1, b2-d2) show that a bimodal grain size
distribution is formed in the samples prepared from the milled powders,
wherein the dark area is the UFG region and the bright area is the CG
region. It is noted that the CG structure (“core”) is enclosed in a
continuously connected UFG network structure (“shell”), which in­
dicates that the harmonic structure is produced. Moreover, as indicated Fig. 2. Grain size and shell fraction in the sintered CoCrFeMnNi HEAs with
different mechanical milling (MM) times.
from Fig. 1(a3-d3), the Kernel average misorientation (KAM) values in
the core and shell regions are relatively low, indicating that the residual
stress in the sintered compacts is low. Fig. 2 shows the effects of milling milled for 50 h, 75 h and 100 h are denoted as Sf= 0%, Sf= 22.4%, Sf=
time on shell area fraction (Sf) and grain size in the sintered samples. 31.7% and Sf= 40.5%, respectively.
Obviously, the shell fraction of HS samples increases with an increase of
milling time, and the values are approximately 22.4%, 31.7% and 3.2. Electrochemical corrosion behavior in the 3.5 wt% NaCl solution
40.5%, respectively. By contrast, the grain size decreased slightly with
increasing mill time. The average grain sizes are 0.96–1.47 µm in the 3.2.1. Open circuit potential results
shell region and 9.26–11.06 µm in the core region, respectively. The electrochemical corrosion behavior of the CoCrFeMnNi HEAs
Therefore, the samples sintered from initial powders and the powders with different microstructures were investigated in 3.5 wt% NaCl

Fig. 1. Microstructure of the sintered CoCrFeMnNi HEAs: (a1–3) CG, Sf= 0%; (b1–3) HS, Sf= 22.4%; (c1–3) HS, Sf= 31.7%; (d1–3) HS, Sf= 40.5%. (a1-d1) OM images,
EBSD (a2-d2) IPF and (a3-d3) KAM images overlaid with high-angle boundaries. CG – coarse-grained samples, HS – harmonic structured samples, Sf - shell
area fraction.

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J. Wang et al. Corrosion Science 209 (2022) 110761

solution at room temperature. Fig. 3 shows the open circuit potential

curves obtained by immersing in 3.5 wt% NaCl solution for 4 h. At the
initial stage of immersion, the potentials of all samples increase rapidly,
indicating that protective oxide films are spontaneously formed. The
OCPs fluctuate slightly with an increase of immersion time, which is
attributed to the breakdown and repassivation of the oxide films [30,
38]. The OCP curves of the HS samples fluctuate more frequently than
that of the CG sample, implying that the inhomogeneous microstructure
leads to the inhomogeneity of oxide films. As shown in Fig. 3, the OCPs
tend to be stable after immersion for 3 h, indicating that the corrosion
reaches a stable state. It is known that the increased OCP suggests the
formation of passive film with good protective properties [39]. The
OCPs of the HS CoCrFeMnNi HEAs are higher than that of the CG
CoCrFeMnNi HEA, indicating that HS samples have more stable passive
films than CG sample. Moreover, the HS sample with the shell fraction of
31.7% has the highest OCP after stabilization, indicating that it has the
Fig. 4. Cyclic polarization curves of the CoCrFeMnNi HEAs with different shell
better thermodynamic stability and corrosion resistance. fractions in 3.5 wt% NaCl solution at room temperature.

