Surface & Coatings Technology 409 (2021) 126899

Contents lists available at ScienceDirect

Surface & Coatings Technology

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

Ultrasonic cavitation erosion behaviors of high-velocity oxygen-fuel

(HVOF) sprayed AlCoCrFeNi high-entropy alloy coating in
different solutions
Zheng Wei a, Yuping Wu a, *, Sheng Hong a, *, Jiangbo Cheng a, Lei Qiao a, Jie Cheng a,
Shuaishuai Zhu a, b
a
College of Mechanics and Materials, Hohai University, 8 Focheng West Road, Nanjing 211100, China
b
Jiangsu Key Laboratory of Advanced Structural Materials and Application Technology, Nanjing Institute of Technology, Nanjing 211167, China

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

Keywords: In this study, an AlCoCrFeNi high-entropy alloy (HEA) coating was fabricated by HVOF spraying process. The
HVOF spraying HEA coating was consisted of the BCC phase (Al-rich phase) and FCC phase (Al-poor phase). The BCC phase was
AlCoCrFeNi high-entropy alloy coating main phase. The mechanical performances and corrosion resistances of the coating and 06Cr13Ni5Mo
Cavitation erosion
martensitic stainless steel were analyzed in detail. The cavitation erosion behaviors and mechanisms of the HEA
Mechanical performance
coating and 06Cr13Ni5Mo steel were investigated in distilled water and 3.5 wt% NaCl solution. The effects of
Corrosion property
microstructures, mechanical properties and corrosion properties on cavitation erosion mechanisms were dis­
cussed through the observation of eroded surface morphologies. The results showed that the cavitation erosion
resistance of the AlCoCrFeNi coating was about 3.5 times that of the 06Cr13Ni5Mo steel in both solutions. In the
3.5 wt% NaCl solution, corrosion damage aggravated cavitation erosion damage, although the enhancement
effect of corrosion on cavitation was limited. The corrosion environment did not change the cavitation erosion
mechanisms of the two materials. The cavitation erosion mechanism of the HEA coating was lamellar spalling
caused by the extension of the interlaminar cracks. Due to the lower plastic deformation resistance, the cavitation
erosion mechanism of the 06Cr13Ni5Mo steel was material spalling caused by plastic deformation and fatigue
fracture.

1. Introduction material by changing the elemental composition. With the development

The flow-handling components of hydraulic machinery are often
damaged by cavitation erosion and corrosion [1–4]. The repeated
impact of the micro-jet causes the deformation, fracture and spalling of
eroded surface, which greatly reduces the service life of the hydraulic
machinery [5–8]. In the marine environment, the surfaces of parts are
also damaged by corrosion. How to prepare the high-performance
coatings on the surface of flow-handling components to resist cavita­
tion erosion and corrosion damage is one of the hot spots in material
surface engineering [5–9].
The cavitation erosion resistance of material is closely related to the
strength and toughness. In the corrosive environment, the corrosion
resistance of material can also influence the cavitation erosion resis­
tance. Researchers try to improve the cavitation erosion resistance of
of new materials, researchers find that some high-performance high-
entropy alloys (HEAs) can be more widely used in surface engineering.
Compared with conventional alloys, the HEAs are consisted of five or
more major elements [10]. Due to the interaction between these ele­
ments, the HEAs often exhibit special performances [11]. It has been
reported that with the increase of Al content, the increase of BCC phase
and the more serious lattice distortion would lead to an improvement in
the mechanical properties of the AlxCoCrFeNi high-entropy alloys
[12,13]. Vahid et al. [14] prepared the AlCoCrFeNi2.1 alloy by vacuum
arc-melter and found it had high strength. Meanwhile, the corrosion
resistance was similar to that of the 304 stainless steel. Tang et al. [15]
found that the fatigue property of the cold-rolled Al0.5CoCrCuFeNi high-
entropy alloy might even outperform many commercial alloys, which
was attributed to the high density of nanotwins during the process of

* Corresponding authors.
E-mail addresses: weizheng159517@163.com (Z. Wei), wuyuping@hhu.edu.cn (Y. Wu), hongsheng@hhu.edu.cn (S. Hong), chengjiangbo@hotmail.com
(J. Cheng), 170408070005@hhu.edu.cn (L. Qiao), chengjie811@qq.com (J. Cheng), zhuss@njit.edu.cn (S. Zhu).

