Journal of Materials Research and Technology 28 (2024) 2572–2581

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Journal of Materials Research and Technology

journal homepage: www.elsevier.com/locate/jmrt

Al and Mo synergistic enhancement of CoCrFeNi high-entropy alloy laser

cladding layer
Wei Zhao a, b, c, *, Zhen Li a, b, c, **, Chenxiao Song b, c, Ming Wang d, Guangchun Xiao b, c,
Hui Zhang b, c, Xiang Li b, c, Kedong Yu b, c, Lianyong Xu a, b
a
School of Materials Science and Engineering, Tianjin University, Tianjin, 300350, China
b
Faculty of Mechanical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan, 250353, China
c
Shandong Institute of Mechanical Design and Research, Jinan, 250031, China
d
Shandong Non-metallic Materials Institute, Jinan, 250031, China

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

Keywords: A CoCrFeNi high-entropy alloy (HEA) coating, enhanced with Al and Mo, was fabricated on Q235 steel using
Laser cladding laser cladding technology. The synergistic enhancement effect of Al and Mo on the coatings was studied. The
High entropy alloy findings revealed that the CoCrFeNi coating mainly comprised the single-phase FCC. In contrast, the BCC and σ
Synergistic effect
phases were observed when Al and Mo were individually doped. The simultaneous doping of both these elements
Wear resistance
High-temperature oxidation
resulted in a coating consisting of the BCC and σ phases. Mo addition led to grain refinement and increased the
kernel average misorientation value; similarly, Al addition further enhanced these effects. The separate additions
of Al and Mo significantly refined the microhardness and wear resistance of the coating. When both elements
were added simultaneously, the microhardness and wear resistance of the coating were further enhanced,
demonstrating the synergistic effects of Al and Mo on these characteristics. Moreover, the individual doping of Al
and Mo decreased the Kp value and the oxide layer’s thickness. Meanwhile, their combined addition reduced the
Kp value by approximately 82.5 % and 89.8 %, respectively. During the initial oxidation stage, rapid oxidation of
Al occurred, thereby decreasing the oxidation rate. In contrast, Mo facilitated the formation of Al2O3.

1. Introduction CoCrFeNi HEA, being extensively investigated, exhibits a thermally

Yeh et al. (2004) proposed the concept of high-entropy alloy (HEA),
which revolutionised the conventional alloy design rule of using one or
two alloying elements as the primary components and opened a new
avenue for the development of alloys [1]. The high configurational en­
tropy (ΔS > 1.5 R, where R is the gas constant) within HEA facilitates the
formation of unidirectional or bidirectional solid solution phases [2–4].
HEA exhibits significant entropy, lattice distortion, slow diffusion, and
cocktail effects, thereby imparting high microhardness [5], excellent
wear resistance [6], corrosion resistance [7] and high-temperature
oxidation resistance [8], which endow their application potential as
coating materials [9]. Laser cladding offers several advantages, such as
rapid cooling and high energy density, enabling excellent metallurgical
bonding between the coating and substrate [10,11]. Consequently, using
laser cladding to fabricate high entropy alloys holds significant potential
for numerous applications.
stable single-phase FCC structure that offers an exceptional combination
of ductility and fracture toughness at ambient and low temperatures
[12]. Nevertheless, CoCrFeNi HEA falls short of meeting industrial
application demands because of inadequate strength and wear resis­
tance [13]. The addition of alloying elements can mitigate these limi­
tations [14]. Including Al has proven to be a successful strategy for
enhancing the performance of CoCrFeNi HEA. Numerous studies have
investigated the microstructure and properties of AlCoCrFeNi HEA [15,
16]. With the increase in the Al molar ratio, the microstructure of Alx
CoCrFeNi HEA transitions from a single FCC solid solution through an
FCC + BCC biphase solid solution to a single BCC solid solution.
Simultaneously, the microhardness rises from 116 HV to 509 HV [17].
The yield and fracture strength of AlxCoCrFeNi HEA increase with a
higher Al content, whereas its plasticity decreases because of the pro­
motion of a hard BCC phase formation by Al [18]. AlCoCrFeNi HEA
demonstrates outstanding wear resistance in high-temperature