3.2.2. Cyclic polarization results

Fig. 4 shows the cyclic polarization curves of the CoCrFeMnNi HEAs Table 2
with different shell fractions in 3.5 wt% NaCl solution. It is seen that the Electrochemical test results of the CoCrFeMnNi HEAs with different shell frac­
cathodic branches of all samples almost coincide, indicating that the tions in 3.5 wt% NaCl solution.
shell fraction has little influence on cathode reaction. In the forward Shell Ecorr Icorr Epit Ipass Erp
scanning process, the current density is basically unchanged with the fraction (VAg/AgCl) (μA/cm2) (VAg/AgCl) (μA/cm2) (VAg/AgCl)
increase of the potential, which indicates that the spontaneous passiv­ (%)
ation occurs. Moreover, it is seen that the current densities of all samples 0 -0.18 0.81 -0.02 3.89 -0.29
fluctuate slightly, which is related to the metastable pitting on the sur­ ± 0.02 ± 0.14 ± 0.01 ± 1.98 ± 0.01
faces. When the applied potential exceeds the pitting potential (Epit), the 22.4 -0.20 0.27 0.05 0.69 -0.32
± 0.02 ± 0.05 ± 0.01 ± 0.13 ± 0.01
current densities increase suddenly, and then the metastable pitting 31.7 -0.17 0.22 0.10 0.56 -0.30
changes to stable pitting. In the reverse scanning process, positive hys­ ± 0.01 ± 0.01 ± 0.01 ± 0.07 ± 0.01
teresis loops appear on the cyclic polarization curves, and the pits on the 40.5 -0.18 0.24 0.07 0.61 -0.32
surface of the samples continue to expand without new pits formation. ± 0.02 ± 0.01 ± 0.04 ± 0.11 ± 0.02
The potential corresponding to the intersection of the reverse scanning
curve and the forward scanning curve is the repassivation potential sample is the highest, indicating that its corrosion rate is the fastest. The
(Erp). After that, the pitting self-repair occurs. Icorr of the HS sample with the shell fraction of 31.7% is the lowest,
Table 2 shows the electrochemical parameters of the CoCrFeMnNi indicating that its corrosion resistance is much better. Moreover, it is
HEAs obtained from the cyclic polarization curves. The corrosion po­ known that the higher Epit means better pitting resistance of passive
tential (Ecorr), corrosion current density (Icorr) obtained by Tafel slope film. The Epit of the HS samples are higher than that of CG sample, which
extrapolation method. The Ecorr and Erp of the samples are approxi­ means that the passive films of HS samples have stronger resistance to
mately equal. According to the literature [40,41], the annual average chloride attack. Improved passivation behavior was also reported in the
corrosion rate of metal materials was proportional to the corrosion HS stainless steels [36,37]. In addition, the Epit of the HS sample with
current density (see Eq. (1)): Sf= 31.7% is higher than that of the samples with Sf= 22.4% and
MIcorr Sf= 40.5%, which indicates that the influence of shell fraction on
v= (1)
nF corrosion resistance is complicated. The current density corresponding
to − 0.05 VAg/AgCl is selected as the passivation current density (Ipass),
Where, v is the annual average corrosion rate, M is the molar mass of the which can be used to represent the dissolution rate of the passive film
metal, Icorr is the corrosion current density, n is the metal valence state, during the passivation process. Obviously, the HS sample with
and F is the Faraday constant. As shown in Table 2, the Icorr of the CG Sf= 31.7% has the lowest Ipass, and the passive film is more stable.
Ecorr: corrosion potential, Icorr: corrosion current density, Epit: pitting
potential, Ipass: passivation current density, Erp: repassivation potential.

3.2.3. Electrochemical impedance spectroscopy results

Fig. 3. Open-circuit potential curves of the CoCrFeMnNi HEAs with different
shell fractions in 3.5 wt% NaCl solution at room temperature.
The corrosion behavior of metals is also closely related to the sta­
bility of passive film, so the characteristics of passive film are analyzed
by EIS. Fig. 5 shows the EIS results of the CoCrFeMnNi HEAs with
different microstructures at OCP. It can be seen from Fig. 5(a) that all
samples show a single capacitive semicircle, indicating that the corro­
sion on the surfaces is controlled by the charge transfer process of
interfacial electrochemical reaction. However, the radius of capacitive
semicircle of the samples with different shell fractions varies greatly.
Namely, it increases with increasing shell fraction firstly, while it de­
creases when the shell fraction exceeds 31.7%. The radius of semicircle
means the resistance of charge transfer, reflecting the difference in
corrosion resistance of the CoCrFeMnNi HEAs with different micro­
structures. Thus, the HS sample with the shell fraction of 31.7% has

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J. Wang et al. Corrosion Science 209 (2022) 110761

Fig. 5. Nyquist (a) and Bode plots (b) of the CoCrFeMnNi HEAs with different microstructures in 3.5 wt% NaCl solution under OCP condition. The equivalent
electron circuit (EEC) model (c) for fitting the EIS experimental data. Solid lines refer to the fitting curves.

