Corrosion Science 196 (2022) 110046

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

High-temperature oxidation of Mg–Ca alloy: Experimentation and density

functional theory
Yue Ming a, Guoqiang You a, b, *, Fanjin Yao a, Sheng Zeng a, Jun Zhang c, Jianhua Zhao a, b,
Wen Zeng a, **
a
College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China
b
National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing 400044, China
c
Environmental Sensing and Modeling, Technical University of Munich, Munich 80333, Germany

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

Keywords: Oxidation resistance of Mg alloys with different amounts of Ca were examined. The oxidation resistance of Mg at
α-Mg 515 ◦ C was significantly improved by alloying with Ca, and Mg alloyed with 1.0 wt% Ca demonstrated the best
Mg2Ca oxidation resistance. Based on these observations, combined with Gibbs free energy and density functional
High temperature
theory calculations, α-Mg and Mg2Ca oxidation models describing the oxidation process are proposed. Oxide
Oxidation
films formed on α-Mg are effective at improving the oxidation resistance, whereas those formed on Mg2Ca are
Oxidation model
unstable, and tend to peel off from the substrate, resulting in further oxidation.

1. Introduction elements are another group of substances considered to be effective at

Magnesium and its alloys are strongly appealing to many industrial
fields, because of their outstanding properties, such as the low density,
high specific strength, high fluidity for casting, satisfactory electric
shielding effect, and excellent machinability [1–3]. However, their high
affinity to oxygen, especially at high temperatures, is a major drawback,
which limits their more widespread applications [4,5]. The Pil­
ling–Bedworth ratio [6] of MgO is 0.80, indicating the loose structure of
MgO, which makes it difficult to provide sufficient protection for the
substrate [7]. Moreover, the vapour pressure of Mg increases as the
temperature increases, which results in micro-cracks in the MgO film
and fractures in the oxide film [3]. Generally, the oxidation resistance of
Mg alloys can be improved via the enhancement of the compactness of
the oxide film, and via the addition of alloying elements, which is
considered to be a simple and effective method. Recently, many re­
searches have been conducted on the oxidation behaviour of Mg alloys.
The element Be has drawn much attention because BeO has a high Pil­
ling–Bedworth ratio (1.70) [6]. For example, the additional micro­
alloying of Mg–9Al–1Zn using 60 wt. ppm Be improved the oxidation
resistance of the Mg alloy at high temperature, which was attributed to
the fine-grained (Mg, Be)O surface film on the AZ91Be60 alloy [8].
However, the toxicity of Be makes it difficult to handle. Rare earth (RE)
improving the oxidation resistance. For example, researches have
demonstrated that dissolved Y in an Mg matrix is beneficial for
enhancing the oxidation resistance of Mg alloys [9–11]. However, once
Y combines with Al to form the stable Al2Y compound, its capacity to
prevent oxidation disappears [12]. Other RE elements, such as Gd, Ce,
and Nd, have also indicated super improvement in oxidation resistance
[13–17]. However, the application of RE elements is limited because of
their high costs.
Another common element that has demonstrated promise into
enhancing the oxidation resistance, but at a low cost, is Ca [18,19].
Inoue et al. [20] reported that Mg–10Al–5Ca (at%) can be melted in air
without cover gas or flux because of a protective oxide film consisting of
three layers: a fine CaO outer film, a fine MgO intermediate film, and a
coarse MgO innermost film. Cheng et al. [21] determined that the
ignition temperature of the AZ91 alloy could be improved from 524 ◦ C
to 770 ◦ C when it is alloyed with 1.69 wt% Ca. Meanwhile, Lee et al.
[22] reported that the ignition temperature of AZ91D alloyed with 5 wt
% Ca was 74.78% higher than that of the AZ91D alloy without Ca, and
exhibited a negligible oxidation rate at 673 K for 180ks with an oxide
film consisting of two layers, a CaO film and MgO film.
However, preliminary reports on the oxidation resistance of Mg–Ca
alloys insisted that only α-Mg contributes to the formation of the oxide

* Corresponding author at: College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China.
** Corresponding author.
E-mail addresses: ygq@cqu.edu.cn (G. You), wenzeng@cqu.edu.cn (W. Zeng).