* Corresponding author. School of Materials Science and Engineering, Tianjin University, Tianjin, 300350, China.
** Corresponding author. Faculty of Mechanical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan, 250353, China.
E-mail addresses: zwapple@yeah.net, zhaowei@qlu.edu.cn (W. Zhao), lizhen2928@163.com (Z. Li).

https://doi.org/10.1016/j.jmrt.2023.12.212
Received 20 September 2023; Received in revised form 6 December 2023; Accepted 22 December 2023
Available online 23 December 2023
2238-7854/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
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W. Zhao et al. Journal of Materials Research and Technology 28 (2024) 2572–2581

environments because of the quick formation of a predominantly Al2O3 During the laser cladding process, 99.9 % of pure argon gas was
and Cr2O3 oxide layer on its surface during wear [19]. Furthermore, employed as the shielding gas at a flow rate of 15 L/min to prevent the
AlCoCrFeNi alloy, one of the typical HEAs containing Al, has garnered oxidation of the HEA coating.
significant interest because of its excellent oxidation resistance. The The HEA coatings underwent grinding using SiC abrasive paper,
remarkable oxidation performance of AlCoCrFeNi HEA is ensured by the followed by polishing with a 0.5-μm diamond polish agent. Subse­
selective oxidation of Al and Cr elements in high-temperature environ­ quently, the phase composition was analysed using X-ray diffraction
ments [20]. Increasing the Al content improves the continuity and in­ (XRD, Ultima IV) with Cu Kα radiation. The XRD was conducted at a
ternal positioning of the Al2O3 oxide layer, leading to progressive tube voltage of 40 kV, a tube current of 40 mA and a scanning speed of
oxidation resistance [21]. 4◦ /min. The elemental composition of the HEA coating was analysed
It is noteworthy that adding an appropriate amount of high melting using EDS, and the results are documented in Table 2. The microstruc­
point elements is a viable method to further upgrade the mechanical ture of the HEA coatings were characterised by field scanning electron
properties and corrosion resistance of HEA [22]. For instance, incor­ microscopy (FSEM, JEOL-7800F) in the backscatter mode and electron
porating 1 at.% Nb into CoCrFeNi HEA increased microhardness from backscattered diffraction (EBSD, Nordly Max3, Oxford) at an acceler­
790 HV to 1008 HV because of the strengthening of the solid solution ated voltage of 20 kV.
and fine crystal strengthening along with the creation of a high-hardness The microhardness of the HEA coating was assessed using a Vickers
Laves phase [23]. Solution and second-phase strengthening are the hardness tester (HXD-1000TMC) under a 1.96-N load and a retention
mechanisms responsible for improving the microhardness and wear time of 15 s. Three measurements were taken at each point, and the
resistance of W-enhanced CoCrFeNiWx HEA coating, with the average value was recorded. The coatings, measuring 15 mm × 15 mm
strengthening effect intensifying with the increase in the W content in surface size, underwent sanding and polishing. Following those, they
[24]. The intermetallic compound created by incorporating an appro­ were subjected to ultrasonic cleaning in anhydrous ethanol for a dura­
priate amount of Mo exhibits excellent thermal stability, wear resistance tion of 10 min. According to the wear test standard ASTM G99-04, the
and oxidation resistance, aligning with the enhancement expectation of sliding dry wear behaviour of the coatings was evaluated at room tem­
CoCrFeNi HEA [25]. Due to the significant differences in the atomic perature using a friction and wear tester (HSR-2M) with a load of 20 N, a
radius and mixing entropy between Mo and the elements Co, Cr, Fe and sliding time of 30 min and a sliding speed of 3 m/min. A WC carbide ball
Ni, the enhancement mechanism of Mo has garnered attention from with a diameter of 4 mm and a hardness of 1424 HV was selected as the
researchers [26]. As the Mo content increases, the microstructure of counterpart for friction. The sample was ultrasonically cleaned imme­
CoCrFeNiMox HEA transitions from typical dendrites to subeutectic, diately for 15 min after the wear experiment to detect the wear
