Corrosion Science 195 (2022) 109984

Contents lists available at ScienceDirect

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

High temperature oxidation behavior and mechanism of Al0.3CuCrFeNi2

high-entropy alloy with a coherent γ/γ’ microstructure
Guoqiang Huang a, *, 1, Jie Wu b, 1, Rui Yuan a, Yingxi Li a, Fanqiang Meng a, *, Penghui Lei c,
Chenyang Lu c, *, Fujun Cao d, Yifu Shen d
a
Sino-French Institute of Nuclear Engineering and Technology, Sun Yat-Sen University, Zhuhai 519082, China
b
College of Electronics and Optical Engineering & College of Microelectronics, Nanjing University of Posts and Telecommunications, Nanjing 210023, China
c
Department of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049, China
d
College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics (NUAA), Yudao Street 29, 210016 Nanjing, China

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

Keywords: In this study, the oxidation behavior of the Al0.3CuCrFeNi2 HEA with a typical coherent γ/γ’ microstructure was
High-entropy Alloy systematically investigated by the isothermal oxidation tests at 600, 750 and 900 ℃ in air. The results show that
γ/γ’ microstructure the oxidation kinetics of the Al0.3CuCrFeNi2 HEA follow the parabolic law at all three temperatures. As the
Oxidation
oxidation temperature increases, the surface segregation of Cu near the grain boundary occurs, leading to
Formation mechanism
different oxidation behavior in the intragranular regions and near the grain boundary regions. The associated
formation mechanisms of the oxide scales are proposed and discussed in detail.

1. Introduction strength-ductility synergy.

In recent years, high entropy alloys (HEAs) have gained great at­
tentions because of their unique microstructural characteristics and
promising properties originated from the novel concept of composition
design [1,2]. Unlike conventional metallic alloys with one or two major
constituents, HEAs are originally defined to have at least five principle
elements in equiatomic or near-equiatomic ratio, and hence endowed
with extreme chemical complexity and high configurational entropies,
which is generally perceived to facilitate the formation of simple solid
solutions with face centered-cubic (FCC) or body-centered-cubic (BCC)
structures, rather than brittle intermetallic compounds (IMCs) [3]. Early
HEA research was primarily focused on seeking single-phase solid-­
solution alloys by carefully controlling configurational entropy [4].
However, single-phase HEAs has been demonstrated experimentally to
generally fail to provide the balanced mechanical properties as required
for real industrial applications [5]. Specifically, the early interested
single-FCC HEAs normally exhibit low yield strength but exceptionally
terrific ductility and strain hardening capacity, which naturally enables
them to serve as a superior base alloy for further strengthening. There­
fore, much effort has been devoted to introducing additional strength­
ening mechanisms into the FCC HEAs to achieve superior
Precipitation strengthening has been demonstrated as an effective
strategy for further improving the mechanical properties of the FCC
HEAs [6]. Various kinds of precipitates like L12, B2, σ, μ, Laves and
carbides, have been introduced into the FCC HEAs as strengthening units
by purposefully adding the related formers [7–9]. Among these rein­
forcing phases, ordered L12-type coherent nanoprecipitates in the FCC
HEAs have attracted a great interest due to their promising strength­
ening effect toward achieving superior strength-ductility synergy
[10–14]. Combining the benefits of a ductile FCC HEA matrix and or­
dered L12-type coherent nanoprecipitates has been experimentally
demonstrated to enable the resulting alloys to achieve an excellent
strength-ductility synergy over a wide range of temperatures. He et al.
[13] reported that a minor addition of strong γ’ phase formers can
introduce coherent nanoscale L12 precipitates in the FCC
CoCrFeNi-based HEA, leading to a high tensile strength of ~1.3 GPa and
a good tensile elongation of 17%. Tong et al. [14] revealed that the
L12-strengthened HEAs are able to get excellent strength-ductility
combinations at both ambient and cryogenic temperatures. In partic­
ular, the newly developed L12 strengthened FCC HEAs have the typical
γ/γ’ microstructure similar to that of the commercial Ni-base superal­
loys, while incorporating both sluggish diffusion and lattice distortion

* Corresponding authors.
E-mail addresses: gqhuang1105@gmail.com (G. Huang), mengfq5@mail.sysu.edu.cn (F. Meng), chenylu@xjtu.edu.cn (C. Lu).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.corsci.2021.109984
Received 17 August 2021; Received in revised form 22 November 2021; Accepted 23 November 2021
Available online 26 November 2021
0010-938X/© 2021 Elsevier Ltd. All rights reserved.
 G. Huang et al. Corrosion Science 195 (2022) 109984

strengthening effects, making them potential candidates for high tem­ 2.2. Isothermal oxidation test
perature structural applications.
To develop the L12 strengthened FCC HEAs with excellent mechan­ Prior to oxidation, the aged slices at three conditions were machined
ical properties at high temperatures, it is crucial to obtain a high volume into square coupons with the dimension of 10 × 10 × 2 mm3, and then
fraction of L12 precipitates with high thermal stability. At the outset, mechanically polished up to 1 µm diamond paste, followed by ultrasonic
near-equiatomic CoCrFeNi-based FCC HEA is a commonly used system cleaning and drying. Isothermal oxidation tests were carried out at 600,
for precipitating L12 phases by adding trace amounts of L12 forming 750 and 900 ◦ C for various holding time ranging from 5 to 100 h in a
elements, such as Al, Ti or both [13]. However, near-equiatomic HEAs muffle furnace in laboratory air. After a required exposure time (5, 10,
with a minor addition of L12 formers, generally produce a relatively low 20, 35, 55, 75 and 100 h), the oxidized coupons were air-cooled outside
L12 phase fraction, and tend to form brittle IMCs (e.g. NiAl-type B2 and the furnace and the weight gain was determined by measuring the total
complex σ phases) [6,15]. In general, the favorable formation of the L12 weight of the coupons and the alumina crucible using an analytical
phases in the near-equiatomic HEAs requires a high ratio of Ni to balance with an accuracy of 10− 4 g. The mass gain results were averaged
L12-former, which can only be achieved by reducing the addition of the from three parallel coupons.
L12-former [16]. Nevertheless, less addition of the L12-former is not
conducive to obtaining a high volume fraction of L12 precipitates.
2.3. Microstructural characterization
Recently, a novel non-equiatomic composition design strategy, i.e.
AxB1+3xCDE, was proposed, which was found to be able to form high
The phase constitution of the aged Al0.3CuCrFeNi2 HEAs and the
content Ni3Al-type L12 precipitates (B3A) while creating a
developed oxide scales at different temperatures were determined using
near-equiatomic FCC matrix (BCDE) in situ [17].
X-ray diffraction (XRD) with Cu Kα radiation at 45 kV and 40 mA with
As a representative HEA that meets the above design strategy, non-
the 2θ angle from 20◦ to 100◦ and a scanning speed of 2◦ /min. The
equiatomic Al0.3CuCrFeNi2 alloy is of particular interest, in which
microstructure of the aged Al0.3CuCrFeNi2 HEAs, and microstructural
expensive Co is completely substituted with Cu and Ni. The higher
characteristics and chemical compositions of the developed oxide scales
valence electron concentration (VEC) values of Cu (11) and Ni (9) than
at different temperatures were characterized by scanning electron mi­
Co (8) favor the formation of single FCC matrix [18]. Moreover, it was
croscope (SEM, Mira3) equipped with an energy X-ray dispersive spec­
found that in the Al0.3CuCrFeNi2 HEA, Cu-rich clusters readily form due
troscopy (EDX) detector. Initial grain structures of the aged
to the positive mixing enthalpy of Cu with other elements, which can
Al0.3CuCrFeNi2 HEAs were identified by electron backscattered
serve as the heterogeneous nucleation sites for the L12 precipitate, help
diffraction (EBSD) with a EDAX detector. For further analyze the
stabilize L12 phase and improve its solvus temperature [19]. For the
microstructure and chemical composition of the specific layer of the
HEAs targeted for service in elevated temperatures, the
oxide scale formed at 900 ◦ C, thin foils extracted from the corresponding
high-temperature oxidation resistance is amongst the most important
oxide layer using focused ion beam (FIB) lift-out method were analyzed
criteria. However, compared to other aspects, such as their phase for­
using a scanning transmission electron microscopy (STEM) equipped
mation criteria, selection criteria, microstructure, mechanical properties
with an energy X-ray dispersive spectroscopy (EDX) system.
and optimization of preparation methods, the high-temperature oxida­
tion of the HEAs is still a relatively new and not yet extensively explored
3. Results
topic. The existing studies have shown the complexity in the
high-temperature oxidation behavior of the HEAs, which is greatly
3.1. Initial microstructure
affected by the temperature [20,21], the atmosphere [22,23], the ratio
of precursor elements forming precipitated phase [24,25], the types and
Fig. 1 shows XRD patterns of the aged Al0.3CuCrFeNi2 HEAs at three
contents of main constituent elements [26–28], the trace elements
different conditions. After three kinds of aging treatment, only FCC
addition [29,30] and the processing routes [31,32]. As for the
peaks are observed for the Al0.3CuCrFeNi2 HEA. The inverse pole figure
Al0.3CuCrFeNi2 HEA, to the best of authors’ knowledge, its
maps and BSE images of the Al0.3CuCrFeNi2 HEAs aged at three different
high-temperature oxidation behavior has not been explored yet to date.
conditions are shown in Fig. 2. The three aged HEAs all have the equi­
Consequently, it is imperative to ascertain its oxidation behavior in
axed grains with basically similar grain size. After isothermal aging at
order to provide appropriate insights to control its oxidation process.
various conditions, homogenously dispersed precipitates with a dark
In this study, the oxidation behavior of the Al0.3CuCrFeNi2 HEA in
the temperature range from 600 ℃ to 900 ℃ in dry air was systemati­
cally investigated. The microstructural characteristics and chemical
compositions of the developed oxide films at various temperatures were
characterized in detail to elucidate the temperature effect on their for­
mation mechanism.