https://doi.org/10.1016/j.corsci.2021.110046
Received 19 August 2021; Received in revised form 20 December 2021; Accepted 21 December 2021
Available online 24 December 2021
0010-938X/© 2021 Elsevier Ltd. All rights reserved.
Y. Ming et al.
film, and the second phase Mg2Ca is beneficial for the oxidation resis­
tance by increasing the melting point [18,23]. Therefore, in this study,
Mg alloyed with 0.3 wt%, 0.5 wt%, 1.0 wt%, 2.0 wt%, and 3.6 wt% Ca
(Mg–xCa, x = 0, 0.3, 0.5, 1.0, 2.0, 3.6) were produced in an electric
resistance furnace, with the following objectives (i) to investigate the
oxidation kinetics of Mg–Ca alloys near the eutectic temperature, (ii) to
characterise the microstructure and oxide film after oxidation via
scanning electron microscopy (SEM) with energy dispersive spectros­
copy (EDS), (iii) to calculate the Gibbs free energy of reactions during
oxidation and the bond characterisations in α-Mg and Mg2Ca based on
density functional theory (DFT), and (iv) to construct oxidation models
of α-Mg and Mg2Ca representing the oxidation process. The research
results can be a useful reference for the design and improvement of
properties of Mg alloys.
2. Experimental and simulation methods
2.1. Experimental methods
Experimental Mg–Ca alloys were produced using pure Mg (99.95 wt
%) and Mg–20 wt% Ca master alloy, in a graphite crucible in an electric
resistance furnace, under the protection of a mixed atmosphere of N2
and SF6. Pure Mg was heated to 700 ◦ C to be melted completely, and
then an Mg–20%Ca master alloy in the required amount for forming the
desired composition was added into the melt when the temperature
reaches 720 ℃. To ensure the complete dissolution of the alloying ele­
ments and melt homogenisation, the alloy melt was maintained at
720 ◦ C for 20 min. The melt was then casted into a columniform steel
mould with a size of Φ80 mm, which was preheated to 180 ◦ C. The
experimental chemical compositions of the Mg-Ca alloys in terms of the
Ca content are tested using X-ray fluorescence (XRF-1800 CCDE), and
the results are listed in Table 1.
An isothermal oxidation test was conducted using a Mettler Toledo
1/1100 SF thermal gravimetric analysis (TGA) apparatus. Specimens
were cut into Φ5 mm × 3 mm pieces from the cast ingots and then
mechanically ground. The TGA test was conducted at 515 ◦ C under
synthetic air (79 vol% high-purity nitrogen and 21 vol% high-purity
oxygen) atmosphere, which was heated at a rate of 15 ◦ C /min and
maintained for 1.5 h.
The microstructure phases were identified via X-Ray Diffraction
(XRD) and using Jade 6.0 software. Oxidation samples for SEM analysis
were prepared in a heat treatment furnace under O2 atmosphere, which
was heated at a rate of 15 ◦ C /min and maintained at 515 ◦ C for 1.5 h.
The microstructures of the cast alloys were examined after grinding and
corrosion. The microstructures, surfaces, and cross sections of the oxide
layers were observed using a JEOL JSM-7800F SEM. Furthermore, the
distribution of the alloying elements was obtained by EDS.
2.2. DFT calculation
The Vienna Ab-initial Simulation Package (VASP) was used to
perform the DFT calculations [24], in which the generalised gradient
approximation (GGA) refined by Perdew, Burke, and Emzerhof (PBE)
was employed [25–28].
Mg2Ca and α-Mg are the common phases in Mg–Ca alloys. The solid
solubility of Ca in α-Mg is very small [29], and Ca is dissolved in the Mg
matrix in the form of a replacement solid solution [30]. In order to avoid
interactions between adjacent cells, a 4 × 4 × 2 supercell Mg with one
Ca-doping atom model was established to represent the α-Mg. The
crystal structures of Mg2Ca and α-Mg are shown in Fig. 1, and the lattice
Table 1
Ca content of Mg–Ca alloys.
Pure Mg Mg–0.3Ca
Measured Ca (wt%) – 0.33
Corrosion Science 196 (2022) 110046
parameters are listed in Table 2. The energy cut-off of the plane wave
was set to 450 eV. Convergence was achieved when the calculated total
energy and force were less than 10− 5 eV/atom and 0.02 eV/Å. The
Monkhorst–Pack grid was employed for k-grid samplings in the Brillouin
zone integration [31], which were 4 × 4 × 2 for Mg2Ca and 2 × 2 × 2 for
α-Mg.
3. Results and discussion
3.1. DFT calculation results
To reveal the bond characteristics, the electron density difference
and electron density were investigated. The electron density difference
is visualised in Fig. 2, where the contour lines range from − 0.03 e/Å3 to
0.03 e/Å3 with an interval of 0.015 e/Å3. The blue area indicates the
acquisition of electrons, whereas the red area indicates the loss of
electrons. The electron density is visualised in Fig. 3, where the contour
lines range from 0.04 e/Å3 to 0.4 e/Å3 with an interval of 0.09 e/Å3. The
red area indicates the high electron density, whereas the blue area im­
plies the low electron density. For Mg2Ca, as shown in Fig. 2(a), the blue
area around the Ca atom indicates the acquisition of electrons, whereas
the red area around the Mg atom indicates the loss of electrons. How­
ever, the charge density of the two atoms themselves is relatively large,
as shown in Fig. 3(a). The loss of electrons between the Ca atoms results
in a low charge density, demonstrating the nature of the metallic bond
between the Ca atoms. Conversely, electrons are obtained between the
Mg atoms, and the charge density between them is also high, which
conforms to the characteristics of covalent bonds. The electron density
between the Mg and Ca atoms is high near the Mg atom, but low near the
Ca atom, indicating that there is an ionic bond between Mg and Ca, as
shown in Fig. 3(a). Past studies have demonstrated that in an AB2 type
Laves phase, a metallic bond exists between the A atoms, a covalent
bond exists between the B atoms, and an ionic bond exists between the A
and B atoms. Mg2Ca is characterised by an AB2 type Laves phase, which
is also confirmed by the results of analysis of chemical bonds in Mg2Ca.
This result is also consistent with the findings of other studies [32–34].
For α-Mg, as shown in Fig. 2(b), the blue area around the Ca atom in­
dicates the acquisition of electrons, whereas the red area around the Mg
atom indicates the loss of electrons, but the charge density of the two
atoms themselves is still relatively large, as shown in Fig. 3(b). The
characteristics of the metallic bond between Mg and Mg are still main­
tained, whereas the characteristic of the ionic bond between Mg and Ca
are observed.
In order to further understand the bonding characteristics, specially
the ionic bonding characteristics, which are dependent on the charge
transfer between atoms [32], the Mulliken charges are analysed. Table 3
outlines the Mulliken charges of Mg2Ca and α-Mg. For α-Mg, the Mg
atoms are classified into eight categories according to the gain and loss
of electrons, as shown in Fig. 4. In α-Mg, although most of the Mg atoms
obtain charges, the other Mg atoms lose charges. By contrast, in Mg2Ca,
all the Mg atoms obtain charges. In both α-Mg and Mg2Ca, the Ca atoms
lose their charges. The number of transferred charges was used to
evaluate the strengths of the ionic bonds. The transferred charge is 1.10
for one Ca atom in Mg2Ca, whereas the transferred charge is 1.09 for
α-Mg. That is, the transferred charge for Ca in Mg2Ca is similar to that in
α-Mg. Therefore, the interaction between Ca and the surrounding Mg in
Mg2Ca is similar to that in α-Mg. It can be inferred that the Ca atoms in
α-Mg and Mg2Ca are involved in the oxidation reaction.
Mg–0.5Ca Mg–1.0Ca Mg–2.0Ca Mg–3.6Ca
0.49 1.06 1.95 3.65
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Y. Ming et al. Corrosion Science 196 (2022) 110046