complete eutectic and even to a hyperfine structure, resulting in morphology. The wear morphology was observed using field scanning
augmented fracture strength [27]. With increased Mo content, the electron microscopy (SEM, JEOL-7800F). The wear volume and
microhardness and wear resistance of CoCrFeNiMox (x = 0, 0.15, 0.2 morphology of wear marks were characterised by a 3D optical micro­
and 0.25) HEA improved, with the solid solution strengthening and fine scope (Contour Elite K, Germany). The wear rate (W) was calculated
crystal strengthening serving as the primary strengthening mechanisms using the following equation:
[26].
V
HEA’s extensive portfolio often generates complex design chal­ W= (1)
L×D
lenges. Currently, numerous studies have simultaneously incorporated
Al and Mo [28–30]. However, the synergistic mechanism between these where V represents the negative volume (mm3), D is the normal load (N),
two elements remains largely unexplored. This study applied laser and L denotes the sliding distance (m).
cladding technology to prepare CoCrFeNi HEA on Q235 steel, incorpo­ After grinding and polishing, the surfaces of the samples were
rating Al and Mo via co-doping. Furthermore, it analysed the synergistic washed with anhydrous ethanol, and the high-temperature oxidation
enhancement mechanism of these two elements on the microstructure, experiment was conducted for 50 h in a muffle furnace (SXL-1200C) at
wear resistance and high-temperature oxidation resistance of the HEA 800 ◦ C. The mass change was calculated by electronic balance, the phase
coating. The results contribute towards a novel concept to the HEA analysis of the oxide layer was conducted using XRD, and the cross-
system design. section analysis was performed via SEM and EDS to evaluate the
oxidation resistance.
2. Experiment procedure
3. Results and discussions
The laser cladding substrate used in this study was Q235 steel
measuring 50 mm × 60 mm × 6 mm. The samples were ground to 3.1. Phase analysis
eliminate surface oxides and then cleaned with anhydrous ethanol to
remove the surface dirt. The HEA coatings utilised in this study were Fig. 1 depicts the XRD results of HEA coatings. S1 is a single-phase
assigned the names S1, S2, S3 and S4, representing CoCrFeNi, AlCoCr­ FCC structure. Adding Al transforms the crystal structure into a BCC
FeNi, CoCrFeNiMo and AlCoCrFeNiMo, respectively. The laser cladding structure (S2). Adding Mo did not change the crystal structure (FCC), but
utilised HEA powder comprising Al, Co, Cr, Ni and Mo in an equal a σ phase (S3) appeared. When Al and Mo are added simultaneous (S4),
atomic ratio (purity >99.5 wt%, particle size: 75–150 μm), with the Fe the coating consists of a BCC phase and σ phase. The σ phase that
element originating from the matrix. The mixed powder is pre-applied precipitated in both S3 and S4 is identified as the Fe3Mo phase
onto the treated Q235 surface using a Na2SiO3 solution, resulting in a (PDF#35–1489). Furthermore, the peak strength of the σ phase is
thickness of approximately 1 mm. The HEA coating is fabricated using a significantly reduced compared with S3, indicating that more Mo is
solid-state fibre laser (IPG-YLS-10000) operating at a maximum power
of 10 kW. Table 1 presents the details of the laser cladding process.
Table 2
Chemical composition of HEA coatings (at.%).
Table 1
Sample Al Co Cr Fe Ni Mo
Processing parameters of the laser cladding.
S1 – 23.9 17.9 38.3 19.9 –
Laser Scanning rate Lap rate Defocusing Spot diameter
S2 16.9 17.3 19.2 33.9 12.7 –
power (W) (mm/s) (%) amount (mm) (mm)
S3 – 14.8 17.8 32.9 16.6 17.9
1000 18 30 35 0.2 S4 11.7 14.2 15.3 30.9 11.4 16.5

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Table 3
Thermodynamic parameters of HEA coatings (ΔHmix/kJ mol− 1,δ/%, ΔSmix/J
mol− 1•K− 1, Δχ , K/kJ⋅mm− 2).
Sample ΔSmix ΔHmix δ Δχ K

S1 11.13 − 2.929 0.35 0.08 0.44

S2 12.88 − 10.65 5.48 0.11 0.44
S3 12.98 − 3.95 3.57 0.15 0.44
S4 14.33 − 8.01 5.31 0.17 0.44

exhibit a tendency to create solid solutions. Adding Al and Mo sub­

stantially increases the δ value and induces lattice distortion, corrobo­
rating the XRD findings.