2. Materials and methods

2.1. Materials

A 2-kg ingot with a nominal composition of Al5.6Cu18.8Cr18.8

Fe18.8Ni37.7 (at%), namely Al0.3CuCrFeNi2, was prepared using a high-
frequency vacuum-induction furnace using pure Fe, Cr, Ni, Cu, and Al
metals. The as-cast Al0.3CuCrFeNi2 HEA ingot was then homogenized at
1100 ◦ C for 2 h. Several slices were cut from the inner part of the ho­
mogenized ingot, which were isothermally aged at 600 ℃ for 60 h, 750
℃ for 20 h and 900 ℃ for 20 h, respectively, to obtain the desired γ/γ’
microstructure. The aging temperatures were selected with aim to match
the target oxidation temperatures used in the present study.
Fig. 1. XRD patterns of the Al0.3CuCrFeNi2 HEAs aged at three
different conditions.

2
­
G. Huang et al.
Fig. 2. Inverse pole figure maps and BSE images of the three Al0.3CuCrFeNi2 HEAs aged at three different conditions: (a), (d) 600 ℃/60 h; (b), (e) 750 ℃/20 h; (c),
(f) 900 ℃/20 h.
contrast, can be observed throughout the whole matrix for all three aged
HEAs, but they exhibit different size and morphology depending on the
aging conditions. After aging at 600 ℃ for 60 h and at 750 ℃ for 20 h, a
mixing of equiaxed-like and needle-shaped precipitates, with virtually
indistinguishable difference in size, is clearly visible. With the aging
temperature further increasing to 900 ℃, only long needle-shaped
precipitates are formed. The variation in the size and morphology of
the precipitates with aging condition in the present study is consistent
with previous report [33]. These precipitates with two typical mor­
phologies can potentially be γ’ phase. It should be mentioned that the
high-temperature oxidation resistance is greatly affected by grain size
and the oxidation behavior usually varies with grain size [34,35]. In the
present study, despite the different aging conditions, the three aged
samples are in the similar grain size. Thus, the effect of grain size on the
oxidation behavior of the Al0.3CuCrFeNi2 HEA will not be discussed in
this study.
3.2. Isothermal oxidation kinetics
Fig. 3a shows the mass gain per unit area versus oxidation time of the
Al0.3CuCrFeNi2 HEA oxidized for 100 h at temperature range from 600
Fig. 3. The kinetic curves of the Al0.3CuCrFeNi2 HEA oxidized for 100 h at 600, 750 and 900 ◦ C in air: (a) Mass gain curves, (b) fitted lines of squared mass gain.
3
Corrosion Science 195 (2022) 109984
to 900 ℃ in air. Clearly, as the oxidation temperature increases, the
oxidation rate accelerates, resulting in a faster mass gain, especially at
900 ◦ C. At each specific temperature, oxidation proceeds rapidly in the
first 5 h and then gradually slows down with the oxidation time
extending. After oxidation for 100 h at 600, 750 and 1000 ◦ C, the cor­
responding mass gains per unit area of the Al0.3CuCrFeNi2 HEA are 0.11,
0.23 and 1.06 mg/cm2, respectively. Given that the oxidation kinetics of
the Al0.3CuCrFeNi2 HEA at the three temperatures obey well the para­
bolic law, the square of the corresponding mass gains (Δm/A)2 was
plotted as a function of oxidation time, as shown in Fig. 3b. Thus, based
on the parabolic law expression [36].
(Δm)
2
= kp t + C (1)
A
where Δm is the mass gain, A is the area, kp is the parabolic rate constant,
t is the oxidation time, and C is the integration constant. kp can be
determined from the slope of (Δm/A)2 vs. t plot. The kp values for the
Al0.3CuCrFeNi2 HEA at 600, 750 and 900 ◦ C are 1.285 × 10− 4,
4.438 × 10− 4 and 1.09 × 10− 2 (mg2⋅cm− 4⋅h− 1), respectively.
G. Huang et al.
3.3. Surface morphologies of the oxide scale
The surface morphologies and the corresponding elemental distri­
butions of the Al0.3CuCrFeNi2 HEA after oxidization for 100 h at 600,
750 and 900 ℃ are shown in Figs. 4–6, respectively. For the sample
oxidized at 600 ◦ C for 100 h, a uniform and continuous surface oxide
scale is formed, as illustrated in Fig. 4. At 750 ◦ C, uneven oxidation
occurs through the entire surface after oxidation up to 100 h, with two
distinct types of oxides in terms of the morphology formed in the
intragranular regions and near the grain boundary regions respectively,
as shown in Fig. 5. The intragranular regions away from grain boundary
are rich in Cr element while the regions near grain boundary are
enriched with obvious Al, Cu, Fe and Ni elements. In particular, obvious
enrichment of the Al, Cu and Ni elements occurs along grain boundaries,
but with few Fe and Cr elements. After oxidation at higher temperature
(900 ◦ C) for 100 h, oxidation still occurs unevenly, but is significantly
increased, thus leading to the formation of raised and lowered oxide
scale from the intragranular regions to the regions near the grain
boundary across the whole surface, as shown in Fig. 6. Again, abundant
Al and Cu elements are observed near the grain boundary regions, while
the distribution of Cr, Fe and Ni elements is significantly different from
that of the sample oxidized at 750 ◦ C for 100 h. Besides Cr element, Fe
element is also mainly concentrated in the intragranular regions, but the
distribution of Ni element is relatively uniform across the intergranular
and intragranular regions, which is only depleted in intragranular region
obviously rich in Cr element. Based on the above preliminary observa­
tions, it is reasonable to assume that grain boundary and temperature
greatly affect the oxidation behavior of the Al0.3CuCrFeNi2 HEA.
Fig. 7 shows the morphological characteristics of the oxides in the
typical regions of the sample surfaces after oxidation at different tem­
peratures for 100 h, as marked by white rectangular box in Figs. 4–6.
Also, EDS point analysis was performed on the representative oxide in
these typical regions to determine their chemical composition, and the
corresponding results are listed in Table 1. For the uniform oxide scale
on the surface of the sample oxidized at 600 ℃ for 100 h, there seem to
Fig. 4. Surface morphology and corresponding elemental distributions of the Al0.3CuCrFeNi2 HEA after oxidization at 600 ℃ for 100 h.
4
Corrosion Science 195 (2022) 109984
be two kinds of phases, i.e. one is the raised particles in white contrast
(Point 1 in Fig. 7a), and the other is the flat and dense particles beneath
these raised particles in dark contrast (Point 2 in Fig. 7a). The compo­
sition of the while one is 56.28 at% O, 4.99 at% Al, 6.31 at% Cr, 6.08 at
% Fe, 10.29 at% Ni, and 16.05 at% Cu, whereas that of the grey one is
43.13 at% O, 4.88 at% Al, 12.03 at% Cr, 11.55 at% Fe, 19.62 at% Ni,
and 16.05 at% Cu. For the sample oxidized at 750 ℃ for 100 h, the
oxides near and far away from grain boundary appear to be very dense,
but show completely different morphology. The former is Al-rich oxide
(Points 3 and 4 in Fig. 7b), amounted to 63.25 at% O, 15.54 at% Al,
5.49 at% Cr, 6.53 at% Fe, 5.22 at% Ni, and 3.97 at% Cu in Point 3 and
51.70 at% O, 17.36 at% Al, 8.16 at% Cr, 7.54 at% Fe, 9.67 at% Ni, and
5.58 at% Cu in point 4, while the latter is Cr-rich oxide ((Point 5 in
Fig. 7c), with 57.12 at% O, 2.65 at% Al, 19.29 at% Cr, 9.37 at% Fe,
7.99 at% Ni, and 3.58 at% Cu. Despite the oxidation behavior of the
sample near and far away from grain boundary at 900 ℃ is similar to
that at 750 ℃ in view of overall morphologies of the surface oxides, the
oxide evolves more fully at 900 ℃ due to higher oxidation temperature,
mainly representing as the change of oxide morphology and composi­
tion in the typical regions of the sample surface. The oxides in the
intragranular central region (Fig. 7d) are octahedral oxides containing
57.12 at% O, 2.65 at% Al, 19.29 at% Cr, 9.37 at% Fe, 7.99 at% Ni, and
3.58 at% Cu, while these at the edge are granular oxides (Fig. 7d), with
57.12 at% O, 2.65 at% Al, 19.29 at% Cr, 9.37 at% Fe, 7.99 at% Ni, and
3.58 at% Cu. The oxide near the grain boundary at 900 ℃ is also Al-rich
oxide, exhibiting similar morphology and composition, but larger size
compared with that of the oxidized sample at 750 ℃.
3.4. Cross-sectional morphologies of the oxide scale
The cross-sectional morphologies and the corresponding elemental
distributions of the Al0.3CuCrFeNi2 HEA after oxidation at 600, 750 and
900 ℃ for 100 h are shown in Fig. 8. Noting that the magnification of
the BSE images (Fig. 8b, d, f) is different from each other in order to
show more clearly the differences of the oxide film formed at different
G. Huang et al. Corrosion Science 195 (2022) 109984