Fig. 1. Crystal structures (a) Mg2Ca and (b) α-Mg.

as shown in Fig. 6(a) and (b). By contrast, in Mg–1.0Ca, Ca is consumed

Table 2
mainly at the grain boundaries, as shown in Fig. 6(c). Furthermore,
Lattice parameters of Mg2Ca and α-Mg.
Mg2Ca is formed, and the remaining Ca is dissolved in the α-Mg. As the
Phase Lattice parameters (Å) further increase of Ca concentration, the amount of Mg2Ca increases and
a b c the second-phase network becomes more visible. The volume fractions
Mg2Ca 6.24 10.06
of the second phase of Mg-1.0Ca, Mg-2.0Ca and Mg-3.6Ca are 8.3%,
α-Mg 12.83 10.21 17.4% and 32.8%, respectively.
Fig. 7 shows the Ca solute atoms in the α-Mg of the Mg–Ca alloys. The
number of Ca solute atoms in the α-Mg increases as the Ca concentration
3.2. Microstructure is increased. The average percentages of Ca solute atoms in the α-Mg of
Mg-xCa (x = 0.3, 0.5, 1.0, 2.0, and 3.6) alloys is 0.08, 0.11, 0.34, 0.40,
Fig. 5 shows the XRD patterns of the as-cast alloys. In Mg, Mg–0.3Ca, and 0.41 at%, respectively.
and Mg–0.5Ca, i.e., the alloys with a low Ca content, only α-Mg is clearly
detected. When the concentration of Ca comes up to 1.0 wt%, the peak
of Mg2Ca can be found. As the further increase of Ca concentration, the 3.3. Oxidation kinetics
peak of Mg2Ca becomes more intense.
Fig. 6 presents the microstructures of the Mg–Ca alloys and the EDS Fig. 8 shows the isothermal oxidation kinetics curves of the as-cast
mapping. The XRD results show that, for Mg–0.3Ca and Mg–0.5Ca, Ca is Mg–Ca alloys at 515 ◦ C in synthetic air. As shown in Fig. 8(a), pure
mainly dissolved in the α-Mg matrix, and segregates at grain boundaries, Mg exhibits two typical stages of oxidation: (i) initial parabolic

Fig. 2. Electron density difference, (a) Mg2Ca and (b) Ca-doped Mg.

Fig. 3. Electron density, (a) Mg2Ca and (b) Ca-doped Mg.

