Corrosion Science 190 (2021) 109633

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

Oxidation behavior of AlCoCrFeNiSix high-entropy alloys at 1100 ℃

Yuantian Li, Ping Zhang *, Jinyong Zhang *, Zheng Chen, Baolong Shen
School of Material Science and Physics, China University of Mining and Technology, Xuzhou, Jiangsu, 221116, China

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

Keywords: AlCoCrFeNiSix high-entropy alloys containing different Si contents (x = 0, 0.2, 0.5, 0.8, 1.0 in molar ratio) were
High-entropy alloys prepared by vacuum arc-melting. The microstructure and oxidation behavior of these alloys at 1100℃ for 200 h
Oxidation were investigated. After adding Si, the alloys mainly consist of BCC and Si-rich precipitates, and both the size and
Silicon content
quantity of the Si-rich precipitates increase with increase in the Si content. A suitable content of Si in the alloys
Silicide
Spallation
improves the oxidation resistance for promoting the formation of a dense single Al2O3 scale, while excessive Si
imposes an adverse effect by forming easy-peeling scales composed of Al2O3 outer layer and mixed oxides inner
layer. Formation and failure mechanisms of the oxide scales on these alloys during oxidation have been
discussed.

1. Introduction
Thermal barrier coatings (TBCs) have been widely used in the pro­
tection of gas-turbine engines and other hot components against high
temperature oxidation [1,2]. Usually, the advanced TBCs consist of a
thermally insulating ceramic topcoat (Y2O3-stabilized ZrO2 (YSZ)) and
an intermediate metallic bond coat (e.g. MCrAlY, M=Co, Ni, Fe or a
mixture) [3–5]. During the oxidation process, the thermally grown oxide
(TGO, mainly Al2O3) layer forms at the interface between ceramic
topcoat and metallic bond coat, and the spalling failure of the TBCs
usually occurs at this interface because of rapid growth of the TGO layer
[6]. Therefore, a bond coat system with a slowly growing TGO will be
beneficial to prolong the service life of TBCs [5,7].
Recently, high entropy alloys (HEAs) have attracted wide attention
due to their novel composition design, unique phase structure and
excellent mechanical properties [8–11]. Among these alloys, AlCoCr­
FeNi was a representative HEAs system, which is considered to be a
candidate high temperature structure material because of its acceptable
yield strength at elevated temperatures and compressive ductility at
room temperature [12–17]. In addition, the AlCoCrFeNi shows similar
elemental compositions to MCrAlY to possibly enable a potential inter­
mediate metallic bond coat material for TBCs. However, the oxidation
resistance of the AlCoCrFeNi was still not desirable despite the Al con­
tent reaching 30 at.%. Butler et al. [18] has been reported that a mixed
oxide scale consisted of external Cr2O3 layer and internal Al2O3 layer
formed on the AlCoCrFeNi after oxidation at 1050℃ for 50 h, and the
oxide scale exhibited poor adhesion.
For the typical Al2O3 forming alloys/coatings, many studies have
been demonstrated that the addition of Si can change the growth
mechanism of oxide scale and significantly improve their oxidation and
hot corrosion resistance [19–21]. Wang et al. [19] have reported that
Si-modified Ni-Al and Ni-Cr-Al alloys exhibit better oxidation protection
by facilitating the formation of Al2O3 scale. Meanwhile, it has been
confirmed that Si can retard the spallation of Al2O3 scale and improve
the adhesion between scale and the substrate [20]. On the other hand,
the formation of SiO2 within the oxide scales would be beneficial to
enhance their oxidation and hot corrosion resistance [21]. In compari­
son with Al2O3/Cr2O3/spinel mixed oxide scale formed on Al0.6CrFe­
CoNi HEAs, the addition of Si promotes the formation of a continuous
Al2O3 scale on Al0.6CrFeCoNiSi0.3 alloy at 800− 1000℃ for 100 h [22].
Cheng et al. [23] have investigated the microstructure of Al0.3CoCrFe­
NiSix HEAs with various amount of Si, but the effect of Si on the
oxidation resistance of the alloys was not revealed. The addition of Si in
the AlCoCrFeNi HEAs leads to the multi-phase structure [24], and would
certainly impose an influence on their oxidation behavior at high tem­
peratures. Thus, in the present work, five kinds of AlCoCrFeNiSix HEAs
containing AlCoCrFeNi (Si0), AlCoCrFeNiSi0.2 (Si0.2), AlCoCrFeNiSi0.5
(Si0.5), AlCoCrFeNiSi0.8 (Si0.8) and AlCoCrFeNiSi1.0 (Si1.0) have been
designed and prepared. The effects of Si content on the microstructure
and oxidation behavior of the alloys at 1100℃ up to 200 h have been
investigated.