better corrosion resistance compared with other samples. From Fig. 5
(b), the impedance modulus of the HS sample with the shell fraction of
31.7% is the largest in the low frequency region, indicating that this
sample has superior charge transfer resistance.
The equivalent electron circuit (EEC) model has been used to study
the passivation behavior and corrosion process of CoCrFeMnNi HEAs
[42–44]. As shown in Fig. 5(c), the equivalent circuit model is used to fit
impedance spectra obtained under OCP condition, and the obtained
parameters of the model are shown in Table 3. Rs is the solution resis­
tance between the working electrode and the reference electrode, Rct is
the charge transfer resistance, and constant phase element (CPE) is the
double layer capacitance between the working electrode and the solu­
tion interface. Considering the dispersion effect caused by the in­
homogeneity, porosity and roughness of the passive film on the surface
of samples, the capacitance is usually a non-ideal capacitance, so the
CPE is used to replace the pure capacitance element in the EEC model
[45]. The impedance of CPE (ZCPE ) can be calculated by Eq. (2):
1 boundary density, local dissolution of the HS samples occurs preferen­
ZCPE =
Q(ωi)n
Where, Q is the admittance of CPE; ω is the angular frequency; i is the
imaginary number (i2 = 1); n is the exponent used to measure surface
inhomogeneity (− 1 ≤ n ≤ 1). n = 1, 0 and − 1 mean a pure capacitor, a
pure resistor and an inductor, respectively [46,47]. As shown in Table 3,
both CG and HS samples have relatively low Σχ 2 values (< 5 ×10− 3),
indicating that the good fitting quality of the used model. All the values
of n are less than 1, suggesting that defective passive films are formed on
the surface of the samples [10]. Rct reflects the corrosion rate of metal in
corrosion solution. The larger Rct means the slower corrosion rate [39].
Table 3
Equivalent electron circuit parameters for impedance spectra of the CoCr­
FeMnNi HEAs with different microstructures in 3.5 wt% NaCl solution.
Shell Rs Q n Rct Σχ 2
fraction (%) (Ω⋅cm2) (Ω− 1⋅cm− 2⋅sn) (Ω⋅cm2)
Obviously, the Rct reaches highest when the shell fraction is 31.7%. All
of the obtained results prove that the passive film formed on the surface
of the HS CoCrFeMnNi HEA with the shell fraction of 31.7% is more
stable than that of other samples, resulting in much better resistance to
pitting. These results are also consistent with the results of CP.
3.3. Corrosion morphology
Fig. 6 shows the corrosion morphology of the CoCrFeMnNi HEAs
with different microstructures after immersion in 0.5 M HCl solution for
72 h. The surface of the CG sample corrodes severely, which indicates
the poor resistance to chloride ion corrosion. By contrast, the corrosion
resistance of HS samples is much better than that of CG sample. The
corrosion occurs preferentially in the shell region. It is known that the
grain boundaries possess high energy, resulting in high electrochemical
activity. Moreover, the elements are easy to diffuse through grain
boundary, leading to the preferential corrosion. Due to the high grain
(2)
tially along the shell region with UFG structure. To further analyze the
pitting depth of the CoCrFeMnNi HEAs with different microstructures,
the morphologies of pits on the cross-section are shown in Fig. 6(a2-d2).
Apparently, the CG sample has the deepest pits, which means poor
resistance to chloride ion corrosion. It is noted that the HS sample with
the shell fraction of 31.7% has the lower pitting depth than the other
samples. In addition, the Volta potential map of the HS CoCrFeMnNi
HEA with the shell fraction of 40.5% obtained using SKPFM is shown in
Fig. 7. The profile along the marked line demonstrates that the differ­
ence in the Volta potential between the core and shell is about
32.32 mV. Previous studies have reported that the more positive Volta
potential means the lower electrochemical activity of the metal [38,
48–50]. Therefore, the shell region is more sensitive to corrosion than
the core region.
3.4. Analysis of the passive film