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Y. Ming et al. Corrosion Science 196 (2022) 110046

Table 3 time. A is defined as the parabolic oxidation rate: the higher the value of
Mulliken charges of Mg2Ca and α-Mg. A, the higher the oxidation rate. After parabolic oxidation, the oxidation
Phase Element Mulliken charge/e Total/e Charge/e of Mg exhibits a power law with a large oxidation rate in the accelerated
oxidation stage. The power law is expressed as follows:
s p d

Mg2Ca Mg (I) 2.83 7.68 10.51 -0.51 ΔW = DtE + F, (2)

Mg (11) 2.83 7.73 10.56 -0.56
Ca 2.28 6.00 0.63 8.90 1.10 where △W (mg⋅cm− 2) is the weight gain, D and F are the fitting con­
α-Mg Mg (1) 2.69 7.31 10.00 0 stants, E is an exponent, and t (s) is the oxidation time. The parameters of
Mg (2) 2.69 7.32 10.01 -0.01
Mg (3) 2.69 7.29 9.98 0.02
the appropriate law for each oxidation curve after curve fitting are
Mg (4) 2.69 7.31 9.99 0.01 shown in Table 4, The coefficient of determination, R2, indicates an
Mg (5) 2.74 7.36 10.10 -0.1 effective curve fitting.
Mg (6) 2.72 7.37 10.09 -0.09 In the first 1000 s, as shown in Fig. 8(b), pure Mg shows the
Mg (7) 2.69 7.33 10.02 -0.02
maximum A value (0.0063) among those of the examined alloys, indi­
Mg (8) 2.70 7.27 9.97 0.03
Ca 2.05 5.99 0.87 8.91 1.09 cating the highest oxidation rate in this stage. However, the A values of
Mg with Ca added alloys demonstrate insignificant differences.
By contrast, pure Mg follows the power law after 1000 s of oxidation.
During this stage, the increment in the thickness of the MgO layer and
the Mg evaporation simultaneously facilitate internal stresses within the
oxide layer, leading to layer cracks [36]. The cracks act as paths that
promote the inward flow of oxygen and the outward evaporation of Mg,
resulting in severe oxidation. For Mg alloyed with Ca, the oxidation
kinetics still maintain a parabolic law. In this study, the oxidation rates
of the Mg–Ca alloys in this stage exhibit smaller A values than those in
the parabolic stages described earlier, with Mg–1.0Ca exhibiting the
lowest oxidation rate among those of the examined alloys. Meanwhile.
the overall specific weight gains of the alloys after isothermal oxidation
for 1.5 h at 515 ◦ C are shown in Fig. 9. The weight gains of Mg,
Mg–0.3Ca, Mg–0.5Ca, Mg–1.0Ca, Mg–2.0Ca, and Mg–3.6Ca are 0.304,
0.079, 0.056, 0.042, 0.057, and 0.065 mg cm–2, respectively. Pure Mg
demonstrates the maximum weight gain, which is 10 times the mini­
Fig. 4. Classification of magnesium atoms.
mum weight gain, i.e., that of Mg–1.0Ca, among those of the examined
alloys. The TGA results illuminate that the oxidation resistance of Mg is
improved by addition of Ca. Researches have shown that the addition of
Ca results in the formation of a CaO oxide layer, which is effective at
enhancing the oxidation resistances of Mg alloys [18,37–39].

3.4. Analysis of the oxide film

Fig. 10 shows SEM images of the surface morphology after

Fig. 5. XRD patterns of as-cast Mg–Ca alloys.
oxidation stage and (ii) accelerated oxidation stage [35]. Compared with
pure Mg, the Mg alloys with Ca exhibit less oxidation weight gain,
indicating better oxidation resistances. Pure Mg follows a parabolic law
in the first 1000 sand thereafter follows a power law. By contrast, Mg
alloys with Ca follow two parabolic laws throughout the oxidation
period. The parabolic law is expressed as follows::
ΔW = At2 + Bt + C,
where △W (mg cm− 2) is the weight gain = , A (mg cm− 2 s− 2), B
(mg cm− 2 s− 1), C (mg cm− 2) are constants, and t (s) is the oxidation
isothermal oxidation for 1.5 h. Because the surfaces of the samples were
ground for oxidation, grinding grooves could be seen on the surface. The
surface morphology of Mg is shown in Fig. 10(a), where an uncompact
oxide layer accompanied by oxides at a large scale is formed on Mg. In
contrast, in 0.3 Ca, an uncompact oxide film is formed on the surface,
where small oxides are dispersed. Whereas, in Mg–0.5Ca, there is only a
small amount of oxide on the oxide film. As the Ca concentration is
increased to 1.0 wt%, a compact and uniform oxide film is formed, and
no oxides can be seen obviously, indicating a good oxidation resistance.
When the Ca concentration increased to 2.0 wt%, as shown in Fig. 10(e),
some oxides are on the surface, and oxide film becomes uncompact.
Finally, in Mg–3.6Ca, an uncompact oxide film is formed on the surface,
and small particles of oxides can be seen obviously.
Fig. 11 presents SEM images of the cross sections of the oxide film.
The oxide film can be observed clearly, and the thickness of the oxide
film can measured. Based on general analysis, Mg–Ca–O oxide films are
formed on the surfaces of Mg–Ca alloys. Fig. 11(a) shows a thick oxide
film with a thickness of 5.32 µm on Mg, characterised by many oxide
particles. According to these observations, combined with the EDS map
scanning results, O atoms diffuse deeply into the substrate, and segre­
gate in some areas, which implies the formation of MgO particle. The
P–B ratio of MgO is 0.80, which indicates that MgO is an incompact film
(1)
with internal tension stresses [6]. In contrast to Mg, the alloy Mg–0.3Ca
was characterised by the formation of a uniform oxide film with a
thickness of 4.26 µm and no apparent oxide particles. According to the
EDS results, Ca is distributed almost homogeneously and is only partially