3.2. Microstructure evolution

Fig. 2 presents the microstructure of the HEA coatings and the cor­
responding chemical composition of various representative regions is
shown in Table 4. It is indicated that the microstructure of sample S1
exhibits the typical dendritic (DR)–interdendritic (ID) structures. The
addition of Al and Mo individually does not significantly alter the
coating’s structure. However, it is notable that Cr enrichment occurs at
Fig. 1. XRD results of the HEA coatings. the ID in both S1 and S2 coatings. Additionally, the presence of a white
Mo–rich phase, constituting approximately 36 % of S3, signifies an
dissolved in the solid solution. Moreover, the addition of Mo and Al enrichment of the σ phase in this region. When both Al and Mo are
shifts the diffraction peaks of FCC and BCC to the left, respectively, due concurrently introduced, the regular structure of the coating is disrupted
to the increase in lattice constants caused by the solid solution of Mo and leading to a 41.7 % reduction in the proportion of the Mo–rich phase
Al with larger atomic radii. compared to S3.
According to Yeh et al. [1], under the effect of high entropy, HEA Fig. 3 depicts the EBSD inverse polar figure (IPF) results of the HEA
tends to create simple solid solution structures rather than intermetallic coating, demonstrating that all samples present equiaxed grains. S2
compounds. However, a further study of HEA revealed that ascertaining exhibits a <101>‖ND preferred orientation, whereas the other three
phase composition only by mixing entropy has limitations. At present, sample groups, particularly S4, exhibit random orientations. According
most studies believe that the parameters used to determine the phase to reports, random crystal orientation occurs because of grain obstruc­
stability conditions are mixing enthalpy (ΔHmix), configurational en­ tion during the solidification process at the solidification front [34].
tropy (ΔSmix), atomic size factor (δ), electronegativity difference (Δχ ) Fig. 4 demonstrates the average grain size and kernel average misori­
and the specific laser energy (K), which can be calculated as follows [31, entation (KAM) value of HEA coating. The grain size of S2 is approxi­
32]: mately 67.54 μm, slightly smaller than that of S1 (73.29 μm). Adding Mo
∑
n substantially refined the grain size, resulting in a 34.3 % decrease in the
ΔSmix = -R ci ln ci (2) grain size for S3 than S1, aligning with previous reports [26,35]. The
i=1 most significant grain refinement effect occurs when Al and Mo are
added simultaneously, leading to a grain size of only 1/2.3 of S1.
∑
n
ΔHmix = 4ΔHij ci cj (3) Moreover, the KAM value of S3 and S4 considerably exceeds that of the
i=1,i∕
=j S1 and S2 samples; this result is attributed to the formation of the brittle
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ and hard σ phase.
∑ n
δ = 100 ci (1-ri /r)2 (4)
i=1 3.3. Microhardness and wear properties
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
∑ n Fig. 5 illustrates the microhardness distribution of HEA coating. The
Δχ = ci (χ i -χ )2 (5) average microhardness of CoCrFeNi HEA coating is about 176.2 HV,
slightly lower than that of Q235 steel (209.8 HV). The average micro­
i=1