0 27.64 2.50 × 10− 5

0.93 1.01 × 105 1.99 × 10− 3 3.4.1. Mott-Schottky analysis
22.4 23.66 2.87 × 10− 5
0.91 1.03 × 105 1.87 × 10− 3
Based on the potential range of the passivation region on the cyclic
5
31.7 27.06 2.58 × 10− 0.91 3.03 × 105 2.31 × 10− 3
polarization curves, − 0.05 VAg/AgCl was chosen to polarize for 0.5 h.
5
40.5 23.71 2.80 × 10− 0.91 2.52 × 105 4.28 × 10− 3
Fig. 8 shows the variation of current density during the potentiostatic

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J. Wang et al. Corrosion Science 209 (2022) 110761

Fig. 6. Surface (a1-d1) and cross-section (a2-d2) morphologies of the corroded specimens after immersion in 0.5 M HCl solution for 72 h, (a1,2) CG, Sf= 0%; (b1,2) HS,
Sf= 22.4%; (c1,2) HS, Sf= 31.7%; (d1,2) HS, Sf= 40.5%.

Fig. 7. SKPFM results of HS CoCrFeMnNi HEA with the shell fraction of 40.5%, (a) topography map; (b) Volta potential map; (c) Volta potential profile along the
marked line AB.

exhibits a relatively low current density. Moreover, the current density

remains at a stable value in the continuous passivation process, indi­
cating the superior stability of the passive film on the sample surface.
The corrosion resistance of passive film is related to its electronic
properties. Mott-Schottky theory has been used to analyze the carrier
density and semiconductor properties of passive film [51,52]. The
capacitance of space charge layer and applied potential should satisfy
the following relationship:
( )
1 1 kT
= E − E fb − for n − typesemiconductor (3)
C2 εε0 eNd e
( )
1 1 kT
= − E − E fb − for p − typesemiconductor (4)
C2 εε0 eNa e
Fig. 8. The current density of the CoCrFeMnNi HEAs with different micro­
structures under potentiostatic polarization at − 0.05 VAg/AgCl for 0.5 h in where, ε is the dielectric constant of passive film (ε = 12 from Ref. [10,
3.5 wt% NaCl solution. ε0] is the vacuum permittivity (8.85 ×10− 12 F⋅m− 1), Nd and Na are the
donor and acceptor density, respectively, K is the Boltzmann constant, T
polarization of the CoCrFeMnNi HEAs with different microstructures. It is the absolute temperature, E is the applied potential, Efb is the flat band
is seen that the current density of all samples decreases rapidly at the potential, e is the electron charge (1.60 ×10− 19 C).
beginning of the passivation process, indicating that the protective Fig. 9 shows the Mott-Schottky curves of the CoCrFeMnNi HEAs with
passive films are formed quickly. As the time increases, the current different microstructures measured in 3.5 wt% NaCl solution. The type
density of the CG sample increases gradually, indicating that the passive of semiconductor can be determined by the positive and negative slope
film is destroyed and the migration rate of metal ions to the passive film- of the linear line. A line with good linearity is selected from the Mott-
solution interface is accelerated. By contrast, the current density of the Schottky curves for fitting (see the solid lines in Fig. 9(a)), and then
HS samples fluctuates, and it is lower than that of CG sample, which the value of Nd is calculated by Eq. (3). Obviously, all passive films on
means that the continuous recovery of the passive film appears in the HS the surface of samples show n-type semiconductor characteristics. It is
samples. In particular, the HS sample with the shell fraction of 31.7% seen from Fig. 9(b) that the values of Nd are nearly 1021 cm− 3. It means