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Y. Ming et al. Corrosion Science 196 (2022) 110046

Fig. 6. SEM and EDS images of Mg-Ca alloys, (a) Mg–0.3Ca, (b) Mg–0.5Ca, (c) Mg–1.0Ca, (d) Mg–2.0Ca, and (e) Mg–3.6Ca.

concentrated on the surface of the oxide film. Fig. 11(c) presents the partially concentrated on the surface of the oxide film. For comparison,
cross sectional oxide morphology of Mg–0.5Ca. The thickness of the Fig. 11(d) shows SEM images of the cross sectional oxide film of
oxide film is determined to be 2.50 µm, which is thinner than that of Mg–1.0Ca. The oxide film is inhomogeneous in terms of thickness, with
Mg–0.3Ca. In addition, Ca is distributed homogeneously, and is only an average thickness of 2.47 µm. An apparent accumulation of Ca with a

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Y. Ming et al. Corrosion Science 196 (2022) 110046

is distributed as a network. In order to further analyse the phases in the

alloy, the A-α-Mg and B-Mg2Ca in Fig. 12(a) are further analysed, with
results shown in Fig. 12(b) and (c). Fig. 12(b) shows the structure of
α-Mg. Combined with the results of EDS, it can be seen that Ca is
distributed uniformly in α-Mg, and that the solid solubility of Ca is low,
as shown in Table 5. Meanwhile, Fig. 12(c) reveals that Mg2Ca has a
network structure. The EDS results indicate that there are many areas
with Ca accumulation, and that the Ca% is lower than that in standard
Mg2Ca (33.3 at%), which can be ascribed to the eutectic structure of
Mg2Ca.
Fig. 13 shows the microstructure of Mg–3.6Ca after oxidation, which

Table 4
Parameters of oxidation curves.
Alloy Kinetics Parameters R2

Mg parabolic law (0 < t < 1000 s) A = − 0.0063 0.98

10
power law (t > 1000 s) D = 4.193 × 10− 0.99
E = 2.29
Mg-0.3Ca parabolic law (0 < t < 1000 s) A = − 0.0057 0.97
parabolic law (t > 1000 s) A = − 0.0063 0.96
Fig. 7. Ca% dependency of Ca solute atoms in α-Mg. Mg-0.5Ca parabolic law (0 < t < 1000 s) A = − 0.0048 0.97
parabolic law (t > 1000 s) A = − 0.0023 0.92
Mg-1.0Ca parabolic law (0 < t < 1000 s) A = − 0.0057 0.97
thickness of 0.81 µm is observed. At the same time, Mg is deficient in parabolic law (t > 1000 s) A = − 0.0012 0.94
areas where Ca is abundant. With further increase in the Ca concen­ Mg-2.0Ca parabolic law (0 < t < 1000 s) A = − 0.0056 0.98
tration, as shown in Fig. 11(e) and (f), the thickness of the oxide film parabolic law (t > 1000 s) A = − 0.0013 0.94
Mg-3.6Ca parabolic law (0 < t < 1000 s) A = − 0.0054 0.96
increase to 2.84 µm and 2.88 µm, for Mg–2.0Ca and Mg–3.6Ca,
parabolic law (t > 1000 s) A = − 0.0014 0.96
respectively. More Ca atoms segregate on the surfaces, with the thick­
nesses of 1.04 µm and 1.50 µm, respectively. At the same time, Mg atoms
are deficient in areas where Ca atoms are abundant.
According to Tan at al.’s study, the oxidation resistance of AZ91
alloyed with 60 ppm (wt.) Be was improved by the formation of a (Mg,
Be)O film. The reinforcement of the oxide film was attributed to Be
enrichment, which formed a (Mg, Be)O solid solution. The fine grain size
of the (Mg, Be)O solid solution can improve the hardness and strength of
the oxide layer [8]. In this study, Mg–Ca–O oxide film on Mg–Ca alloys
shows good protection, which can be attributed to the solid solution of
Ca atoms in MgO or Mg atoms in CaO, which improve the hardness and
strength of the oxide film against the internal stress, resulting in the
improvement of oxidation resistance.