Fig. 5. Surface morphology and corresponding elemental distributions of the Al0.3CuCrFeNi2 HEA after oxidization at 750 ℃ for 100 h.

Fig. 6. Surface morphology and corresponding elemental distributions of the Al0.3CuCrFeNi2 HEA after oxidization at 900 ℃ for 100 h.

locations. Despite the differences in the microstructure and composition
of the surface oxide films formed at three temperatures, their thickness
increase significantly with the increasing of oxidation temperature,
which is in good agreement with the mass gain results. As shown in
Fig. 8a and b, a flat, uniform and continuous oxide scale is obtained after
oxidation at 600 ℃ for 100 h, with no obvious change in the elemental
distributions beneath it. When oxidized at 750 ℃ for 100 h, a contin­
uous oxide scale with non-uniform thickness is formed on the sample
surface, where the oxide film is thicker in the intragranular region and
thinner near the grain boundary region, as indicated in Fig. 8c and d. In

5
G. Huang et al. Corrosion Science 195 (2022) 109984

Fig. 7. Morphological characteristics of the oxides in the typical regions (as marked by white rectangular box in Figs. 4–6) of the Al0.3CuCrFeNi2 HEA after oxi­
dization at various temperatures: (a) 600 ℃; (b), (c) 750 ℃; (d), (e), (f) 900 ℃ for 100 h.

elemental distributions of the typical oxide films formed after oxidation

Table 1
at 600, 750 and 900 ℃ for 100 h. As shown in Fig. 9, at 600 ℃, the oxide
Chemical composition (at%) of the representative oxides corresponding to the
scale is continuous and dense with the average thickness of ~0.64 µm,
points marked by red cross shown in the Fig. 7.
and has a typical duplex structure consisting of an outer layer enriched
Position O Al Cr Fe Ni Cu with Fe and O and an inner layer rich in Cr and O, which is usually
1 56.28 4.99 6.31 6.08 10.29 16.05 observed for the chromia-forming alloys (such as Fe-Ni-Cr alloys) after
2 43.13 4.88 12.03 11.55 19.62 8.79 high temperature oxidation [39–41]. Ni, Cu and Al are relatively uni­
3 63.25 15.54 5.49 6.53 5.22 3.97
formly distributed throughout the oxide scale. For the oxide scale
4 51.70 17.36 8.16 7.54 9.67 5.57
5 57.12 2.65 19.29 9.37 7.99 3.58 formed at 750 ℃, the thin oxide scale near the grain boundary region
6 54.80 1.57 23.24 6.51 10.31 3.57 (Fig. 10a) is duplex with an outer layer enriched with Al, Fe, Ni, Cu and
7 67.04 1.74 10.73 10.75 8.06 1.68 O, and an inner layer rich in Al and O, while the thick oxide scale in the
8 64.25 17.05 6.77 4.16 4.96 2.81 intragranular region (Fig. 10b) is mainly composed of an thin outer layer
9 52.78 22.59 9.52 4.48 6.14 4.49
rich in Fe and O, a thick middle layer rich in Cr and O mixed with several
particles enriched with Cu and Ni, and an internal oxidation zone of Al.
the case of 900 ◦ C, an obviously thickened oxide film but still with un­ In particular, the enrichment of Cu element can be clearly observed
even thickness is formed, where the thickest part is still in the intra­ under the thin oxide scale near the grain boundary region. In the case of
granular region and the thinnest at the grain boundary, as shown in 900 ℃, the thin oxide scale near the grain boundary region comprises an
Fig. 8e and f. It is apparent that at 750 and 900 ◦ C, the microstructure outermost (Al, Ni)-rich layer with alloyed Cu, Cr and Fe, a middle (Cr,
and composition of the thick oxide film in the intragranular region is Fe, Al)-rich oxide layer, and an innermost layer of Al oxide, while the
clearly different from that of the thin oxide film near the grain boundary thick oxide scale in the intragranular region predominantly displays a Cr
region. This coincides well with the surface morphologies and element oxide thick layer, with a thin layer of (Fe, Ni)-rich oxide overlying it and
distributions of the oxide scale formed at 750 and 900 ◦ C, as shown in an obvious internal oxidation zone of Al below it. Again, Cu element is
Figs. 5 and 6. In particular, Cu element is found to be enriched in the found to be enriched near the grain boundary region, even at the oxi­
region close to the grain boundary, leading to the formation of numerous de/substrate interface right above the grain boundary where obvious Cu
Cu clusters in the vicinity, which has been previously reported to occur segregation occurs. It should be noted that at 900 ℃, the middle (Cr, Fe,
in the Al0.3CuCrFeNi2 HEA [19,33]. Moreover, Cu segregation is Al)-rich oxide layer formed near the grain boundary region seems to
observed at the oxide/substrate interface right above the grain bound­ have a smooth transition with the Cr oxide thick layer formed in the
ary. Similar phenomenon that Cu segregated at the oxide/alloy interface intragranular regions, suggesting that they are likely to have the same
during high temperature oxidation of Cu containing alloys has also been origin, but subsequently undergo the different evolution.
found by other researchers [37,38]. Considering the significantly
different microstructure and composition of the oxide film formed in the
3.5. Phase structures of the oxide scale
intragranular regions and near the grain boundary regions, it can be
claimed that there is a significant difference in the oxidation behavior
Fig. 12 shows the XRD patterns of the Al0.3CuCrFeNi2 HEA oxidized
near and far from the grain boundary when the Al0.3CuCrFeNi2 HEAs are
in air at 600, 750 and 900 ℃ for 100 h. It is clear that for the
oxidized at 750 ℃ and 900 ℃.
Al0.3CuCrFeNi2 HEA, the FCC matrix phase can be easily detected under
Given the different microstructure and composition of the oxide
all three oxidation conditions. This signifies that the oxide films formed
films formed at different temperatures or in different regions at the same
at the three temperatures are relatively thin and can be completely
temperature, the detailed cross-sectional microstructure and chemical
penetrated by X-rays. At 600 ℃, the oxide scale mainly consist of Cr2O3,
composition of the representative oxide film corresponding to the three
Fe2O3 and/or Fe3O4. With the increasing temperature, in addition to
temperatures was further revealed. Figs. 9–11 show the cross-sectional
Cr2O3, new peaks of Al2O3, NiFe2O4, NiAl2O4 and Fe(Cr, Al)2O4 are
microstructures at higher magnification and the corresponding
detected in the oxide scale after oxidation at 750 ◦ C. When the oxidation