6
J. Wang et al.
Fig. 9. Mott–Schottky plots (a) and the donor densities (b) of the passive films formed on the CoCrFeMnNi HEAs with different microstructures at − 0.05 VAg/AgCl in
3.5 wt% NaCl solution. Solid lines refer to the fitting curves.
that the passive films formed on the sample surface are in a highly
disordered state, which is consistent with previous results of CoCr­
FeMnNi HEAs [10,23,52,53]. According to the point defect model pro­
posed by Macdonald et al. [54] (Fig. 10), oxygen vacancy and cation
interstitial are the main defects related to n-type semiconductor, while
cation vacancy gives p-type characteristic to passive film [55]. The ox­
ygen vacancy and cation interstitial are formed at the metal matrix/film
interface and consumed at the film/solution interface, while cation va­
cancy is opposite. In this study, the passive films of samples contain a
large number of n-type point defects, which are conducive to the
migration of metal ions in the corrosion process. According to reaction
(3), oxygen vacancies accumulate on the metal matrix/film interface,
and chloride ions in the solution can be adsorbed on the oxygen va­
cancies. Therefore, Nd can be used to measure the affinity of the passive
film for chloride ions and the pitting nucleation ability [55,56]. Nd is the
lowest in the passive film of the HS CoCrFeMnNi HEA with the shell
fraction of 31.7%, indicating that it is not easily damaged by chloride
ions and has good resistance to pitting. It is also seen from Fig. 4 that the
pitting potential of the HS CoCrFeMnNi HEA with the shell fraction of
31.7% is higher than that of other samples. However, the Nd increases
gradually when the shell fraction increases to 40.5%, implying that the
corrosion resistance tends to deteriorate with continuously increasing
shell fraction.
3.4.2. XPS analysis of passive films
Fig. 11 shows the XPS results of the passive films formed on the
surface of the CoCrFeMnNi HEAs with different microstructures
immersed in 3.5 wt% NaCl solution for 4 h. Fig. 11(a1-d1) show that the
spectra of Co 2p3/2, the appearance of Co2+ satellite peaks (786.3 eV) is
related to monopole charge-transfer transitions [55,57]. Fig. 11(a2-d2)
Fig. 10. Schematic representation of the physicochemical reactions taking place within the passive films of the HEAs, based on the PDM. m is metal atom; MM is
metal cation in a metal site; Vm is vacancy in metal site; Vx+
M is cation vacancy; VO is oxygen vacancy; Mi is cation interstitial; M
anion in an anion site.
Corrosion Science 209 (2022) 110761
show the spectra of Cr 2p3/2, which is divided into three peaks of
metallic Cr0 (573.8 eV), metal oxide Cr3+ ox (575.8 eV) and hydroxide
Cr3+
hy (577.4 eV). The increase of chromium content in passive film is
beneficial to improve the pitting corrosion resistance. Three peaks of Fe0
in metal state (706.6 eV), Fe3+ 3+
ox in oxide (710.1 eV) and Fehy in hy­
droxide (711.9 eV) are observed in Fig. 11(a3-d3). Iron oxide species
prevail in the passive film of the HS CoCrFeMnNi HEA with the shell
fraction of 31.7%, while iron hydroxide species predominate in the
passive films of the other samples. Fig. 11(a4-d4) show the Mn 2p3/2
spectra of the CoCrFeMnNi HEAs with different shell fractions. Three
peaks, i.e., metallic Mn0 (638.3 eV), metal oxide Mn2+ ox (640.2 eV) and
Mn4+ox (641.8 eV), can be observed. The presence of manganese signifi­
cantly reduces the stability of the passive film [13]. Unstable manganese
oxide forms due to its low passivation coefficient, which reduces the
resistance of steel to electrochemical corrosion [58]. Therefore, the high
content of manganese oxide in the passive film is harmful to the corro­
sion resistance of HEAs. Fig. 11(a5-d5) show the Ni 2p3/2 spectra of the
HEAs with different shell fractions. Three peaks, i.e., metallic Ni0
(852.3 eV), oxide Ni2+ 2+
ox (855.3 eV) and hydroxide Nihy (856.2 eV), can
be observed. Nickel is less susceptible to oxidation than iron and chro­
mium, so the metallic nickel appears [59]. In addition, the detected
depth of XPS is approximately 10 nm and the passive film on the sample
surface is generally few nanometers, so the metallic peaks appear. The
lower metallic peak for the HS sample with the shell fraction of 31.7% is
attributed to the formation of a thicker passive film. Fig. 11(a6-d6) show
the spectra of O 1 s, which is divided into O2- (529.6 eV), OH- (531.2 eV)
and H2O (532.2 eV). O2- and OH- correspond to the oxides and hy­
droxides in the passive film and H2O corresponds to the bound water in
the passive film. The bound water can act as an efficient species to
capture dissolved metal ions, forming a new film that resists further
’’ x+
δ+
is cation in solution; OO is oxygen
7
J. Wang et al. Corrosion Science 209 (2022) 110761