3.5. Microstructure after oxidation

To further elucidate the roles of α-Mg and Mg2Ca during oxidation,

the alloy Mg–3.6Ca, which had the maximum amount of Mg2Ca, was
further examined after oxidation. For comparison, the microstructure
without oxidation is shown in Fig. 12. The microstructure of Mg–3.6Ca
after oxidation is shown in Fig. 13.
As shown in Fig. 12, the microstructure of Mg–3.6Ca before oxida­
Fig. 9. Weight gains of Mg-Ca alloys after isothermal oxidation for 1.5 h.
tion consist of α-Mg and Mg2Ca interdendritic intermetallic, and Mg2Ca

Fig. 8. Oxidation kinetics of as-cast alloys at 515 ◦ C in O2 for (a) 7020 s and (b) 1000 s.

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Y. Ming et al.
Fig. 10. SEM images of surface morphology after isothermal oxidation for 1.5 h, (a) Mg, (b) Mg–0.3Ca, (c) Mg–0.5Ca, (d) Mg–1.0Ca, (e) Mg-–2.0Ca, (f) Mg–3.6Ca.
seems to mimic the two-phase microstructures of the as-cast alloys. As
shown in Fig. 13(a), protuberances, like oxidised ridges and depressions,
are present on the oxidised microstructure, which are surrounded by
folds. According to the EDS mapping results, O is distributed relatively
uniformly, whereas Ca and Mg show aggregation and dissipation. The
areas that Ca aggregated and Mg dissipated locate in the depressions and
protuberances. With these findings, combined with the previously pre­
sented analysis of the non-oxidised microstructure, it can be speculated
where the area that Ca aggregated and Mg dissipated is the area with
oxidised Mg2Ca, and that the areas where Mg aggregated and Ca dissi­
pated are those with the oxidised α-Mg. Furthermore, the surface of the
oxidised α-Mg is smooth, whereas the surface of the oxidised Mg2Ca is
uneven. Simultaneously, granular phases are observed in these areas.
The analysis of EDS result 1 in Table 6 shows that these phases are of the
oxidised Mg2Ca particles. In addition, in α-Mg after oxidation, the Ca
content varies, significantly to ten times the Ca content before oxidation.
This is due to the diffusion of Ca atoms from the substrate. By contrast, in
Mg2Ca, the Ca content shows insignificant differences after oxidation,
which can be attributed to the stable structure of Mg2Ca resulting in
difficulty in atom diffusion.
In order to further analyse the microstructure after oxidation, the
representative A-α-Mg area, B-Mg2Ca depression area and C-Mg2Ca
protuberances area were analysed. Fig. 13(b) shows the oxidised
structure of α-Mg, featuring light-coloured and dark-coloured areas.
According to the results of the EDS mapping results, the light-coloured
areas indicate Ca-aggregated regions, whereas the dark-coloured areas
indicate Ca-depleted regions. Meanwhile, Mg and O are distributed
uniformly. Based on these observations, Ca aggregates during the
oxidation of α-Mg, which can be ascribed to the surface-active nature of
Ca. However, the reason for Ca aggregation needs further study. The
structure of the Mg2Ca depression area after oxidation is shown in
Fig. 13(c), revealing that the network structure remains the same before
and after oxidation. EDS mapping results indicate that the light-coloured
areas possess accumulated Ca but lacked Mg. Moreover a Ca–O-enriched
particle is clearly shown on the right. Based on these findings, combined
with EDS result for point 6 in Table 5, the particle is identified as oxi­
dised Mg2Ca. Fig. 13(d)shows the structure of the Mg2Ca protuberances.
A curve showing Ca accumulation is observed in this area. The line is
deemed to be a grain boundary with Ca accumulation, which is related
to the fact that Ca is a surface-active element. The network structure
before oxidation was retained on the left side of the curve. The network
structure is that of Mg2Ca, where an oxidised Mg2Ca particle is present,
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Corrosion Science 196 (2022) 110046
according to the EDS result for point 7 in Table 6. Furthermore, a large
particle can be seen obviously on the upper right of the figure. Based on
the EDS result for point 8, the particle is composed mainly of MgO. It is
inferred that the particle is an oxide inclusion formed during the pouring
of the ingot.
In line with the analysis above, the oxidation process of α-Mg and
Mg2Ca in the Mg–Ca alloy is speculated. For α-Mg, Ca aggregates during
the oxidation process. At the same time, Mg and Ca in α-Mg react with O
to form the Mg–Ca–O oxide layer, which is relatively stable and able to
protect the substrate from oxidation. For Mg2Ca, during the oxidation
process, O reacts with Mg2Ca, forming Mg-Ca-O oxide layer. However,
the structure is unstable, and protuberances are developed. This struc­
ture is similar to the oxide ridge structure formed during the ignition of
Mg alloys, as shown in area C of Fig. 10(a), where protuberances peel off
from the substrate, forming the depression structure shown in area B in
Fig. 10(a). This reduces the protective effect on the substrate, resulting
in further oxidation.
3.6. Oxidation process calculation
Lee et al. [40] revealed that the oxidation of Mg alloys involves
intergranular and intragranular oxidation. The oxidation behaviours of
the alloying elements over the two different phases can be dissimilar
because of the compositional differences between the solid solution and
the second phase. In this study, the Gibbs free energies of the possible
reactions are calculated to assess the oxidation difference between α-Mg
and Mg2Ca. It is assumed that the Mg2Ca exists in the stoichiometric
composition (33.33 at% Ca). Possible reactions can be proposed for
α-Mg and Mg2Ca as follows.
Possible reactions for α-Mg:
2Mg(s) + O2 (g) = 2MgO(s), (3)
( ( )2 )
ΔG(1) = ΔGo(1) + RTln (
αMgO
)
αMg 2 ∗PO2
2Ca(s) + O2 (g) = 2CaO(s), and (4)
( )
(αCaO )2
ΔG(2) = ΔGo(2) + RTln
(αCa )2 ∗PO2
Possible reactions for Mg2Ca:
Y. Ming et al. Corrosion Science 196 (2022) 110046