* Corresponding authors.
E-mail addresses: zhangping0095@cumt.edu.cn (P. Zhang), jyzhang@cumt.edu.cn (J. Zhang).

https://doi.org/10.1016/j.corsci.2021.109633
Received 16 January 2021; Received in revised form 1 June 2021; Accepted 20 June 2021
Available online 21 June 2021
0010-938X/© 2021 Elsevier Ltd. All rights reserved.
Y. Li et al.
Fig. 1. XRD patterns of the five HEAs in as-cast state.
2. Experimental procedures
The AlCoCrFeNiSix (x = 0, 0.2, 0.5, 0.8, 1.0) HEAs ingots were
prepared by vacuum arc melting. The mixture of high purity (99.9 wt.%)
Fig. 2. BSE images of the five HEAs in as-cast state.
(a) Si0, (b) Si0.2, (c) Si0.5, (d) Si0.8, (e) Si1.0.
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Corrosion Science 190 (2021) 109633
constituent elements Al, Co, Cr, Fe, Ni and Si were placed on water-
cooled copper crucibles, and each button was re-melted by six times
to obtain chemical homogeneity.
The AlCoCrFeNiSix HEAs ingots were cut into 5 mm × 5 mm × 10
mm specimens, mechanically ground to 1200# and then ultrasonically
cleaned. The oxidation behavior of these alloy were characterized at
1100℃ up to 200 h in an open-ended tube electric furnace in air. The
alloy specimen was placed in an alumina crucible so that the total
weight change including spalled oxides could be obtained. Prior to the
oxidation test, the crucible was calcined at 1400℃ for the purpose of no
mass change itself during oxidation test. The heating rate of the oxida­
tion test to 1100℃ was 10℃/min. During the oxidation process, the
mass changes of the alloy specimens (total mass of the specimen with
possible spalled oxides contained in the crucible) with different holding
times were weighed in an electronic balance with an accuracy of 0.0001
g. Three measurements for each specimen were conducted and the
average value with standard deviation was given.
The phase constitutions of the AlCoCrFeNiSix HEAs before and after
oxidation were characterized using X-ray diffraction (XRD, Bruker D8
Advance) with Cu-Kα radiation at 40 kv and 40 mA. The morphology
and chemical composition of the alloys were identified using scanning
electron microscopy (SEM, SU3500) with energy dispersive spectrom­
eter (EDS). Detailed microstructural characterizations of the alloys and
Y. Li et al. Corrosion Science 190 (2021) 109633