Fig. 11. High resolution XPS spectra of the passive films formed on the CoCrFeMnNi HEAs with different microstructures after immersion for 4 h in 3.5 wt% NaCl
solution. (a1)-(d1) Co 2p3/2, (a2)-(d2) Cr 2p3/2, (a3)-(d3) Fe 2p3/2, (a4)-(d4) Mn 2p3/2, (a5)-(d5) Ni 2p3/2 and (a6)-(d6) O 1 s.

8
J. Wang et al.
corrosion [60,61].
The fractions of cationic and metallic species of Cr, Fe, Ni, Mn and Co
in the passive films of the HS CoCrFeMnNi HEAs with different shell
fractions are shown in Fig. 12. Chromium is one of the main elements in
the high entropy alloy system. The existence of chromium is beneficial to
the improvement of the corrosion resistance of materials, and chromium
oxide/hydroxide plays the most important role in improving the
corrosion resistance of HEAs. It is known that the presence of Cr3+ ox can
improve the corrosion resistance of passive films, while Cr3+ hy has a
negative effect on compactness of passive films [62,63]. As shown in
Fig. 12(b), the Cr3+ 3+
ox /Cr hy ratio of the HS sample with the shell fraction
of 31.7% is the largest. In addition, except for the HS sample with the
shell fraction of 31.7%, the manganese oxide content in passive films of
the other samples is high (Fig. 12(a)), which also leads to the reduction
of resistance to chloride ion attack. Therefore, the passive film of the HS
sample with the shell fraction of 31.7% has a higher Cr3+ 3+
ox /Crhy ratio and
a lower content of manganese oxide, resulting in a better protective
effect on the matrix.
4. Discussion
4.1. Effect of harmonic structure design on corrosion resistance of
CoCrFeMnNi HEAs
Due to the different microstructure, treatment technology and solu­
tion medium, the effect of grain size on corrosion properties of materials
is quite complicated. Grain boundary has the characteristics of high
energy and unstable structure, and there are more defects at grain
boundary than inside grain. Therefore, corrosion tends to occur prefer­
entially at grain boundary. For the HS samples, the network structured
UFG exists in the shell region. As the grain size decreases, the grain
boundary density increases obviously. The corrosion of the HS CoCr­
FeMnNi HEAs occurs preferentially in the UFG region (Fig. 6(b1-d1)).
However, the high corrosion rate is also conducive to the formation
of passive film on the sample surface in the passivation environment
[64]. As indicated in Fig. 13, the metal elements in the HEA matrix at
grain boundaries are disordered and have high kinetic energy. Thus,
they are more easily diffused to the surface through the grain boundary,
and then combine with the ions in the medium to form a protective oxide
film. Compared with HS CoCrFeMnNi HEAs, the CG sample has much
larger grain size and lower grain boundary density, resulting in a lower
passivation rate. The passive film finally formed on the CG sample
surface is thin and defective (Fig. 13(a)). As indicated in Fig. 9,
Mott-Schottky results also prove that the donor density is the highest in
the passive film of CG sample. Dissolved oxygen and chloride ions in
solution preferentially attack the defective position, resulting in pitting
occurrence. The passive film on nanocrystalline structure is more
compact and uniform due to the fine distribution of grain boundary and
triple junction, while the CG structure has loose passive film [26]. The