Fig. 11. SEM images of cross sections of oxide layers, (a) Mg, (b) Mg–0.3Ca, (c) Mg–0.5Ca, (d) Mg–1.0Ca, (e) Mg–2.0Ca, (f) Mg–3.6Ca.

2Mg2 Ca(s) + O2 (g) = 2CaO(s) + 4Mg(s), (5) (( ) )

αMgO 2 (αCa )
( ) ΔG(4) = ΔGo(4) + RTln ( )
(αCaO )2 (αMg )4 αMg2 Ca ∗PO2
ΔG(3) = ΔGo(3) + RTln ( )
αMg2 Ca 2 ∗PO2
where △G is the change in the Gibbs free energy (J), △G0 is the stan­
Mg2 Ca(s) + O2 (g) = 2MgO(s) + Ca(s), and (6) dard Gibbs free energy (J), R represents the gas constant, T is the tem­
perature (K) which the reaction occurs, and α is the activity. Research
has shown that the partial pressure of O2 is 0.21 at the gas/oxide

8
Y. Ming et al.
Fig. 12. Microstructure of Mg–3.6Ca before oxidation, (a)Mg–3.6Ca, (b)Part A, and (c) Part B.
interface [41]. MgO, CaO and Mg2Ca are deemed to be solids, thus αMgO,
αCaO and αMg2Ca are equal to 1. Therefore, instead of elemental activities,
the atomic concentrations of Mg and Ca were calculated. The results of
the reactions in α-Mg are shown in Fig. 14.
Fig. 14 shows the ΔG of the reactions in α-Mg. The calculations have
shown that both MgO and CaO formation are thermodynamically
favourable and they form on the surface at 515 ◦ C in an air atmosphere.
Furthermore, the results show that MgO forms prior to CaO and that
with an increment in Ca content, the difference of ΔG between the two
compounds decreases. However, these calculations do not account for
the diffusion of Ca atoms from the substrate to the surface, which leads
to an increase in the Ca content on the surface, thereby affecting the
oxidation. The previously presented analysis shows that the Ca content
of the oxidised α-Mg in Mg-3.6Ca reaches 4 at%. Based on this data,
ΔG(1) is − 1022015.2 J, and ΔG(2) is − 1031234.9 J, demonstrating that
CaO forms prior to MgO. Therefore, the critical Ca content where
ΔG(1) = ΔG(2) is calculated to be 0.419 at%. When the accumulated Ca
content is higher than 0.419 at%, CaO will be preferentially formed on
the surface. Furthermore, for Mg2Ca, ΔG(3) and ΔG(4) are calculated to
be − 1049957.1 J and − 1002430.5 J, respectively, indicating that
Mg2Ca tends to form CaO after oxidation.
For α-Mg, the calculated Gibbs free energy shows that MgO is pref­
erentially formed. During the oxidation process, Ca atoms diffuse from
the substrate to the oxidised surface to enhance the surface Ca concen­
tration, leading to ΔG(2) < ΔG(1) , which implies that CaO is preferen­
tially generated, resulting in Mg–Ca–O oxide film. By contrast, during
the oxidation of Mg2Ca, CaO is the first to be generated, resulting in an
Mg–Ca–O oxide layer. Mg2Ca is stable at high temperatures, and atoms
are comparatively difficult to diffuse, resulting in a relatively unchanged
Gibbs free energy.
9
Corrosion Science 196 (2022) 110046
3.7. Oxidation mechanism
Based on the above analysis, oxidation models for α-Mg and Mg2Ca
of the Mg–Ca alloys are proposed. The oxidation model of α-Mg is shown
in Fig. 15. During the oxidation process, Ca atoms dissolve in the α-Mg,
diffuse to the oxidation surface, and accumulate in certain regions.
When the Ca content reaches the critical value, which is 0.419 at%, CaO
is preferentially formed on the surface, as shown in Fig. 15(b). The
formation of CaO consumes Ca atoms, resulting in the aggregation of Mg
atoms which promotes the generation of MgO. Hence, an Mg–Ca–O
oxide film with CaO aggregates on the surface is formed. This type of
film is effective at protecting the substrate. When the Ca solid solubility
is very low, some of the CaO aggregates on the surface of the oxide layer.