Table 1 regions are rich in Cr and Fe elements, and the element segregation
Chemical compositions of the five HEAs in Fig. 2. degree in the alloys increases with increasing the Si content. The Si
Element (at. %) content in the inter-dendrite zone is higher than that in the dendrite
Specimens zone, while Co element is almost uniformly distributed. In addition, it
Al Co Cr Fe Ni Si
can be seen that the grain boundaries (GBs) become clear and coarse in
Si0 Nominal 20.00 20.00 20.00 20.00 20.00 – the alloys containing Si content exceeds 0.5, as shown in Fig. 2(c) – (e).
19.4 21.0 18.6 19.7 21.3 –
Si0.2 Nominal 19.23 19.23 19.23 19.23 19.23 3.85
Some needle-like precipitations are observed along the GBs and their
DR 18.7 20.7 17.8 19.3 20.4 3.1 volume fraction increases evidently with increasing the Si content. Ac­
ID 12.9 20.7 23.8 22.0 15.9 4.7 cording to the XRD and EDS analyses, it can be determined that these
Si0.5 Nominal 18.18 18.18 18.18 18.18 18.18 9.10 precipitations are intermetallic Cr3Si.
DR 26.7 19.7 10.1 13.5 24.0 6.0
Fig. 3 demonstrates the representative TEM bright-field (BF) images
ID 14.2 17.6 17.0 17.6 15.0 18.6
Si0.8 Nominal 17.24 17.24 17.24 17.24 17.24 13.80 of Si1.0 alloy, the corresponding selected-area electron diffraction
DR 33.2 20.1 6.3 9.6 25.8 5.0 (SAED) patterns and the high resolution TEM (HRTEM) morphology
ID 13.2 18.3 18.7 19.5 15.9 14.4 taken from different regions are given in the insets. As presented in Fig. 3
Si-rich phase 2.2 15.4 31.8 20.2 9.6 20.8 (a), a periodic, nano-scale structure with a size of about 100 nm con­
Si1.0 Nominal 16.67 16.67 16.67 16.67 16.67 16.67
DR 32.5 19.8 5.4 10.0 25.7 6.6
sisting of alternating bright and dark interconnected phases, which has
ID 9.3 16.8 24.1 18.2 13.1 18.5 been identified as a modulated plate structure consisted of disordered
Si-rich phase 2.3 14.4 30.5 20.2 8.9 23.7 phase (A2) and ordered phase (B2) formed by spinodal decomposition
mechanism [26,27]. The SAED pattern along the [111] zone axis of the
selected-area A in Fig. 3(a) exhibits a standard BCC and another set of
oxides were studied by FEI Tecnai F20 transmission electron microscope
weaker super-lattice (as labeled by the red circle in Fig. 3(a)) is detected,
(TEM).
suggesting the existence of an ordered BCC (B2) phase [25,28]. The
HRTEM image and corresponding schematic diagram of the interface
3. Results and discussion demonstrate the interfacial coherency between A2 and B2. As shown in
Fig. 3(b), the precipitates (dark contrast) have been determined as Cr3Si.
3.1. Microstructure of the alloys As a result of tilting the zone axis, there are two sets of diffraction pat­
terns. The SAED patterns of the selected-area C in Si1.0 alloy indicate that
Fig. 1 shows XRD profiles of the AlCoCrFeNiSix HEAs. Single BCC the precipitate structure is also a standard BCC structure. In Fig. 3(c), the
phase is identified in Si0 alloy. With the addition of Si, a super-lattice HRTEM image and corresponding schematic diagram at the interface of
reflection (100)B2 related to the ordered BCC phase occurs near 2θ ≈ two typical structures of BCC matrix and Cr3Si show that the orientation
31◦ , indicating that the presence of phase separation in Si-containing of the two phases is relatively consistent, but there is a slight difference
alloys [25]. Moreover, some silicide phases are clearly detected in the in orientation.
alloys contained the Si content exceeds 0.8.
The BSE images of the AlCoCrFeNiSix HEAs are presented in Fig. 2, 3.2. Oxidation kinetics of the alloys at 1100 ℃
and the EDS results of the marked phases are listed in Table 1. It can be
seen that the Si0 alloy shows a single even BCC structure with a mean The kinetics curves of the five alloys being oxidized at 1100℃ for
chemical composition similar to the nominal composition. After adding 200 h are presented in Fig. 4. It can be seen that the oxidation kinetics of
Si into the base alloy, typical cast dendrite structure is presented in the all the five alloys can be approximately fitted by the parabolic law
alloys due to constitutional segregation [26], as shown in Fig. 2(b)–(e).
Based on the EDS analysis results in Table 1, it is clear that the dark Δm
( )2 = kp t (1)
dendrite regions are rich in Al and Ni elements, the gray inter-dendrite A

Fig. 3. (a) Bright-field (BF) TEM image for the

matrix region of Si1.0 alloy (the corresponding
selected-area electron diffraction (SAED) pat­
terns and high resolution bright-field (HRTEM)
morphology are displayed on the right of (a));
(b) BF image for the precipitate of Si1.0 alloy
(the corresponding SAED patterns in the
selected-area C and HRTEM morphology
marked by the red dotted line are given on the
right of (b)); (c) BF image of Si1.0 alloy at the
interface between matrix and precipitate (the
corresponding HRTEM image taken from the
matrix/ precipitate region of the Si1.0 alloy in
the red dotted frame and corresponding sche­
matic diagram are displayed on the right of (c))
(For interpretation of the references to colour in
this figure legend, the reader is referred to the
web version of this article).