Fig. 12. The composition variation of passive films of the CoCrFeMnNi HEAs with different shell fractions. (a) cationic fractions; (b) ratio of Cr3+
9
Corrosion Science 209 (2022) 110761
corrosion resistance of the HS CoCrFeMnNi HEAs is better than that of
the CG sample, mainly due to the regular distribution of the
three-dimensional network structured UFG. Nanomaterials could
change the nucleation mechanism of passive film from gradual to
instantaneous, thus increasing the growth rate of passive film [65]. At
the same time, the unique three-dimensional UFG network structure
accelerates the passivation of the whole HS sample surface (Fig. 13
(b-d)). The electrochemical test results also confirm that the pitting
potentials of the HS CoCrFeMnNi HEAs are higher than that of the CG
sample, and the donor densities in the passive films are lower. Thus, the
passive films have better stability and are not easy to be broken down.
As mentioned above, the corrosion of the samples occurs preferen­
tially along the grain boundary. However, the higher reaction rate in the
shell region also creates the passive film more quickly, and the donor
densities in the passive films of the HS samples are lower than that of the
CG sample. Therefore, compared with CG CoCrFeMnNi HEA, the HS
CoCrFeMnNi HEAs show much better resistance to pitting. Moreover,
compared with conventional bimodal structure with irregular CG and
UFG distribution, the harmonic structure has a regularly continuous
network UFG structure. Namely, based on macroscopic scale, the UFG
structure in the HS materials distribute much more homogeneously than
that in the bimodal structured materials. As indicated in Fig. 6, the
corrosion occurs initially in the UFG region, and propagates along the
UFG region. Thus, the regular network UFG structure may promote the
appearance of corrosion much more homogeneously than the irregular
CG/UFG structure.
4.2. Effect of shell fraction on corrosion resistance of the HS CoCrFeMnNi
HEAs
As shown in Fig. 7, the Volta potential of the UFG structure is lower
than that of the CG structure, which accelerates corrosion in shell re­
gion. The UFG in the shell region is easy to be corroded and serves as the
anode, and the CG in the core region serves as the cathode, constituting
the micro-galvanic couple. It is known that a large cathode to anode area
ratio is not beneficial to galvanic corrosion, which accelerates the
corrosion rate of the anode and leads to destructive corrosion. When the
shell fraction is 22.4%, the area ratio of cathode to anode is large. The
high anodic reaction rate generates the corrosion reaction violently and
also promotes the protective oxide film to form rapidly (Fig. 13(b)).
Thus, the HS samples have much better corrosion resistance than the CG
sample. However, due to the large area ratio of cathode to anode, the
passivation rate in the UFG region is too high, while the reaction rate in
the CG region is low, which leads to the non-uniform passive film for­
mation. According to the Mott-Schottky results (Fig. 9), the donor
density of the HS CoCrFeMnNi HEA with Sf= 22.4% is larger than that of
the samples with Sf= 31.7% and Sf= 40.5%, which also proves its poor
stability. When the shell fraction is increased to 31.7%, the reaction rate
in the CG region is accelerated due to the reduced cathode to anode area
3+
ox /Crhy .
J. Wang et al. Corrosion Science 209 (2022) 110761