P hardness of S2 and S3 samples is roughly 3.9 times and 4.5 times that of
K= (6)
Dv
where R is the universal gas constant, ci and cj denote the percentages of
atoms of the elements of the i and j species, respectively, ΔHij refers to
the mixed enthalpy of elements i and j, ‾r stands for the average atomic
radius, ri is the atomic radius, χ i signifies the Pauling electronegativity, χ
is the average Pauling electronegativity, and Tm represents the melting
point of the alloy.
Using the experimental data, the researchers proposed the conditions
for the formation of a solid solution: 11 ≤ ΔSmix ≤ 19.5 J/mol⋅K, − 22 ≤
ΔHmix ≤ 7 kJ mol− 1 and 0 ≤ δ ≤ 8.5 % [26]. A small Δχ value and an
appropriate K value can facilitate solid solution formation [33]. Table 3
presents the thermodynamic parameters of the S1–S4 HEA coating. It is
evident that all HEA coatings meet the aforementioned conditions and
S1 samples, respectively, indicating that adding Al and Mo alone en­
hances the coating’s microhardness. Including Al alters the coating
phase from FCC to BCC, generating higher microhardness. The solid
solution strengthening induced by Mo addition and the formation of a σ
phase with high microhardness play pivotal roles in the considerable
increase in microhardness. In addition, the mean microhardness of S4
increased by 46.2 % and 25.4 % compared to S2 and S3, respectively,
suggesting that the doping of the Al and Mo elements was able to syn­
ergistically improve the microhardness of the coatings. The increase of
microhardness caused by the simultaneous doping of Al and Mo can be
attributed to the formation of σ phase, the transformation of crystal
structure, the strengthening of fine crystal and the strengthening of solid
solution effect.
Fig. 6(a) presents the friction coefficient of the coatings. The coef­
ficient increases rapidly in the initial stage of wear before stabilising

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Fig. 2. SEM images of the HEA coatings: (a) S1; (b) S2; (c) S3; (d) S4.

surface due to the relatively soft matrix’s inadequate load-bearing ca­

Table 4
pacity and self-lubrication. These grooves result from the extrusion
Chemical composition of various regions remarked in Fig. 2.
caused by the reciprocating motion-induced thrust, resulting in plastic
Sample Area Al Co Cr Fe Ni Mo deformation and material flow [37]. In contrast, the wear surface of S2
S1 A – 22.9 17.2 37.3 22.6 – appears relatively smooth, featuring numerous parallel grooves char­
B – 24.8 24.7 32.9 17.6 – acteristic of abrasive wear. The EDS analysis verifies the formation of an
S2 C 16.8 18.7 13.2 33.9 17.4 –
oxide layer during the wear process of S2, albeit without significant
D 11.4 20.6 22.6 31.3 14.1 –
S3 E – 18.8 15.7 36.9 15.9 12.7
spalling. The higher microhardness of S2 effectively maintains the
F – 17.3 17.4 31.1 14.6 19.6 presence of the oxide layer, thereby enhancing wear resistance. Ac­
S4 G 12.1 14.4 14.1 33.9 14.2 11.3 cording to Archard’s classic wear formula, microhardness and wear
H 9.7 14.1 14.8 28.0 15.5 17.9 resistance exhibit a positive correlation [38]. Interestingly, the behav­
iour of S3 contradicts this relationship—despite having a narrower and
gradually. S1 exhibits a significantly higher friction coefficient than the shallower wear surface than S2, it does demonstrate some spalling pits.
other three sample groups, along with a larger curve amplitude. The inclusion of Mo introduces the σ phase, which enhances the cutting
Furthermore, S3 demonstrates a slightly greater friction coefficient than resistance and hampers plastic deformation during the initial wear
S2 and a substantially higher coefficient than S4. Fig. 6(b) shows that the phase. The σ phase increases microhardness and reduces plasticity and
wear rate of S4 is the smallest (0.66 × 10− 5 mm3/mN), representing toughness, leading to the initiation and propagation of cracks on the
approximately 1/18.2, 1/3.3 and 1/4.7 of the wear rates observed in S1, surface and subsurface regions of the coating under fatigue loads during
S2 and S3, respectively. Fig. 7 displays the typical wear surface track of sliding. In essence, the brittleness and resistance to deformation become
the coating after 30 min. It reveals that the width and depth of the wear weaker with the improvement of micro-cutting resistance [11]. The σ
marks follow the sequence S1 > S3 > S2 > S4. Remarkably, a shaped-off phase distributed along the ID serves as the coating’s frame, limiting
zone is prominently visible at the bottom of the abrasion marks in S1, plastic deformation during wear.
whereas the surfaces of the other samples remain comparatively flat. Synergistic doping of Al and Mo results in a flatter wear surface,
The wear mechanism was further investigated by observing the wear which starkly contrasts with the other three sample groups, implying a
morphology and chemical composition of representative coating regions synergistic effect in refining the coating’s wear resistance. Al facilitates
using SEM and EDS techniques. Fig. 8 and Table 5 present the corre­ the formation of a high-hardness BCC phase. In contrast, Mo dissolves
sponding results. Notably, the wear surface of S1 exhibits abundant into the BCC phase with its large atomic radius, inducing lattice
oxidising debris (region A), which is attributed to the intense friction distortion that hinders the dislocation slip deformation. Furthermore, it
between the coating and the counterpart, causing severe surface further enhances the strength and hardness of the BCC phase. However,
oxidation. These oxide layers detach as debris with the progression of an optimal amount of the σ phase positively affects the initial wear phase
wear. Unfortunately, these oxidised debris fail to generate a self- without excessively compromising the coating’s plasticity. Furthermore,
lubricating effect and contribute to numerous spalling pits on the grain refinement and changes in KAM values are crucial factors that
worn surface, leading to significant adhesive wear. Furthermore, a affect wear resistance. When the coating is subjected to external loads
localised contact between the matrix and counterpart produces elevated involving squeezing and scratching, more grain boundaries obstruct
temperatures at the contact points, forming “solder joints”. Under shear overall coating stripping and lamellar stripping [39,40]. Moreover, the
forces prompted by reciprocating motion, these solder joints rupture, KAM value exhibits a positive correlation with dislocation density. A
leading to localised adhesive wear, commonly observed in low-hardness greater dislocation density contributes to improved hardness, strength,
matrices [36]. In addition, wide and deep grooves emerge on the wear deformation fatigue resistance and fatigue wear resistance of the coating