3
Y. Li et al.
Fig. 4. Oxidation kinetics curves of the five HEAs at 1100 ◦ C for 200 h: (a) Mass change as a function of time, (b) Mass change as a function of the square root of time.
Fig. 5. XRD patterns of the five HEAs after oxidation at 1100 ◦ C for 200 h.
− 2
Where Δm A is mass gain per unit area (mg∙cm ), t is the oxidation time
(h) and kp is the oxidation rate constant (g2 cm-4∙s-1). The parabolic
oxidation rate constant values kp can be determined by the plots of the
weight gain per area unit versus the square of oxidation time, as shown
in Fig. 4(b). Obviously, Si0.2 alloy exhibits the smallest mass gain in
comparison with other alloys and follows the parabolic law in the
overall oxidation process with a nearly constant slope. The kp values of
Si0.2 alloy is calculated of about 0.38 × 10-11 g2 cm-4s-1, which is much
lower than that of other alloys. The kinetics of Si0, Si0.5, Si0.8 and Si1.0
alloys can be divided into two stages, an initially fast stage (before 20 h)
and a lately slower stage (during 20− 200 h). The fitted oxidation rates
kp values of Si0 alloy for two stages are 0.58 × 10-9 g2 cm-4s-1 and 2.80 ×
10-11 g2 cm-4s-1, respectively, slightly higher than that of Si0.5 alloy but
smaller than that of Si0.8 alloy. Si1.0 alloy has the largest oxidation rate,
which exhibits kp value of 1.16 × 10-9 g2 cm-4s-1 and 1.50 × 10-10 g2 cm-
4 -1
s , respectively. Usually, the lowest kp value indicates the best oxida­
tion resistance performance. Therefore, it can be concluded that a
suitable content of Si addition possesses a positive effect on the oxida­
tion resistance of AlCoCrFeNi at 1100℃ for 200 h.
3.3. Microstructure of the alloys after oxidation
Fig. 5 displays the XRD patterns conducted on the surfaces of the five
alloys after oxidation at 1100℃ for 200 h. Alumina (α-Al2O3: JCPDS file
No. 75-1864) is considered to be the major constituent in all the oxide
scales of the alloys. For Si0 alloy, small amount of Fe-base spinel oxides
are detected and the peak of the BCC phase is still recognizable due to
spallation of the oxide scale locally. Some new silicides (Cr15Co9Si6:
4
Corrosion Science 190 (2021) 109633
JCPDS file No. 29-0446 and Cr13Ni5Si2: JCPDS file No. 54-0370) are
observed in Si0.2 and Si0.5 alloys after 200 h oxidation. For Si0.8 and Si1.0
alloys, Cr3Si (JCPDS file No. 07-0186) phase can still be identified.
Fig. 6 presents the surface morphologies of the oxide scales formed
on the five alloys after oxidation at 1100℃ for 200 h, and the corre­
sponding EDS results of the marked sites are listed in Table 2. It can be
seen that all the alloys after oxidation are covered by dark oxide scales.
The dark oxide scales can be identified as α -Al2O3 by EDS, which is
consistence with the results of XRD analysis in Fig. 5. The serious
spallation of the Al2O3 scale is presented on Si0 alloy after 200 h
oxidation, and some gray spinel oxides rich in Fe, Cr, Co and Ni are
found underneath the Al2O3 scale, as shown in Fig. 6(a). The Al2O3 scale
formed on the Si0.2 alloy after oxidation for 200 h is relative dense and
compact, no obvious spallation is observed (Fig. 6(b)). However, for
Si0.5, Si0.8 and Si1.0 alloys, the rumpling, cracking and spalling of the
Al2O3 scales with different degrees are found after 200 h oxidation
(Fig. 6(c)–(e)), and the mixed oxides composed of Cr, Ni, Fe, Si and O are
observed beneath. In addition, numerous tiny whiskers oxides are also
found on the Al2O3 scales of all the alloys. These whiskers oxides are
probably θ-Al2O3. It has been reported that the θ-Al2O3 is a metastable
oxide, which will transform to stable α-Al2O3 during high temperature
oxidation process [29].
Typical cross-section BSE images of the five alloys after oxidation at
1100℃ for 200 h are shown in Fig. 7. The corresponding EDS results of
the marked phases are listed in Table 3. The oxide scale formed on the
Si0 alloy is about 18 μm thick, and consists of a double-layer structure, as
shown in Fig. 7(a). Combined with the cross-section mapping analysis of
Si0 alloy presented in Fig. 8(a), it can be seen that the outer layer of the
scale (location 1) is identified as Al2O3, and the relatively loose inner
layer of the scale (location 2) is a mixture of spinel. Additionally, a
continuous Al-depletion layer with a thickness of ~28 μm is observed
beneath the oxide scale (Fig. 8(a)). As shown in Figs. 7(b) and 8 (b), a
single and compact Al2O3 scale with a thickness of about 5 μm is found
on the Si0.2 alloy after oxidation. In addition, compared with the Al-
depletion zone in Si0 alloy, a thinner Al-depleted region (~20 μ m)
with higher Al content exists beneath the Al2O3 scale. Thus, it can be
concluded that the addition of Si in AlCoCrFeNi alloy improved the
oxidation resistance by promoting the formation of a dense single Al2O3
scale.
However, excessive Si addition in this study imposes an adverse ef­
fect on the oxidation resistance of the AlCoCrFeNi alloy. For Si0.5, Si0.8
and Si1.0 alloys, as shown in Fig. 7(c) – (e), the oxide scales formed on
these alloys after 200 h oxidation have transformed into a double-layer
structure again, i.e., the Al2O3 outer layer and the mixed oxides inner
layer. Moreover, compared with the oxide scale formed on Si0 alloy, the
thickness of the mixed oxides inner layer increases obviously, and the
cracking and peeling of the Al2O3 outer layer become more serious.
Combined with the cross sectional mapping analysis of Si1.0 alloy shown
in Fig. 8(c), it can be seen that the mixed oxides inner layers consist
Y. Li et al. Corrosion Science 190 (2021) 109633