Fig. 13. Schematic diagram of passive film formation on CoCrFeMnNi HEAs with different microstructures. (a) CG, Sf= 0%; (b) HS, Sf= 22.4%; (c) HS, Sf= 31.7%;
(d) HS, Sf= 40.5%.

ratio. At the same time, the galvanic corrosion effect also promotes the
passivation rate over the surface of sample, forming a uniform passive
film (Fig. 13(c)). Fig. 9(b) also shows that the donor density of the
passive film is relatively low, and its stability is improved. However, as
shown in Fig. 13(d), when the shell fraction continuously increases to
40.5%, the area ratio of anode to cathode is close to 1:1, and the passive
film in the shell region grows slowly. Meanwhile, the density of grain
boundaries on the surface increases with increasing shell fraction. As an
anode, a large area of UFG region would generate high-density defects at
the grain boundaries [31]. Thus, the diffusion of chloride ions in the
shell regionbecomes easier, which accelerates the dissolution of passive
film. As a result, the rate of passive film formation is reduced and
preferential dissolution plays a dominant role in the CoCrFeMnNi HEA
with Sf= 40.5%.
Therefore, it is seen that the shell fraction highly influences the
corrosion resistance. The shell region can cause the corrosion reaction
easily and promote rapid passive film formation. Thus, it is seen that the Fig. 14. Comparison of corrosion resistance of CoCrFeMnNi HEAs with
different microstructures in the 3.5 wt% NaCl solution.
corrosion resistance improves as shell fraction increases from 22.4% to
31.7%. However, the continuously increased UFG region can restrain
the passive film formation rate and increase the number of defects in the Compared with conventional homogeneous structured materials, the
passive film. Thus, the corrosion resistance deteriorates gradually with HS materials exhibited a good balance of high strength and high
continuously increasing shell fraction. Namely, there is an optimized ductility [34,67,68]. Overall, the harmonic structure design not only
core-shell volume fraction for enhancing corrosion resistance in mate­ enhances the synergy of strength and ductility of CoCrFeMnNi HEAs, but
rials with bimodal grain size distribution. The similar tendency is also also improves the corrosion resistance. Thus, creating heterogeneous
reported in the bimodal structured Al6063 alloy [30]. In the present structure design in the structural materials may provide an effective way
work, the HS CoCrFeMnNi HEA with Sf= 31.7% not only promotes the to achieve excellent mechanical properties and good corrosion
rapid formation of passive film, but also has fewer defects in the passive resistance.
film than the other samples. Moreover, its passive film contains rela­
tively lower manganese oxides content and higher Cr3+ 3+
ox /Crhy content.
5. Conclusions
Thus, the shell fraction of approximately 30% is the optimized design for
corrosion resistance of the HS CoCrFeMnNi HEAs. In this study, a series of HS CoCrFeMnNi HEAs with different shell
In addition, the corrosion resistance of the HS CoCrFeMnNi HEAs are fractions were prepared by mechanical milling and powder metallurgy.
also compared with other CG or UFG CoCrFeMnNi HEAs in 3.5 wt% The effects of the peculiar core-shell structure and its volume fraction on
NaCl solution. As shown in Fig. 14, the electrochemical parameters Ecorr corrosion behavior and passive film formation of the materials were
and Icorr of the HS samples are compared with those of other CoCr­ investigated at room temperature. Based on the analysis, conclusions are
FeMnNi HEAs in the literature [10,22,44,66]. It is noteworthy that the summarized as follows:
HS CoCrFeMnNi HEAs show better corrosion resistance than other CG or
UFG samples. Namely, the HS samples have higher Ecorr than CG or UFG (1) The process of activation, passivation and breakdown occurs in
samples with similar Icorr. The core-shell structure generates galvanic both CG and HS samples. However, the passivation ability of the
corrosion, accelerating the formation of passive films and improving the HS samples is much better than that of the CG sample, which is
pitting resistance. mainly related to the rapid passive film formation rate in UFG

10
J. Wang et al.
region. The charge transfer is the dominant corrosion mechanism
in both CG and HS samples.
(2) The corrosion of HS samples preferentially occurs in the shell
region because of the high grain boundary density and the
different Volta potential between shell and core. The CG sample
shows much worse corrosion resistance to chloride ions than the
HS samples.
(3) The donor density of the passive film decreases as the shell
fraction increases from 0% to 31.7%. When the shell fraction
continuously increases to 40.5%, the donor density increases
slightly. Moreover, the Cr3+ 3+
ox /Cr hy ratio of the HS sample with
shell fraction of 31.7% is the highest. Therefore, the shell fraction
of approximately 30% is the optimized design for corrosion
resistance of the HS CoCrFeMnNi HEAs. Compared with homo­
geneous CG or UFG structure, heterogeneous structure design
may provide new opportunities to enhance the corrosion resis­
tance of structural materials.
CRediT authorship contribution statement
Jiapan Wang: Methodology, Validation, Investigation, Experiments,
Writing – original draft. Zhe Zhang: Conceptualization, Methodology,
Writing – review & editing, Supervision, Project administration, Re­
sources. Hailong Dai: Methodology, Investigation, Experiments. Hir­
oshi Fujiwara: Methodology, Validation. Xu Chen: Conceptualization,
Methodology, Resources, Supervision, Project administration. Kei
Ameyama: Resources, Supervision, Project administration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data Availability
Data will be made available on request.
Acknowledgments
This work was partially supported by the National Natural Science
Foundation of China (52075368, 12011540001, 51605325) and the
JSPS Grant-in-Aid for Scientific Research of Japan (No. JP18H05256
and No. JP18H05455).
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