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W. Zhao et al.
Fig. 3. Inverse pole figure of ND of the HEA coatings: (a) S1; (b) S2; (c) S3; (d) S4.
Fig. 4. Average grain size and average KAM value of the HEA coatings.
[41,42]. The larger dislocation density refines the hardness and strength
of the coating, increases the deformation fatigue resistance and im­
proves the fatigue wear resistance.
3.4. High-temperature oxidation resistance
Fig. 9 shows that during the initial oxidation stage, oxygen reacts
directly with the alloying elements on the coating’s surface, forming an
oxide layer and rapidly increasing mass. With the progression of the
oxidation process, the growth and formation of the oxide layer are
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Journal of Materials Research and Technology 28 (2024) 2572–2581
Fig. 5. Microhardness distribution of the HEA coatings.
determined by the diffusion rate of ions [43]. The weight changes of the
S1–S4 coatings after 50 h were measured as 46.2, 26.4, 34.6 and 11.3
mg⋅cm2, respectively. This result indicates that Al and Mo individually
contribute to improving high-temperature oxidation resistance in the
coating. Furthermore, adding both elements separately further enhances
the high-temperature oxidation resistance of the coating. According to
Wagner’s theory, the oxidation kinetics of the coating adheres to the
W. Zhao et al.
Fig. 6. (a) Friction coefficients and (b) wear rates of the HEA coatings.
Fig. 7. 3D morphologies of the surface track after 30 min of wear in (a) S1; (b) S2; (c) S3; (d) S4 and (e) their corresponding 2D morphologies of the HEA coatings.
parabolic law, and the parabolic rate function can be estimated as fol­
lows [44]:
(Δm)2
= KP × t (7)
A
where Δm is the mass gain of the sample (mg), A is the surface area of the
sample (cm2), Kp is the parabolic oxidation rate constant and t is the
oxidation time (h). The Kp of S1 is the largest, which is about 3.02, 1.76
and 17.27 times of S2, S3 and S4, respectively.
Fig. 10 illustrates the XRD results for the coatings after oxidation at
800 ◦ C for 50 h. The oxide layer formed on S1 is primarily composed of
Fe2O3 and Cr2O3. Additionally, Al2O3 is observed in the oxide layer
when Al is added (S2), and CoMoO4 forms in the oxide layer when Mo is
added (S3). In S4, the oxide layer is composed of all the aforementioned
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Journal of Materials Research and Technology 28 (2024) 2572–2581
oxides (see Fig. 9).
Fig. 11 depicts the cross-sectional morphology of the coating after
undergoing 50 h of oxidation at 800 ◦ C. Notably, the oxide layer
thickness of S1 measures approximately 53.3 μm. However, poor density
of the oxide layer leads to visible defects such as grooves and holes. The
introduction of Al (S2) improves the density of the oxide layer, whereas
Mo (S3) reduces the presence of defects. Consequently, the oxide layer
thickness is reduced by 60 % and 44 %, respectively. Interestingly, when
Al and Mo are added simultaneously (S4), the oxide layer’s thickness is
reduced to 13.1 μm, indicating a synergistic enhancement of high-
temperature oxidation resistance from the combined effect of these el­
ements. Fig. 12 demonstrates the element distribution in the cross-
section of the oxide layer in S4. The inner layer of the oxide layer pri­
marily comprises of dense Al2O3 and Cr2O3, whereas the outer layer
comprises relatively loose Fe2O3 and CoMoO4. The distribution of these
W. Zhao et al. Journal of Materials Research and Technology 28 (2024) 2572–2581