Fig. 6. Surface SEM images of the five HEAs after oxidation at 1100℃ for 200 h.
(a) Si0, (b) Si0.2, (c) Si0.5, (d) Si0.8, (e) Si1.0.

mainly of Cr, Ni, Fe, Si and O. Fig. 9 shows the TEM bright-field images
Table 2
with corresponding SAED patterns and HRTEM morphology of the oxide
Chemical compositions of the five HEAs in Fig. 6.
scale formed on the Si1.0 alloy after oxidation. Both α- and θ-Al2O3 are
Element (at. %) detected in the oxide scale, and the top-left inserted SAED pattern next
Position
Al Co Cr Fe Ni Si O to the long stick α-Al2O3 can be identified as mixed oxides. It should be
Si0 No.1 35.4 – – – – – 64.6
noted that no SiO2 sub-layer is observed in the oxide scales of the alloys
No.2 52.4 – – – – – 47.6 containing the Si contents even reached to 0.8 and 1.0. This reveals that
No.3 4.2 11.9 13.0 15.5 3.8 – 51.6 the selective oxidation of Si has not occurred, although compared with
No.4 7.8 23.7 24.7 25.6 14.2 – 4.0 other elements such as Ni, Fe and Cr, Si has a higher affinity with O.
Si0.2 No.5 43.7 56.3
However, beneath the oxide scales, the internal oxidation is observed,
– – – – –
Si0.5 No.6 41.9 – – – – – 58.1
No.7 10.0 10.0 27.0 13.2 4.0 10.8 25 and mainly happen in the silicide phases of the alloy, as shown in Fig. 8
Si0.8 No.8 43.4 – – – – – 56.6 (c). This phenomenon implied that the inward diffusion of oxygen
No.9 14.8 1.6 37.2 2.0 1.1 5.6 37.7 through the scale occurs, and these silicide phases presented at grain
No.10 2.2 66.0 6.3 0.4 24.4 0.7
–
boundaries of the alloys can act as a diffusion channel for oxygen.
Si1.0 No.11 37.0 – – – – – 63.0
No.12 5.7 15.8 33.0 20.1 5.8 5.1 14.5
No.13 5.6 17.7 38.1 23.2 5.3 6.0 4.1 3.4. Discussion

It has been demonstrated that adding nonmetallic Si significantly

affects the microstructure of the AlCoCrFeNi HEAs that may be attrib

5
Y. Li et al.
Fig. 7. Cross-section BSE images of the five HEAs after oxidation at 1100℃ for 200 h. (a) Si0, (b) Si0.2, (c) Si0.5, (d) Si0.8, (e) Si1.0.
uted to the strongest binding strength between Si and other constituent
elements. In addition, the high mixing entropy (ΔSmix ) effect obviously
reduces the Gibbs free energy of the alloy system, increases the mutual
solubility between components, inhibits the phase separation of the
alloy during solidification, and promotes the formation of simple solid
solutions. For the design of HEA systems, many theoretically predicted
parameters (such as ΔSmix , ΔHmix , δ, Ω, VEC) have been calculated
6
Corrosion Science 190 (2021) 109633
and summarized as HEAs’ empirical design parameters [30,31]. It has
been proposed that mixing entropy, mixing enthalpy and atomic radius
parameter are the effective parameters affecting phase stability in HEAs
[32]. The criteria for the formation of simple solid solution are − 22 kJ ∙
mol− 1 ≤ ΔHmix ≤ 7 kJ ∙ mol− 1, 11 J/(K ∙ mol)≤ ΔSmix ≤19.5 J/(K ∙
mol) and 0≤ δ ≤8.5 %. In addition, the valence electron concentration
(VEC) is also an important parameter for the formation of BCC/FCC
Y. Li et al. Corrosion Science 190 (2021) 109633