https://doi.org/10.1016/j.surfcoat.2021.126899
Received 23 September 2020; Received in revised form 13 December 2020; Accepted 19 January 2021
Available online 26 January 2021
0257-8972/© 2021 Elsevier B.V. All rights reserved.
Z. Wei et al. Surface & Coatings Technology 409 (2021) 126899

deformation. The excellent comprehensive property makes some HEAs Table 1

have superior cavitation erosion resistances. Nair et al. [16] used mi­
crowave hybrid technology to prepare AlCoCrFeNi coatings and found
that the cavitation corrosion resistance of the AlCoCrFeNi coating was
about 3 times that of SS316L stainless steel and the cavitation erosion
resistance of the material would decrease in the NaCl solution.
In addition to choosing the suitable coating, the preparation tech­
nology of the coating is one of the most important factors to influence
the coating performance. As a widely used thermal spraying technology,
the high-velocity oxygen-fuel (HVOF) spraying has the characters of
high flame flow velocity and low spraying temperature, which results in
a lower oxide content and compact structure in the coatings [17–19].
Although the HVOF spraying technology has been used in the surface
consolidation and protection [1–3,17–20], little researches have been
reported on the HVOF sprayed HEA coatings and their cavitation erosion
resistances. With the development of HEA powder preparation tech­
nology and HVOF spraying technology, it is necessary to explore the
application potential of HEAs in hydraulic machinery.
In this paper, the AlCoCrFeNi coating (HEA coating) was fabricated
by HVOF spraying. The phase compositions of the coating and powder
were identified. The mechanical properties and corrosion properties of
the AlCoCrFeNi coating and 06Cr13Ni5Mo steel were investigated. In
different solutions, the cavitation erosion behaviors of the AlCoCrFeNi
coating and 06Cr13Ni5Mo steel were studied. By comparing the mass
losses and evaluating morphologies of the eroded surfaces, the effects of
microstructures, mechanical properties and corrosion resistances on
cavitation erosion behaviors were investigated and the cavitation
erosion mechanisms were discussed.
The chemical composition of the 06Cr13Ni5Mo steel.
Element Cr Ni Mo Mn C Fe
Composition (wt%) 12.90 5.70 0.73 0.58 0.045 Bal.
studied with the Taguchi method. Then, the optimized spraying pa­
rameters were obtained and listed in Table 2.
2.2. Coating characterization
The phase compositions of the coating and powder were identified by
X-ray diffractometer (XRD, RIGAKU Ultimate IV, Japan). The mor­
phologies of the coatings were analyzed by scanning electron micro­
scope (SEM, Zeiss Merlin Compact, Germany) with energy dispersive
spectrometer (EDS, Zeiss Merlin Compact, Germany). The porosity was
measured by optical microscope (OM, BX51M Olympus, Japan). At a
magnification of 200, ten pictures of different areas were used to eval­
uate the porosities by DT2000 image analysis software. Microhardness
tests were performed on a Vickers hardness tester (HXD-1000TM,
Taiming, Shanghai). The load and holding time were 300 g and 15 s,
respectively. For the sake of reducing the error, at least 10 repeat
measurements were measured. The nano-mechanical properties of the
HEA coating and 06Cr13Ni5Mo steel were performed by a nano-
indenter (Agilent G200, USA, Berkovich tip). The max load was 10
mN and the loading speed was 10 mN/min. At least 5 repeat measure­
ments of each sample were measured. All the samples for tests were
ground with emery papers and then polished to mirror surface.