6
G. Huang et al.
Fig. 8. Cross-sectional view and corresponding elemental distributions of the Al0.3CuCrFeNi2 HEA after oxidation at various temperatures: (a) (b) 600 ℃; (c) (d)
750 ℃; (e) (f) 900 ℃ for 100 h.
temperature further rises to 900 ℃, apart from the increase in the
number of NiAl2O4 peaks, similar diffraction peaks to these obtained at
750 ◦ C but with increased intensity are observed, thus suggesting similar
oxidation mechanism at 750 and 900 ◦ C.
Combining the XRD results with the previous microstructural and
compositional analysis of different oxide films formed at the three
temperatures, the phase composition of each sub-layer comprising the
specific oxide film can be identified. At 600 ℃, the duplex oxide scale
has an outer Fe2O3& Fe3O4 layer and an inner Cr2O3 layer; At 750 ℃, a
thin and uniform duplex oxide scale consisting of an outer [NiAl2O4 + Fe
(Cr, Al)2O4] spinel layer and an inner Al2O3 layer is formed near the
grain boundary regions, while a thick and non-uniform duplex oxide
scale consisting of an outer NiFe2O4 layer, a middle Cr2O3 layer and an
internal Al2O3 zone is developed in the intragranular regions; At 900 ℃,
the oxide scale formed near the grain boundary region consists of an
outer NiAl2O4 spinel layer, a middle Fe(Cr, Al)2O4 layer and an inner
Al2O3 layer, while that formed in the intragranular region is composed
of a very thin NiFe2O4 outer layer, a thick Cr2O3 middle layer and a
continuous inner Al2O3 layer with an internal Al2O3 zone below it.
3.6. TEM-STEM analysis
For the Al0.3CuCrFeNi2 HEA, it is clear that the higher temperature
facilitates the establishment of a continuous Al2O3 layer, especially for
the intragranular region, due to its austenitic microstructure usually
7
Corrosion Science 195 (2022) 109984
exhibiting the lower intrinsic diffusivity for Al than ferritic microstruc­
ture [42]. At 900 ℃, a visually continuous Al2O3 inner layer is formed,
but significant internal oxidation occurs below it in the intragranular
region. Therefore, the Al2O3 layers formed in the intragranular region
and near the grain boundary region were further examined by
TEM-STEM to reveal their detailed microstructure and chemical
composition. The samples were taken from the specified regions by
focused ion beam (FIB) milling. Figs. 13 and 14 show the STEM images
and the corresponding EDS maps of the Al2O3 layers formed in the
intragranular region and near the grain boundary region respectively,
along with the associated SAED patterns of the corresponding areas. As
shown in Figs. 13 and 14, for two TEM-STEM samples taken from the
vicinity of the aluminum oxide formed in the intragranular region and
near the grain boundary region, the SAED patterns reveal that the upper
oxide layer of Cr-rich is Cr2O3, the middle oxide layer is Al2O3, and the
lower layer is γ/γ’ matrix, which agrees well with the EDS and XRD
results. However, the detailed microstructure of Al2O3 layer formed in
the two regions is obviously different. The Al2O3 layer formed in the
intragranular region (Fig. 13) contains a large number of pores holes,
with several long pegs of Al2O3 embedded in the lower alloy matrix,
while that formed near the grain boundary region (Fig. 14) is highly
dense, but has detached from the underlying substrate. Such spallation is
likely to occur during the cooling process due to no sign of a thin
re-oxidation layer forming beneath it, which to some extent reflects the
relatively weak interfacial adhesion of the Al2O3 layer formed near the
G. Huang et al. Corrosion Science 195 (2022) 109984

Fig. 9. Cross-sectional microstructure at higher magnification and corresponding elemental distributions of the oxide film formed after oxidation at 600 ℃ for 100 h.

Fig. 10. Cross-sectional microstructure at higher magnification and corresponding elemental distributions of the oxide film formed after oxidation at 750 ℃ for
100 h: (a) the near-grain-boundary region; (b) the intragranular region.

8
G. Huang et al. Corrosion Science 195 (2022) 109984

Fig. 11. Cross-sectional microstructure at higher magnification and corresponding elemental distributions of the oxide film formed after oxidation at 900 ℃
for 100 h.

Fig. 12. XRD patterns of the Al0.3CuCrFeNi2 HEA after oxidation in air at 600, 750 and 900 ℃ for 100 h.

9
G. Huang et al. Corrosion Science 195 (2022) 109984

Fig. 13. TEM observation and analysis of the aluminum oxide layer formed in the intragranular region after oxidation at 900 ℃ for 100 h: (a) STEM image and (b)
EDS mappings for O, Al, Ni, Cr, Fe and Cu.

Fig. 14. TEM observation and analysis of the aluminum oxide layer formed near the grain boundary region after oxidation at 900 ℃ for 100 h: (a) STEM image, (b)
EDS mappings for O, Al, Ni, Cr, Fe and Cu, (c) selected area diffraction patterns of corresponding points 1–3 in (a).

grain boundary region with the lower substrate. In fact, the intrinsic
microstructure of the formed Al2O3 layer greatly determines its own
adhesion to the substrate. For the Al2O3 layer formed in the intra­
granular region, the long pegs embedded in the alloy substrate facilitate
the mechanical anchoring of the Al2O3 layer to the substrate [43,44].
Also, the pores inside the Al2O3 layer are favorable to the release of the
stress generated in its growth process, thereby protecting the oxide scale
from falling off and cracking [45]. These two microstructural factors
work together to improve the interfacial adhesion of the oxide scale
formed in the intragranular region. However, the pores also provide
channels for the outward diffusion of metal cations and the inward
diffusion of oxygen, thereby accelerating the oxidation process.
4. Discussion
In this study, the surface oxide scales with different microstructures
and compositions are observed on the Al0.3CuCrFeNi2 HEA after
oxidation at 600, 750 and 900 ℃ for 100 h in air. All above results
indicate the obvious temperature effect on the oxidation behavior of the
Al0.3CuCrFeNi2 HEA. In the following, the formation mechanisms of the
corresponding surface oxide scales at temperature range from 600 to
900 ℃ are proposed and discussed in detail.
According to the isothermal oxidation test results (Fig. 3), the
oxidation kinetics of the Al0.3CuCrFeNi2 HEA are known to follow the
parabolic law at temperature range from 600 to 900 ℃. This suggests
that the oxidation of the Al0.3CuCrFeNi2 HEA is a typical diffusion
controlled process, which consists of the initial rapid oxidation stage
involving the adsorption of oxygen on the alloy surface and its chemical