However, as the Ca content increases, the Ca atoms that diffuse to the
surface increase in number, resulting in CaO fully covering the surface of
the Mg–Ca–O oxide film.
The oxidation model of Mg2Ca is shown in Fig. 16. During the
oxidation process, CaO is preferentially formed compared to MgO.
Because Mg2Ca is a high-temperature stable phase, the Mg and Ca atoms
hardly diffuse. Moreover, it is difficult to replenish Ca atoms to form CaO
aggregation areas. Therefore, the oxidation of Mg2Ca involves the in situ
oxidation of Mg and Ca atoms, which finally forms an Mg–Ca–O oxide
layer. This oxide film that forms on Mg2Ca is unstable, and will peel off
the substrate, resulting in further oxidation and an increase in weight
gain in oxidation kinetics.
For the Mg–Ca alloys examined in this study, when the Ca content is
low, only α-Mg is present in the alloy, and the oxide layer exhibits a
protective effect on the substrate. By contrast, when the Ca is high, the
microstructure is composed of α-Mg and Mg2Ca, and the Ca dissolved in
α-Mg reaches a saturation value. Whereas, the oxide layer formed by
α-Mg exhibits a protective effect, the oxide layer of Mg2Ca is easy to peel
off, which is not good for protecting the alloy from oxidation. Moreover,
Y. Ming et al. Corrosion Science 196 (2022) 110046

Fig. 13. Microstructure of Mg–3.6Ca after oxidation, (a)Mg–3.6Ca, (b)Part A, (c) Part B, and (d) Part C.

Table 5
EDS analysis of Mg–3.6Ca before oxidation.
Position Chemical composition (at%)

Mg Ca

1 88.5 11.5
2 87.6 12.4
3 99.6 0.4
4 99.5 0.5

Table 6
EDS analysis of Mg–3.6Ca after oxidation.
Position Chemical composition (at%)

Mg Ca O

1 41.7 29.0 29.3

2 82.8 12.2 5.0
3 80.8 13 6.0
Fig. 14. ΔG of reactions for α-Mg.
4 90.1 4.9 4.9
5 89.4 4.7 5.9 as the Ca content is further increasesd, the Mg2Ca content continues to
6 47.4 20.8 31.7
increase, resulting in a decrease in the oxidation resistance.
7 45.0 19.0 35.9
8 51.8 4.6 43.6
4. Conclusion

(1) Addition of Ca leads to a reduction in the oxidation rate of Mg.

Among the tested alloys, Mg–1.0Ca shows the best oxidation

10
Y. Ming et al.
Fig. 15. Schematic diagram of oxidation process of α-Mg.
Fig. 16. Schematic diagram of oxidation process of Mg2Ca.
resistance. An Mg–Ca–O oxide film is formed on the surface to
protect the substrate.
(2) Based on the Gibbs free energy and DFT calculations and analysis
of oxidation, oxidation models of α-Mg and Mg2Ca describing the
oxidation process are proposed.
(3) The oxide layer formed on α-Mg is effective at improving the
oxidation resistance, whereas the oxide layer formed on Mg2Ca is
not stable. Protuberances will develop on the oxide layer formed
on Mg2Ca, which then peel off from the substrate, forming
depression structure, and resulting in further oxidation.
CRediT authorship contribution statement
Guoqiang You: Conceptualization, Methodology. Yue Ming: Data
curation, Writing – original draft. Fanjin Yao: Data curation, Writing –
original draft. Sheng Zeng: Writing – review & editing. Jun Zhang:
Visualization, Investigation. Jianhua Zhao: Supervision. Wen Zeng:
Methodology, Software.
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.
11
Corrosion Science 196 (2022) 110046
Data availability statement
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
We appreciate the financial support from Guangdong Province Key
Field R&D Program Project, China (NO. 2020B010186002), Dongguan
Key Technology Key Project, China (NO. 2019622134013), and Na­
tional Natural Science Foundation of China, China (NO. U2037601).
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