Fig. 8. SEM morphologies of the wear surfaces of the (a) S1; (b) S2; (c) S3; (d) S4.

playing a prominent role in the reaction. Al is continuously consumed

Table 5
with the progression of the reaction, forming an Al-depleted region on
EDS point analysis data from Fig. 7 (at%).
the surface. Consequently, the reaction between Cr and oxygen, char­
Region Al Co Cr Fe Ni Mo O acterised by a relatively faster diffusion rate, becomes dominant. This
A – 8.5 14.6 28.7 7.3 – 40.9 outcome leads the dense Al2O3 and Cr2O3 to nucleate and grow on the
B – 19.9 21.3 34.7 17.8 – 6.3 metal surface, acting as a barrier to the diffusion of oxygen during the
C 18.7 8.2 11.3 31.7 10.4 19.7
–
initial oxidation stage [46]. Obtaining these dense oxide layers at the
D – 10.7 17.3 24.2 11.2 18.2 18.4
E 12.7 8.3 9.6 26.9 8.2 10.4 23.9 initial oxidation stage is the key to improve the oxidation resistance of
the coating, which is also the main reason why S2 shows better oxidation
resistance compared with S1 after the addition of Al element. None­
oxides is primarily influenced by oxidation kinetics. theless, these oxides face challenges in fully inhibiting the outward
The oxide layer formation was analysed using the Gibbs free energy diffusion of metal cations and subsequent interaction with oxygen,
function method. Fig. 13 depicts that the Gibbs free energy of all leading to the formation of less compact oxide layers, such as Fe2O3 and
oxidation reactions within the temperature range of 200–800 ◦ C is CoMoO4. It is crucial to note that the Gibbs free energy solely indicates
negative, indicating spontaneity. From a thermodynamic standpoint, a the tendency of spontaneous reactions. At the same time, the final
higher absolute value of Gibbs free energy corresponds to a greater oxidation product is influenced by both the elemental composition and
driving force for the reaction. During the initial oxidation stage, oxygen alloy kinetics. The diffusion of metal cations leads to vacancies in the
diffuses inward rapidly at approximately 1.8 × 10− 12 s− 1 [45], with Al oxide layer, which can condense into pores and other defects. These

Fig. 9. (a) Oxidation kinetic curves and (b) linear fit curves of the HEA coatings at 800 ◦ C.

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metals and oxides, respectively. Notable changes occur upon the sepa­
rate addition of Al and Mo. The grains become noticeably refined,
resulting in an increased density of grain boundaries and a more pro­
nounced short-range diffusion path along these boundaries. Conse­
quently, the diffusion rate of ions is reduced, decreasing the critical
concentration required for metal oxidation. This event, in turn, leads to
the selective oxidation of specific metals. Literature suggests that the
addition of Mo effectively promotes the formation of Al2O3 [48]. In
essence, the presence of Mo enhances the content of Al2O3 and its pro­
tective effect. It is through their combined efforts that the
high-temperature oxidation resistance of the coating is improved.