10
G. Huang et al.
reaction with metal cations, and the subsequent stable oxide growth
stage controlled by the diffusion transportation of oxygen anions and/or
metal cations [46]. In the initial stage of oxidation, only thermody­
namically stable oxides are likely to form on the alloy surface. According
to the Gibbs free energy-temperature map of metal oxides, the Gibbs free
energies of the oxides related to the involved elements in the
Al0.3CuCrFeNi2 HEA are all negative at temperature range from 600 to
900 ℃, with their magnitudes ordered in Al2O3 < Cr2O3 < FeO < Fe3O4
< NiO < Fe2O3 < CuO [47,48]. This signifies that the alloying elements
on the surface of the Al0.3CuCrFeNi2 HEA compete with each other to be
oxidized, with the oxygen affinity (i.e. oxide forming ability) in the
order of Al > Cr > Fe > Ni > Cu. In this case, the alloying elements with
higher oxygen affinity can be oxidized prior to those with lower oxygen
affinity. However, the formation of the initial oxide film on the alloy
surface is also greatly influenced by the kinetic conditions, which are
highly related to the oxidation temperature and solute concentrations
[47,49]. For the Al0.3CuCrFeNi2 HEA, although Al2O3 is most favored to
form thermodynamically in the initial oxidation stage at 600, 750 and
900 ℃, no external Al2O3 layer is formed in all three cases, indicating
that the formation of a continuous external Al2O3 layer in the initial
stage is not kinetically supported under all three conditions. This is
mainly due to the low bulk Al content and the slow diffusion of Al from
the substrate bulk to the alloy/oxide interface, which make the surface
Al content not reach the critical Al concentration required to form a
continuous external Al2O3 layer. Consequently, high content (~18.8 at
%) Cr with oxygen affinity second only to Al is expected to preferentially
react with oxygen to form the Cr2O3 layer on the whole alloy surface in
the initial oxidation stage at the three temperatures. This expectation
seems to be correct at 600 ℃, but at 750 and 900 ℃, the oxides with
different morphologies and compositions are initially formed in the
intra-grain regions and near the grain boundary regions, respectively. As
shown in the Supplementary materials (Fig. S1 and Fig. S2), just 5 h
after oxidation at 750 and 900 ℃ respectively, the Cr-rich oxides only
form in the intra-grain regions, whereas the oxides rich in Al, Cu and Ni
tend to form near the grain boundary regions. At 750 ℃, Fe is present
throughout the whole surface oxide scale, with slight enrichment in the
Cr-rich oxides formed in the intragranular regions, while at 900 ℃ it is
mainly enriched in the intragranular regions where the Cr-rich oxides
are located, especially along their edges. This suggests that the surface
states of the Al0.3CuCrFeNi2 HEA are distinctly different in the intra­
granular regions and near the grain boundary regions in the early stages
of oxidation at 750 and 900 ℃, thereby leading to the occurrence of
different oxidation reactions. Here, for the Al0.3CuCrFeNi2 HEA oxidized
at 750 and 900 ℃, a question that how the different surface states in the
intragranular regions and near the grain boundary regions are generated
naturally arises.
For the M-Cr type alloys (M is Ni, Fe or Ni + Fe) with the Cr content
close to 18 wt%, it is well known that an exclusive Cr2O3 scale can be
easily formed on the alloy surface in the initial stage of high-temperature
oxidation [50]. Specially, the Cr2O3 is preferentially formed at the grain
boundaries, followed by sideways diffusion of Cr and spreading of
Cr2O3, which is caused by the significantly high Cr flux due to the rapid
diffusion of Cr along grain boundaries [35,49]. Adding a certain amount
of Al into the M-Cr type alloys may lead to the formation of a continuous
external Al2O3 scale above a certain temperature. However, in the pre­
sent study, only internal Al2O3 layer was formed near the grain
boundary regions at both 750 and 900 ℃. This indicates that the Cr2O3
is still expected to form first, which helps to reduce the oxygen pressure
and thereby promotes the formation of Al2O3 below it [51]. Meanwhile,
it is reasonable to assume that higher Cr content near the grain
boundaries should be more favorable for the formation of Cr2O3, but this
is not the case. The unexpected absence of Cr2O3 near the grain
boundaries (see Figs. 5, 6, Figs. S1 and S2) suggests that the surface
conditions of the Al0.3CuCrFeNi2 HEA near the grain boundaries do not
support the formation of Cr2O3. Therefore, there must be other factors
affecting the surface conditions of the Al0.3CuCrFeNi2 HEA near the
11
Corrosion Science 195 (2022) 109984
grain boundaries.
Considering that the Cu content of the Al0.3CuCrFeNi2 HEA studied
in the present work is significantly higher than that of the Ni-Fe-Cr-Al
type alloy, it can be speculated that it is likely that high content Cu
leads to different surface states in the intragranular regions and near the
grain boundary regions when oxidized at 750 and 900 ℃. Doi et al. [52].
revealed the occurrence of Cu segregation at oxide/alloy interface on the
Ni-Cr alloy containing alloyed Cu just 300 s after oxidation at 923 K in
the dusting environment of 60 vol% CO- 26 vol% H2-11.5 vol%
CO2-2.5 vol% H2O by hard X-ray photoelectron spectroscopy (HX-PES),
which is considered to be able to suppress the dissociative absorption of
CO. A quite recent work by Hayashi et al. [53]. found that the addition of
Cu into FCC Fe-Ni-Cr-Al and Ni-Cr-Al based alloys is beneficial for the
formation of external Al2O3 scale. The beneficial effect of Cu is explained
to be due to the decreased oxygen concentration on the alloy surface. In
the present study, the alloy surfaces oxidized at 750 and 900 ℃ for 5 h
both show a clear enrichment of Cu, as shown in the Supplementary
materials (Fig. S1 and Fig. S2). After oxidation at 750 and 900 ℃ for
100 h, Cu element is found to be enriched in the subsurface close to the
grain boundary, and Cu segregation layer forms below the oxide scale
right above the grain boundary (Fig. 11). It can be anticipated that Cu
segregation occurs at the air/alloy interface in the early stages of
oxidation at 750 and 900 ℃, which effectively reduces the oxygen
pressure on the alloy surface to the point where the Cr cannot be
oxidized. Thus, the [Fe(Cr, Al)2O4 + NiAl2O4] and NiAl2O4 spinel layer
first form near the grain boundary regions in the initial stages of
oxidation at 750 and 900 ℃, respectively. It has been reported that the
increase of Cu content in the Ni-Cr-Al alloy can lead to the change of
initial oxide film formed after 4 h of oxidation in air at 1000 ℃ from the
Cr2O3 to the NiAl2O4 [53]. It should be mentioned that prior to the
formation of spinel-type oxides, such as Fe(Cr, Al)2O4 and NiAl2O4,
other oxides, like NiO and Cu2O, may also form in the earlier stage of
initial oxidation, which requires further study in the future.
Once the oxide layer is initially formed over the entire alloy surface,
the oxidation process will be kinetically controlled by the diffusion
through the oxide. After the initial formation of Cr2O3 layer at 600 ℃,
the Fe cations diffuse outward through the Cr2O3 layer more rapidly due
to its much higher diffusion coefficient in the Cr2O3 layer than the other
elements of the Al0.3CuCrFeNi2 HEA, resulting in the formation of an Fe-
rich oxide layer on the top of Cr2O3 layer [54]. The early establishment
of the protective Cr2O3 layer is well known to greatly reduce the oxygen
pressure at the Cr2O3/alloy interface, thereby promoting the selective
oxidation of Al beneath it [51]. If the Al content near the Cr2O3/alloy