Table 3 δ) can be considered to predict the phase formation of HEA systems, and
Chemical compositions of the five HEAs in Fig. 7. it has been concluded that Ω ≥1.1 and δ ≤6.6 % favor the formation of
Element (at. %) solid solution phase, and if Ω ≤1, the intermetallic compound will form
Position priority [30]. Based on the empirical design rules, the parameters for
Al Co Cr Fe Ni Si O
AlCoCrFeNiSix HEAs have been calculated. From Fig. 10, it can be seen
Si0 No.1 40.3 – – – – – 59.7 that, with increasing Si content in the alloy, ΔSmix increases from 13.38
No.2 8.4 21.5 19.3 23.5 14.6 12.7
J/(K ∙ mol) to 14.90 J/(K ∙ mol), ΔHmix decreases from -12.32 kJ mol− 1
–
No.3 6.8 24.3 27.1 26.4 15.4 – –
Si0.2 No.4 25.2 20.9 10.5 16.3 24.5 2.6 – to -27.33 kJ mol− 1, δ increases from 5.78 % to 6.63 % and Ω decreases
No.5 3.0 18.9 39.8 25.3 6.6 6.4 – from 2.19 to 0.92. Fig. 10(c) shows the correlation between the VEC and
No.6 39.7 – – – – – 60.3 Si content. Si element has the capacity to reduce the VEC value (de­
Si0.5 No.7 39.5 60.5
– – – – –
creases from 8 to 6.664) and translate BCC + FCC phase to BCC phase in
No.8 – – 1.0 – 26.0 – 73.0
No.9 6.8 4.8 6.1 4.9 11.1 40.3 26.0 AlCoCrFeNi HEAs. Thus, Si is an effective BCC former and stabilizer.
No.10 1.4 14.8 44.8 20.2 5.7 13.1 – However, these parameters are usually used to be criteria of the for­
No.11 17.5 20.6 15.3 18.7 18.8 9.1 – mation of simple solid solution. If there is formation of substantial
Si0.8 No.12 40.4 – – – – – 59.6 intermetallic in HEAs, the current results might be slightly deviated with
No.13 37.2 0.6 0.8 2.3 1.8 1.0 56.3
No.14 17.9 20.7 11.1 18.6 19.4 12.3 –
the HEA’s empirical rules. In the present work, as shown in Fig. 2, both
No.15 32.6 2.9 13.9 5.3 13.5 3.2 28.6 Si0 and Si0.2 alloys present BCC structure, while Si0.5, Si0.8 and Si1.0 al­
Si1.0 No.16 39.7 – – – – – 60.3 loys have BCC + silicide structure, and both the size and quantity of the
No.17 10.3 5.4 3.2 6.0 21.0 6.1 48.0 silicide increase with increase in the Si content.
No.18 68.2 6.3 25.3 0.2
– – –
For the typical Al2O3 forming alloys/coatings, it has been widely
demonstrated that Si is an effective alloying element to enhance
phase in alloy [32]. FCC phase is found to be formed at higher VEC (≥ oxidation resistance of the alloys /coatings [19–21]. Similarly, in the
8.0), while BCC phases forms at VEC<6.87, and a mixture of FCC and present work, a suitable content of Si in AlCoCrFeNi alloy (Si0.2) im­
BCC phases coexists at 6.87≤ VEC<8.0. Similarly, Zhang et al. has re­ proves the oxidation resistance of the alloy at 1100℃ by promoting the
ported that both thermodynamic and atomic radius parameters (Ω and formation of a dense single Al2O3 scale. However, the alloys without Si

Fig. 8. SEM-EDS mappings of alloys after oxidation at 1100 ◦ C for 200 h.

(a) Si0, (b) Si0.2, (c) Si1.0.

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Y. Li et al. Corrosion Science 190 (2021) 109633

Fig. 9. TEM bright-field images taken from of the scale formed on Si1.0 alloy after oxidation at 1100℃ for 200 h, and corresponding SAED patterns at various regions.