4. Conclusions

Four different CoCrFeNi HEA coatings were fabricated using laser

cladding technology on the Q235 steel surface. The impact of separately
adding Al and Mo on the microstructure and properties of the coatings
was investigated, revealing several noteworthy observations.

(1) The CoCrFeNi coating consisted of a single-phase FCC structure.

Fig. 10. XRD results of the HEA coatings after oxidation at 800 ◦ C for 50 h.
defects provide diffusion pathways for ions, thereby accelerating the
oxidation reaction. Adding Al primarily affects the initial oxidation
stage, whereas introducing Mo reduces oxide layer defects and enhances
its density (Fig. 10(c)). Moreover, the critical concentration of oxide
formation is a crucial factor in the oxidation process, expressed as [47]:
√̅̅̅ √̅̅̅̅̅̅
N>
V a π Kp
⋅ (8)
Vb 2D
where N is the critical concentration in the metal when the oxide film is
formed; D is the mutual diffusion coefficient of metals; Kp is the para­
bolic rate constant of oxidation; Va and Vb are the molar volumes of
However, adding Al led to a transformation into a single-phase
BCC structure, and the introduction of Mo resulted in the
appearance of the σ phase. When Al and Mo were doping
simultaneously, the coating comprised both BCC and σ phases,
with the smallest grain size, only about 1/2.3 of CoCrFeNi HEA.
Furthermore, the KAM value increased by 17.2 % compared to
CoCrFeNi HEA.
(2) Al and Mo synergistically enhanced the microhardness and wear
resistance of the coatings. The average microhardness of S2 and
S3 was approximately 3.9 and 4.5 times higher than that of S1,
respectively. Additionally, the microhardness of S4 has increased
by 46.2 % compared to S2 and by 25.4 % compared to S3.
Similarly, the wear rate of S4 was considerably lower, only about
1/18.2, 1/3.3, and 1/4.7 of S1, S2 and S3, respectively. The
improved microhardness and wear resistance were attributed to

Fig. 11. Cross-sectional micromorphologies after oxidation at 800 ◦ C for 50 h: (a) S1; (b) S2; (c) S3; (d) S4.

2579
W. Zhao et al.
Fig. 12. Corresponding element distribution of micromorphologies of the S4 after oxidation at 800 ◦ C for 50 h shown in Fig. 10(d).
Fig. 13. Gibbs free energy of NiO, CoO, Fe2O3, Cr2O3, Al2O3 and CoMoO4 with
temperature.
the crystal structure modification, reinforcement from solid so­
lution strengthening and the crystal’s support.
(3) The oxidation resistance of the coatings varied as follows: S1 <
S3 < S2 < S4. The dense and slow-growing Al2O3 layer hindered
ion diffusion and reduced the oxidation rate. In contrast, adding
Mo effectively promoted the formation of Al2O3, further
enhancing the oxidation resistance.
Declaration of competing interest
1. There is no conflicts of interest.
2. The work was supported by the National Nature Science Foun­
dation of China (No. 51805285, 51,605,237), the Projects of Shandong
Province “Youth innovation Science and Technology Support Plan”
(2021KJ026), Shandong Province Science and Technology Smes Ability
Improvement Project (2023TSGC0021, 2023TSGC0114), and the Inte­
gration Project of Science-Education-Industry of Qilu University of
Technology (Shandong Academy of Sciences) (2023PY020,
2580
Journal of Materials Research and Technology 28 (2024) 2572–2581
2022PY029).
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.
Acknowledgements
The work was supported by the National Nature Science Foundation
of China (No. 51805285, 51605237), the Projects of Shandong Province
“Youth innovation Science and Technology Support Plan” (2021KJ026),
Shandong Province Science and Technology Smes Ability Improvement
Project (2023TSGC0021, 2023TSGC0114), and the Integration Project
of Science-Education-Industry of Qilu University of Technology (Shan­
dong Academy of Sciences) (2023PY020).
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