interface is above a certain critical level, a continuous, protective Al2O3
layer can be formed, otherwise an internal oxide zone of Al2O3 will be
produced [55]. Here, no internal oxidation of Al was found after oxi­
dization at 600 ℃ for 100 h, which is mainly due to that the growth rate
of the duplex-layer oxide scale is higher than that of oxygen penetration.
Finally, the duplex-layer oxide scale consisting of an outer Fe2O3&Fe3O4
layer and an inner Cr2O3 layer is formed on the Al0.3CuCrFeNi2 HEA
surface after oxidization at 600 ℃ for 100 h.
In the case of 750 and 900 ℃, with the initial formation of the Cr2O3
and the spinel-type oxides (Fe(Cr, Al)2O4 and NiAl2O4) in the intra-grain
regions and near the grain boundary regions respectively, the oxygen
pressure at the oxide/alloy interface is effectively reduced. Thus, the
temperature-dependent selective oxidation of Al begins to occur in the
intragranular regions and near the grain boundary regions at both
temperatures. At 750 ℃, a thin continuous Al2O3 inner layer is formed
beneath the (Fe(Cr, Al)2O4 + NiAl2O4) layer near the grain boundary
regions, while Al is only internally oxidized below the Cr2O3 layer in the
intra-grain regions. This is mainly attributed to the faster Al trans­
portation flow near the grain boundary than in the grain interior,
resulting in the Al content in the near-surface region adjacent to the
grain boundary exceeding the critical Al concentration required to form
a continuous Al2O3 layer. Moreover, the lower oxygen pressure beneath
the [Fe(Cr, Al)2O4 + NiAl2O4] layer, which requires a lower critical Al
G. Huang et al.
level to form a continuous Al2O3 layer, is also beneficial for the estab­
lishment of the continuous Al2O3 layer near the grain boundary. At
900 ℃, a thicker continuous and compact Al2O3 inner layer is formed
near the grain boundary, whereas an inner Al2O3 layer that looks dense
but has micropores inside, is developed in the intergranular regions,
with significant internal oxidation of Al occurred beneath it. It is
apparent that the higher temperature, capable of accelerating the
transportation of Al to the alloy surface, contributes to the development
of a continuous Al2O3 inner layer below the initially formed oxide layer,
especially near the grain boundary regions. Nevertheless, it seems that at
900 ℃, the Al supply to alloy surface in the grain interiors is still
insufficient to establish a continuous and dense Al2O3 inner layer. Thus,
at either 750 or 900 ℃, the continuous and dense Al2O3 inner layer
formed near the grain boundary can better impede the oxygen pene­
tration and the outward diffusion of metal cations, while the formation
of the Al2O3 internal oxidation zone and the non-dense Al2O3 inner layer
in the intragranular regions allows Fe and Ni cations to diffuse up and
through the upper Cr2O3 layer and form the outward-growing NiFe2O4
layer at 750 and 900 ℃, respectively. As a consequence, the thickness of
the surface oxide scale in the intragranular regions is significantly higher
than that near the grain boundary, especially at 900 ℃. It should be
mentioned that more obvious enrichment of Fe in the surface oxide scale
formed near the grain boundary at 750 ℃ than at 900 ℃ is likely due to
the longer required time to form a continuous and dense Al2O3 inner
layer caused by the relatively low temperature, which allows more Fe
cations to diffuse into the upper oxide layer.
From the above discussion, the oxidation mechanisms of the
Al0.3CuCrFeNi2 HEA after isothermal oxidation at 600, 750 and 900 ℃
for 100 h are schematically summarized in Fig. 15. At 600 ℃, a rela­
tively uniform Cr2O3 layer is first formed on the alloy surface, followed
by the formation of Fe2O3&Fe3O4 layer above it due to the faster
diffusion of Fe in the Cr2O3 layer. As a result, a duplex-layer oxide scale
consisting of an outer Fe2O3&Fe3O4 layer and an inner Cr2O3 layer is
formed after oxidation for 100 h, as shown in Fig. 15a. At 750 and
900 ℃, the surface segregation of Cu near the grain boundaries leads to
different oxidation behavior near the grain boundary regions and in the
intragranular regions. The spinel-type oxide layer (Fe(Cr, Al)2O4
+ NiAl2O4 at 750 ℃ and NiAl2O4 at 900 ℃) is first formed near the
grain boundary regions, while the Cr2O3 layer is formed in the intra­
granular regions. In fact, the initial formation and subsequent growth of
both the spinel-type oxides near the grain boundary regions and the
Cr2O3 in the intragranular regions compete against each other, which is
obviously affected by temperature. At higher temperatures, the initial
Fig. 15. The schematic illustration of the proposed oxide growth.
12
Corrosion Science 195 (2022) 109984
formation of the spinel-type oxide is restricted to closer to the grain
boundaries, and the subsequent lateral growth covers the adjacent Cr2O3
layer. With the formation of the initial spinel-type oxide layer and Cr2O3
layer, the resulting reduced oxygen pressure at oxide/alloy interface
triggers the selective oxidation of Al. Due to the relatively high Al
concentration caused by the faster Al transportation near the grain
boundary, a continuous and dense Al2O3 inner layer is formed below the
initial spinel-type oxide layer at both temperatures, with its thickness
thicker at 900 ℃ than at 750 ℃. Unlike this, because of the slowing of Al
supply in the intragranular regions towards the near-surface region of
the alloy, the Al concentration near the Cr2O3/alloy interface cannot
reach the critical Al level to form continuous and dense Al2O3 layer,
leading to the formation of an internal oxidation zone of Al below the
Cr2O3 layer at 750 ℃; at 900 ℃, the elevated temperature effectively
accelerates the transport of Al and an visually continuous but actually
non-dense Al2O3 inner layer with an internal Al2O3 zone immediately
below is generated beneath the Cr2O3 layer. Due to the non-dense nature
of the oxidation products below the Cr2O3 layer in the intragranular
regions, the Fe and Ni cations can easily diffuse up and through the
Cr2O3 layer, with the NiFe2O4 layer formed above it at 750 and 900 ℃
respectively. In the meantime, the initial Cr2O3 layer covered by the
NiAl2O4 layer at 900 ℃ is developed into Fe(Cr, Al)2O4. Thus, after
oxidation at 750 and 900 ℃ for 100 h, a thin duplex-layer oxide scale
consisting of an outer spinel-type oxide layer and an inner Al2O3 layer is
formed near the grain boundary regions, with the more obvious overlap
between the NiAl2O4 layer and the Cr2O3 layer at 900 ℃, while in the
intragranular regions, a thick oxide scale composed of a thin NiFe2O4
layer, a thick Cr2O3 layer, and an internal Al2O3 zone (Fig. 15b) and of a
thin NiFe2O4 layer, a thick Cr2O3 layer, and a non-dense Al2O3 inner
layer with an internal Al2O3 zone below it (Fig. 15c) is formed at 750
and 900 ℃ respectively.
On the basis of the in-depth understanding on the oxidation mech­
anism of the Al0.3CuCrFeNi2 HEA at different temperatures, it can be
asserted that fine grains are favorable to its oxidation resistance since
high grain boundary density is beneficial to supply more Cu and Al to the
alloy surface, which enables the initial oxide layer to change from the
Cr2O3 layer to the NiAl2O4 layer, and facilitates the subsequent estab­
lishment of a continuous and dense Al2O3 inner layer. Therefore, the
thermomechanical processing for the Al0.3CuCrFeNi2 HEA is recom­
mended to optimize grain size in the future work. In addition, the
adhesion between the Al2O3 inner layer and the alloy substrate requires
further amelioration. Addition of the rare earth elements (REs), such as