Fig. 10. Calculated parameters for the stabilized solid solution phase for the five HEAs.

(Si0) or with higher Si content (Si0.5, Si0.8 and Si1.0) exhibit relative poor oxidation behavior of the AlCoCrFeNi alloy, inferred from the micro­
oxidation resistance by forming easy-peeling scales composed of Al2O3 structural evolution of the alloys before and after oxidation at 1100℃
outer layer and mixed oxides inner layer. The effect of Si content on the for 200 h can be classified into three groups, as summarized

8
Y. Li et al.
Fig. 11. Schematic diagram of oxidation behavior for AlCoCrFeNiSix HEAs at 1100 ◦ C for 200 h. (a) Si0, (b) Si0.2, (c) Si≥0.5.
schematically in Fig. 11.
The formation of protective Al2O3 scale on the alloys at high tem­
perature is mainly attributed to the selective oxidation of Al [33].
Thermodynamically, the standard Gibbs free energies of the relevant
oxides formation at 1100℃ calculated by HSC chemistry software are in
the following sequence: ΔGoAl2O3 (-825.04 kJ/mol)＜ ΔGoSiO2 (-666.13
kJ/mol)＜ ΔGoCr2O3 (-518.75 kJ/mol)＜ ΔGoFe2O3 (-311.0 kJ/mol)＜
ΔGoNiO (-232.8 kJ/mol)＜ ΔGoCo3O4 (-192.4 kJ/mol). Thus, for the five
alloys presented in this work, the Al2O3 forms primarily on the surfaces
of the alloys at the initial stage of the oxidation process, as shown in
Figs. 6 and 11. The selective oxidation occurs in the external oxidation
process of materials system, which requires a certain concentration of
solute metal [34]. As the oxidation continues, Al in the upper part of the
alloy is consumed gradually, i.e., an Al-depletion zone forms beneath the
Al2O3 scale. Moreover, the sluggish diffusion effect of the high entropy
alloy will further weaken the advantage of selective oxidation. There­
fore, once the Al content in the residual alloy is not enough to form
Al2O3 exclusively, other oxides will form, as shown in Fig. 11(a). The
critical concentration of solute elements (NB ) in the alloys can be
(0)
expressed as:
[ ∗
]1/2
πg Do ∙Vm
NB(0) > ∙NO(S)
2b DB ∙VOX
Where, NB is affected by NO (oxygen partial pressure), DB (diffusion
(0) (S)
coefficient of solute elements) and Do (diffusion coefficient of oxygen).
Where g∗ is the critical volume fraction of oxide, b is valence state of
metal. Vm is molar volume of metal. VOX is molar volume of the oxide
layer. Usually, the higher Do produces a bigger NO , and both will in­
(S)
crease the NB ,
(0)
while expanding solute diffusion coefficient (DB ) will
result in a lower NB . The solid solution of Si in the BCC structure
(0)
essentially increases the DB value, that is, reduces the critical concen­
tration of Al to selective oxidation. Therefore, compared with Si0 alloy,
only single Al2O3 scale forms on the surface of the Si0.2 alloy after 200 h
oxidation, as shown in Fig. 11(b). Similar oxidation mechanism has also
been revealed in Ni-Al alloys or Fe-Al alloys by Si alloying [35–39].
However, for the alloys containing higher Si content (Si0.5, Si0.8 and
Si1.0), the existence of Si in the alloys is not only solid solution in BCC,
but also the formation of silicide phase because the larger negative
mixing enthalpy between Si and other constituent elements. As shown in
Figs. 7 and 8, the oxide scales formed on these alloys are composed of
Al2O3 outer layer and mixed oxides inner layer, and the wrinkle and
spallation of the Al2O3 outer layer occurs due to the disordered growth
of the mixed oxides inner layer. Obviously, microstructural character­
istic of the higher Si alloys have a significant effect on the oxidation
Corrosion Science 190 (2021) 109633
behavior of the alloys. Once the Al2O3 scale formed priority loses its
protection due to cracking or spalling, the inward diffusion of oxygen
proceeds. Since the Al content in the residual alloys is not sufficient for
selective oxidation, other active elements such as Si, Cr or Fe will react
with oxygen to form inner oxides, as shown in Figs. 7(e) and 11 (c).
Moreover, in the higher Si alloys, substantial silicide (i.e. Cr3Si) pre­
cipitates distribute nonuniformly along GBs, which will act as short-cut
paths for the inward diffusion of oxygen during oxidation, as shown in
Fig. 8(c).
In addition, according to the volume change of the relative oxides
during the transition from the metal lattice to the cationic lattice,