Y, has been proved to be an effective strategy to improve the adhesion of
the oxide scale with alloy substrate and slow down the growth rate of the
scale [56–58]. Thus, alloying the Al0.3CuCrFeNi2 HEA with REs can be
applied for improving both the adhesion and the oxidation resistance. In
summary, the oxidation resistance of the Al0.3CuCrFeNi2 HEA can be
further improved in the future by refining grains or adding trace REs
elements.
5. Conclusions
In the present study, the oxidation behavior of the Al0.3CuCrFeNi2
HEA at 600, 750 and 900 ◦ C in air was systematically investigated. The
isothermal oxidation kinetics of the Al0.3CuCrFeNi2 HEA follow the
parabolic law at all three temperatures, with the oxidation rate
increasing with the temperature, especially at 900 ℃. After oxidation at
the three temperatures for 100 h, the corresponding mass gains per unit
area of the Al0.3CuCrFeNi2 HEA are 0.11, 0.23 and 1.06 mg/cm2,
respectively. Raising the temperature induces progressively different
oxidation behavior in the intragranular regions and near the grain
boundary regions. This can be attributed to the surface segregation of Cu
near the grain boundary in the initial oxidation stage, which leads to
different surface states in the intragranular regions and near the grain
boundary regions, and thereby affects the initial oxide formation as well
as the subsequent oxide development. At 600 ℃, the entire surface of
G. Huang et al.
the alloy is uniformly oxidized, resulting in the formation of a uniform
and continuous oxide scale consisting of an outer Fe2O3& Fe3O4 layer
and an inner Cr2O3 layer; at 750 and 900 ℃, the oxide scale near the
grain boundary typically comprises an external spinel-type oxide layer
and an internal Al2O3 layer at both temperatures, while that in the
intragranular regions is composed of an outer NiFe2O4 thin layer, an
intermediate Cr2O3 thick layer and an internal Al2O3 zone at 750 ℃/a
non-dense Al2O3 inner layer with an internal Al2O3 zone immediately
below at 900 ℃.
CRediT authorship contribution statement
Guoqiang Huang: Conceptualization, Methodology, Validation,
Investigation, Formal analysis, Writing – original draft. Jie Wu: Inves­
tigation, Formal analysis, Writing – review & editing. Rui Yuan:
Investigation, Formal analysis. Yingxi Li: Investigation, Formal anal­
ysis. Fanqiang Meng: Supervision, Writing – review & editing. Penghui
Lei: Investigation, Formal analysis. Chenyang Lu: Supervision, Writing
– review & editing. Fujun Cao: Investigation, Formal analysis. Yifu
Shen: Investigation, Formal analysis, Writing – review & editing. All
authors read and contributed to the manuscript.
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
The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also forms part of an ongoing study.
Acknowledgements
This study was financially supported by the National Natural Science
Foundation of China (Grant No. 12075179). Jie Wu acknowledges the
financial support of Natural Science Foundation of Jiangsu Province
(Grant No. BK20200746), General Projects Of Natural Science Research
in Universities of Jiangsu Province (Grant No. 20KJB460008) and Start-
Up Fund from Nanjing University of Posts and Telecommunications
(Grant No. NY220077).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.corsci.2021.109984.
References
[1] Y.F. Ye, Q. Wang, J. Lu, C.T. Liu, Y. Yang, High-entropy alloy: challenges and
prospects, Mater. Today 19 (2016) 349–362.
[2] E.P. George, D. Raabe, R.O. Ritchie, High-entropy alloys, Nat. Rev. Mater. 4 (2019)
515–534.
[3] Y. Zhang, Y.J. Zhou, J.P. Lin, G.L. Chen, P.K. Liaw, Solid-solution phase formation
rules for multi-component alloys, Adv. Eng. Mater. 10 (2008) 534–538.
[4] Y. Zhang, T.T. Zuo, Z. Tang, M.C. Gao, K.A. Dahmen, P.K. Liaw, Z.P. Lu,
Microstructures and properties of high-entropy alloys, Prog. Mater. Sci. 61 (2014)
1–93.
[5] D.B. Miracle, O.N. Senkov, A critical review of high entropy alloys and related
concepts, Acta Mater. 122 (2017) 448–511.
[6] T. Yang, Y.L. Zhao, B.X. Cao, J.J. Kai, C.T. Liu, Towards superior mechanical
properties of hetero-structured high-entropy alloys via engineering
multicomponent intermetallic nanoparticles, Scr. Mater. 183 (2020) 39–44.
[7] D. Choudhuri, B. Gwalani, S. Gorsse, M. Komarasamy, S.A. Mantri, S.G. Srinivasan,
R.S. Mishra, R. Banerjee, Enhancing strength and strain hardenability via
deformation twinning in fcc-based high entropy alloys reinforced with
intermetallic compounds, Acta Mater. 165 (2019) 420–430.
[8] K. Ming, X. Bi, J. Wang, Precipitation strengthening of ductile
Cr15Fe20Co35Ni20Mo10 alloys, Scr. Mater. 137 (2017) 88–93.
13
Corrosion Science 195 (2022) 109984
[9] Y.L. Zhao, T. Yang, Y. Tong, J. Wang, J.H. Luan, Z.B. Jiao, D. Chen, Y. Yang, A. Hu,
C.T. Liu, J.J. Kai, Heterogeneous precipitation behavior and stacking-fault-
mediated deformation in a CoCrNi-based medium-entropy alloy, Acta Mater. 138
(2017) 72–82.
[10] Z.G. Wang, W. Zhou, L.M. Fu, J.F. Wang, R.C. Luo, X.C. Han, B. Chen, X.D. Wang,
Effect of coherent L12 nanoprecipitates on the tensile behavior of a fcc-based high-
entropy alloy, Mater. Sci. Eng. A 696 (2017) 503–510.
[11] W. Lu, X. Luo, Y. Yang, K. Yan, B. Huang, P. Li, Nano-precipitates strengthened
non-equiatomic medium-entropy alloy with outstanding tensile properties, Mater.
Sci. Eng. A 780 (2020), 139218.
[12] X. Huang, L. Huang, H. Peng, Y. Liu, B. Liu, S. Li, Enhancing strength-ductility
synergy in a casting non-equiatomic NiCoCr-based high-entropy alloy by Al and Ti
combination addition, Scr. Mater. 200 (2021), 113898.
[13] J.Y. He, H. Wang, H.L. Huang, X.D. Xu, M.W. Chen, Y. Wu, X.J. Liu, T.G. Nieh,
K. An, Z.P. Lu, A precipitation-hardened high-entropy alloy with outstanding
tensile properties, Acta Mater. 102 (2016) 187–196.
[14] Y. Tong, D. Chen, B. Han, J. Wang, R. Feng, T. Yang, C. Zhao, Y.L. Zhao, W. Guo,
Y. Shimizu, C.T. Liu, P.K. Liaw, K. Inoue, Y. Nagai, A. Hu, J.J. Kai, Outstanding
tensile properties of a precipitation-strengthened FeCoNiCrTi0.2 high-entropy
alloy at room and cryogenic temperatures, Acta Mater. 165 (2019) 228–240.
[15] W.H. Liu, Z.P. Lu, J.Y. He, J.H. Luan, Z.J. Wang, B. Liu, M.W. Chen, C.T. Liu,
Ductile CoCrFeNiMox high entropy alloys strengthened by hard intermetallic
phases, Acta Mater. 116 (2016) 332–342.
[16] D. Li, C. Li, T. Feng, Y. Zhang, G. Sha, J.J. Lewandowski, P.K. Liaw, Y. Zhang, High-
entropy Al0.3CoCrFeNi alloy fibers with high tensile strength and ductility at
ambient and cryogenic temperatures, Acta Mater. 123 (2017) 285–294.
[17] Y.J. Liang, L.J. Wang, Y.R. Wen, B.Y. Cheng, Q.L. Wu, T.Q. Cao, Q. Xiao, Y.F. Xue,
G. Sha, Y.D. Wang, Y. Ren, X.Y. Li, L. Wang, F.C. Wang, H.N. Cai, High-content
ductile coherent nanoprecipitates achieve ultrastrong high-entropy alloys, Nat.
Commun. 9 (2018) 1–8.
[18] C. Ng, S. Guo, J. Luan, Q. Wang, J. Lu, S. Shi, C.T. Liu, Phase stability and tensile
properties of Co-free Al0.5CrCuFeNi2 high-entropy alloys, J. Alloy. Compd. 584
(2014) 530–537.
[19] B. Gwalani, V. Soni, D. Choudhuri, M. Lee, J.Y. Hwang, S.J. Nam, H. Ryu, S.
H. Hong, R. Banerjee, Stability of ordered L12 and B2 precipitates in face centered
cubic based high entropy alloys-Al0.3CoFeCrNi and Al0.3CuFeCrNi2, Scr. Mater. 123
(2016) 130–134.
[20] G. Laplanche, U.F. Volkert, G. Eggeler, E.P. George, Oxidation behavior of the
CrMnFeCoNi high-entropy alloy, Oxid. Met. 85 (2016) 629–645.
[21] Y.K. Kim, Y.A. Joo, H.S. Kim, K.A. Lee, High temperature oxidation behavior of Cr-
Mn-Fe-Co-Ni high entropy alloy, Intermetallics 98 (2018) 45–53.
[22] C. Stephan-Scherb, W. Schulz, M. Schneider, S. Karafiludis, G. Laplanche, High-
temperature oxidation in dry and humid atmospheres of the equiatomic
CrMnFeCoNi and CrCoNi high- and medium-entropy alloys, Oxid. Met. 95 (2021)
105–133.
[23] W. Kai, F.C. Chien, F.P. Cheng, R.T. Huang, J.J. Kai, C.T. Liu, The corrosion of an
equimolar FeCoNiCrMn high-entropy alloy in various CO2/CO mixed gases at 700
and 950◦ C, Corros. Sci. 153 (2019) 150–161.
[24] A. Erdogan, K.M. Doleker, S. Zeytin, Effect of Al and Ti on high-temperature
oxidation behavior of CoCrFeNi-based high-entropy alloys, JOM 71 (2019)
3499–3510.
[25] Z.Y. Ding, B.X. Cao, J.H. Luan, Z.B. Jiao, Synergistic effects of Al and Ti on the
oxidation behaviour and mechanical properties of L12-strengthened FeCoCrNi
high-entropy alloys, Corros. Sci. 184 (2021), 109365.
[26] W. Kai, C.C. Li, F.P. Cheng, K.P. Chu, R.T. Huang, L.W. Tsay, J.J. Kai, Air-oxidation
of FeCoNiCr-based quinary high-entropy alloys at 700-900 ℃, Corros. Sci. 121
(2017) 116–125.
[27] J. Lu, Y. Chen, H. Zhang, L. Li, L.M. Fu, X.F. Zhao, F.W. Guo, P. Xiao, Effect of Al
content on the oxidation behavior of Y/Hf-doped AlCoCrFeNi high-entropy alloy,
Corros. Sci. 170 (2020), 108691.
[28] N.K. Adomako, J.H. Kim, Y.T. Hyun, High-temperature oxidation behaviour of low-
entropy alloy to medium-and high-entropy alloys, J. Therm. Anal. Calorim. 133
(2018) 13–26.
[29] M. Vilémová, K. Illková, Š. Csáki, F. Lukáč, H. Hadraba, J. Matějíček, Z. Chlup,
J. Klečka, Thermal and oxidation behavior of CoCrFeMnNi alloy with and without
yttrium oxide particle dispersion, J. Mater. Eng. Perform. 28 (2019) 5850–5859.
[30] J. Lu, H. Zhang, L. Li, A.H. Huang, X.Z. Liu, Y. Chen, X.C. Zhang, F.W. Guo, X.
F. Zhao, Y-Hf co-doped Al1.1CoCr0.8FeNi high-entropy alloy with excellent
oxidation resistance and nanostructure stability at 1200 ◦ C, Scr. Mater. 203 (2021),
114105.
[31] Y. Wang, M. Zhang, J. Jin, P. Gong, X. Wang, Oxidation behavior of CoCrFeMnNi
high entropy alloy after plastic deformation, Corros. Sci. 163 (2020), 108285.
[32] Z.P. Tong, H.L. Liu, J.F. Jiao, W.F. Zhou, Y. Yang, X.D. Ren, Laser additive
manufacturing of CrMnFeCoNi high entropy alloy: microstructural evolution, high-
temperature oxidation behavior and mechanism, Opt. Laser Technol. 130 (2020),
106326.
[33] B. Gwalani, D. Choudhuri, V. Soni, Y. Ren, M. Styles, J.Y. Hwang, S.J. Nam, H. Ryu,
S.H. Hong, R. Banerjee, Cu assisted stabilization and nucleation of L12 precipitates
in Al0.3CuFeCrNi2 fcc-based high entropy alloy, Acta Mater. 129 (2017) 170–182.
[34] S. Pour-Ali, M. Weiser, N.T. Nguyen, A.R. Kiani-Rashid, A. Babakhani, S. Virtanen,
High temperature oxidation behaviour of AISI 321 stainless steel with an ultrafine-
grained surface at 800 ◦ C in Ar-20 vol% O2, Corros. Sci. 163 (2020), 108282.
[35] J.H. Kim, D.I. Kim, S. Suwas, E. Fleury, K.W. Yi, Grain-size effects on the high
temperature oxidation of modified 304 austenitic stainless steel, Oxid. Met. 79
(2013) 239–247.
G. Huang et al.
[36] Y. Xu, W. Li, L. Qu, X. Yang, B. Song, R. Lupoi, S. Yin, Solid-state cold spraying of
FeCoCrNiMn high-entropy alloy: an insight into microstructure evolution and
oxidation behavior at 700–900 ◦ C, J. Mater. Sci. Technol. 68 (2021) 172–183.
[37] J.H. Kim, D.I. Kim, J.H. Shim, K.W. Yi, Investigation into the high temperature
oxidation of Cu-bearing austenitic stainless steel using simultaneous electron
backscatter diffraction-energy dispersive spectroscopy analysis, Corros. Sci. 77
(2013) 397–402.
[38] H. Shi, R. Fetzer, A. Jianu, A. Weisenburger, A. Heinzel, F.B. Lang, G. Müller,
Influence of alloying elements (Cu, Ti, Nb) on the microstructure and corrosion
behaviour of AlCrFeNi-based high entropy alloys exposed to oxygen-containing
molten Pb, Corros. Sci. 190 (2021), 109659.
[39] W. Wei, S.J. Geng, D.B. Xie, F.H. Wang, High temperature oxidation and corrosion
behaviours of Ni-Fe-Cr alloys as inert anode for aluminum electrolysis, Corros. Sci.
157 (2019) 382–391.
[40] W. Wei, S.J. Geng, C. Gang, F.H. Wang, Growth mechanism of surface scales on Ni-
Fe-Cr alloys at 960 ◦ C in air, Corros. Sci. 173 (2020), 108737.
[41] S. Zhang, S. Hayashi, S. Ukai, N.H. Oono, Effect of Co addition on the high-
temperature oxidation behavior of oxide-dispersion-strengthened FeCrAl alloys,
Corros. Sci. 184 (2021), 109391.
[42] M.P. Brady, Y. Yamamoto, B.A. Pint, M.L. Santella, P.J. Maziasz, L.R. Walker, On
the loss of protective scale formation in creep-resistant, alumina-forming austenitic
stainless steels at 900 ◦ C in air, Mater. Sci. Forum 595 (2008) 725–732.
[43] D. Pilone, F. Felli, A. Brotzu, High temperature oxidation behaviour of TiAl-Cr-Nb-
Mo alloys, Intermetallics 43 (2013) 131–137.
[44] Y. Pan, X. Lu, M.D. Hayat, F. Yang, C. Liu, Y. Li, X.Y. Li, W. Xu, X.H. Qu, P. Cao,
Effect of Sn addition on the high-temperature oxidation behavior of high Nb-
containing TiAl alloys, Corros. Sci. 166 (2020), 108449.
[45] J. Ju, C. Yang, S.Q. Ma, M.D. Kang, K.M. Wang, J.J. Li, H.G. Fu, J. Wang, Effect of
temperature on oxidation resistance and isothermal oxidation mechanism of novel
wear-resistant Fe-Cr-B-Al-C-Mn-Si alloy, Corros. Sci. 170 (2020), 108620.
[46] C. Wagner, Theoretical analysis of the diffusion processes determining the
oxidation rate of alloys, J. Eelectrochem. Soc. 99 (1952) 369–380.
14
Corrosion Science 195 (2022) 109984
[47] D. Zou, Y. Zhou, X. Zhang, W. Zhang, Y. Han, High temperature oxidation behavior
of a high Al-containing ferritic heat-resistant stainless steel, Mater. Charact. 136
(2018) 435–443.
[48] X. Cheng, K. Du, D. Wang, Effect of doping Al on the high-temperature oxidation
behavior of Ni-11Fe-10Cu alloy, Oxid. Met. 93 (2020) 417–431.
[49] J.H. Kim, B.K. Kim, D.I. Kim, P.P. Choi, D. Raabe, K.W. Yi, The role of grain
boundaries in the initial oxidation behavior of austenitic stainless steel containing
alloyed Cu at 700C for advanced thermal power plant applications, Corros. Sci. 96
(2015) 52–66.
[50] V.P. Deodeshmukh, S.J. Matthews, D.L. Klarstrom, High-temperature oxidation
performance of a new alumina-forming Ni-Fe-Cr-Al alloy in flowing air, Int. J.
Hydrog. Energy 36 (2011) 4580–4587.
[51] M.P. Brady, I.G. Wright, B. Gleeson, Alloy design strategies for promoting
protective oxide-scale formation, JOM 52 (2000) 16–21.
[52] T. Doi, K. Kitamura, Y. Nishiyama, N. Otsuka, T. Kudo, M. Sato, E. Ikenaga,
S. Ueda, K. Kobayashi, Analysis of Cu segregation to oxide-metal interface of Ni-
based alloy in a metal-dusting environment, Surf. Interface Anal. 40 (2008)
1374–1381.
[53] S. Hayashi, D. Kudo, R. Nagashima, H. Utsumi, Effect of Cu on oxidation behaviour
of FCC Fe-Ni-Cr-Al and Ni-Cr-Al based alloys, Corros. Sci. 163 (2020), 108273.
[54] R.E. Lobnig, H.P. Schmidt, K. Hennesen, H.J. Grabke, Diffusion of cations in
chromia layers grown on iron-base alloys, Oxid. Met. 37 (1992) 81–93.
[55] D.J. Young, High Temperature Oxidation and Corrosion of Metals. Alloy oxidation
II: Internal Oxidation, Elsevier, 2008, pp. 261–333.
[56] Y.X. Xu, J.T. Lu, W.Y. Li, Z. Yang, Y.Y. Dang, X.W. Yang, Effect and role of alloyed
yttrium on the fireside corrosion behaviour of Ni-Fe based alloys for 750 ◦ C ultra-
supercritical boiler applications, Corros. Sci. 143 (2018) 148–156.
[57] S. Wang, Z.B. Zheng, K.M. Zheng, J. Long, J. Wang, Y.Y. Ren, Y.M. Li, High
temperature oxidation behavior of heat resistant steel with rare earth element Ce,
Mater. Res. Express 7 (2020), 016571.
[58] J. Lu, H. Zhang, Y. Chen, L. Li, X.Z. Liu, W.W. Xiao, N. Ni, X.F. Zhao, F.W. Guo,
P. Xiao, Y-doped AlCoCrFeNi2.1 eutectic high-entropy alloy with excellent
oxidation resistance and structure stability at 1000 ◦ C and 1100 ◦ C, Corros. Sci.
180 (2021), 109191.