Pilling-Bed worth Ratio (PBR), the volume ratio between the oxide and
the metal consumed, is the key factor for the growth stress in the oxide
scale, which is a significant criterion to judge the integrity of the oxide
scale. PBR value of oxide scale on the alloy is related to the alloy
composition. Assuming there is no stress relaxation during the cooling,
the PBR, oxide scale strain (εγ ) at the oxidation temperature can be
evaluated from the room temperature data based on following equations
[40,41]:
da M0
PBR = (Single oxidized layer) (3)
xd0 A’a
(2)
da (M0B + fyuM0A )
PBR = (Multi-oxide layer) (4)
(1 + f )yd0∗ A’a
fM0A M0B fM0A M0B
d∗0 = + s= + (5)
uS yS ud0A yd0B
where d is the density at room temperature (the subscripts “a/o”
represent the metal and oxides, respectively). d∗0 is the average density of
the mixed oxide scales. da is the density of the alloy before oxidation,
independent of the oxidation process and measured by drainage method.
A’a = (1-a-…-b) AM + ∙∙∙ + bBM + aCM (at.%), is the effective atomic
mass of the alloy. M is the molar mass of a molecule (the subscripts “oA”
and “oB” represent the different oxides). x, y and u are the number of
oxidized metal atoms in the corresponding oxides. f is the estimated
value. It must be pointed out that no single spinel oxide can be formed
on the surface of the alloy. The average density of the mixed oxides scale
is closely related to each oxide and its volume fraction. It is hard to
accurately quantify the d∗0 value. Thus, it is assumed that only Al2O3
forms preferentially on all the alloys at the initial stage of oxidation. The
relevant calculation values related to the five alloys are summarized
schematically in Fig. 12. It can be seen that the PBR value of the oxide
scale increases with increasing the Si content, which leads to large
stresses according to the relationship between PBR and εγ (εγ =
9
Y. Li et al.
Fig. 12. PBR calculated value for the single Al2O3 scale for the five HEAs in the
initial stage of oxidation.
[1 − (PBR)1/3 ]) [40,41]. Thus, the serious spallation of the oxide scales is
observed on the surfaces of the alloys containing higher Si content, such
as Si0.5, Si0.8 and Si1.0 alloys.
4. Conclusion
The effect of Si content on the microstructure and oxidation behavior
of AlCoCrFeNiSix (x = 0, 0.2, 0.5, 0.8, 1.0) high-entropy alloys at 1100℃
were studied. The microstructure of the alloys changes from single BCC
to BCC + silicide phases with addition of Si. The silicide phases are
identified as Cr3Si, and both their size and quantity increase with
increasing Si content. A suitable addition of Si in the alloys is beneficial
to the formation of Al2O3 scale priority by reduces the critical concen­
tration of Al selective oxidation, but an excess of Si in the alloys destroys
the integrality of the Al2O3 scale due to formation and disordered
growth of mixed oxides underneath. The Cr3Si presented at grain
boundaries of the alloys acts as a diffusion channel for oxygen to form
internal oxidation. After 200 h oxidation at 1100℃, Si0.2 alloy exhibits
the best oxidation resistance.
Authorship contributions
Please indicate the specific contributions made by each author (list
the authors’ initials followed by their surnames, e.g., Y.L. Cheung). The
name of each author must appear at least once in each of the three
categories below.
Category 1
Conception and design of study: Ping Zhang, Yuantian Li;
acquisition of data: Yuantian Li, Ping Zhang;
analysis and/or interpretation of data: Yuantian Li, Ping Zhang,
Jinyong Zhang, Zheng Chen, Baolong Shen;
Category 2
Drafting the manuscript: Yuantian Li, Ping Zhang;
revising the manuscript critically for important intellectual content:
Yuantian Li, Ping Zhang, Jinyong Zhang, Zheng Chen, Baolong Shen;
Category 3
Approval of the version of the manuscript to be published (the names
of all authors must be listed): Yuantian Li, Ping Zhang*, Jinyong Zhang*,
Zheng Chen, Baolong Shen.
Declaration of Competing Interest
The authors report no declarations of interest.
10
Corrosion Science 190 (2021) 109633
Acknowledgement
The work was supported by the Fundamental Research Funds for the
Central Universities (Grant No. 2017XKQY009).
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