2. Experimental procedures 2.3. Performance testing

2.1. Coating deposition In order to investigate the effects of the corrosion behaviors on
cavitation erosion resistances, the corrosion resistance of the coating
The HEA powder used for this work was prepared by vacuum water and 06Cr13Ni5Mo steel should be tested firstly. The cyclic potentiody­
atomization, as shown in Fig. 1. The HEA powder consisted of five ele­ namic polarization tests and electrochemical impedance spectroscopy
ments (Al, Co, Cr, Fe, Ni) with equal molar ratio. The size of the powder (EIS) tests were carried out in 3.5 wt% NaCl solution using the CS
was approximately in the range of 20 μm–45 μm, as shown in Fig. 1(a, electrochemical workstation (CS2350, Wuhan Corrtest Instruments Co.,
b). The 06Cr13Ni5Mo martensitic stainless steel was selected as sub­ Ltd., China). The three electrodes system used in this study consisted of a
strate, which was often used in manufacturing of the flow-handling working electrode (samples), a platinum sheet electrode and an Ag/AgCl
components of hydraulic machinery [21]. The chemical composition
of the 06Cr13Ni5Mo steel is listed in Table 1. Prior to spraying, the dust Table 2
and rust on the substrate were removed by sandpaper, then ultrasoni­ Processing parameters in HVOF spraying.
cally cleaned and degreased in acetone for 30 min, dried in electric blast
Spray parameter
drying oven at 80 ◦ C for 30 min and grit-blasted by 30 mesh Al2O3. The
distance and pressure of applying grit-blasted were 100 mm and 0.65 Oxygen flow (L/min) 802.2
Kerosene flow (L/h) 24.6
MPa, respectively. A commercial HVOF thermal spraying system
Argon carrier gas flow (L/min) 10.9
(Praxair Tafa JP8000, USA) was selected to deposit the HEA coating on Spray distance (mm) 370
the substrate. The effect of HVOF spray parameters (spraying distance, Powder feed (rpm) 5
oxygen flow and kerosene flow) on the porosity of the HEA coating were Relative traverse speed (mm/s) 280

Fig. 1. SEM morphologies of HEA powders with magnification of (a) 500× and (b) 2000×.

2
Z. Wei et al. Surface & Coatings Technology 409 (2021) 126899

reference electrode. After soaking in the solution for 2 h, the values of

open circuit potential (OCP) were stabilized. The electrochemical
impendence spectroscopies (EIS) of the samples were performed by
applying an amplitude perturbation voltage of 10 mV over frequency
range from 10+5 Hz to 10− 2 Hz. The EIS data were analyzed by the
software Zsimpwin3.21. The samples were polarized from 0.4 V below
the OCP to the anodic current density value of 0.5 mA/cm2 then
reversing back to the initial potential. The scanning rate of cyclic
potentiodynamic polarization was 0.5 mV/s.
In accordance with the ASTM G32-10 standard test method [22], the
cavitation erosion resistances of the HEA coating and 06Cr13Ni5Mo
steel was tested by a magnetostrictive cavitation erosion facility, as
shown in Fig. 2(a). The cavitation erosion tests were performed in
distilled water and 3.5 wt% NaCl solution. The samples were connected
to the cavitation erosion test apparatus. The size of the sample was
shown in Fig. 2(b). The surfaces of samples were 3 mm below the test
liquid level. The frequency and double vibratory amplitude were 20 ±
0.5 kHz and 60 ± 5 μm, respectively. After the cavitation erosion test,
the samples were washed for 15 min, and then dried at 70 ◦ C for 30 min. Fig. 3. XRD patterns of the HEA powder and coating.
The mass losses of the samples were measured with an analytical bal­
ance with an accuracy of 0.1 mg. coating are presented. The EDS results of the area A and area B are listed
in Table 3. The Al element is not detected in the light gray phase, while
3. Results and discussions the remaining elements are evenly distributed in the two phases. It also
indicates the light gray phase is the FCC phase and the dark gray phase is
3.1. Microstructural characterization the BCC phase. The differences of elements content between the FCC
phase and BCC phase lead to the differences of mechanical properties
The XRD patterns of the HEA powder and coating are shown in Fig. 3. and corrosion properties between two phases.
The HEA powder is consisted of the BCC phase (JCPDS 54-0387) and
FCC phase (JCPDS 33-0397). The BCC phase is main phase. Some reports 3.2. Mechanical property
showed that Al had the highest negative average enthalpy of mixing
between other element in AlCoCrFeNi high-entropy alloy, which indi­ Fig. 5 illustrates the microhardness curve following the change of
cated that the Al-rich phase (BCC, JCPDS 54-0387) was preferentially distance from the substrate/coating interface. The average microhard­
formed, then a little Al-poor phase (FCC, JCPDS 33-0397) was formed ness of the HEA coating (552.12 ± 23.3 HV0.3) is about 2 times that of
[23,24]. The diffraction peaks of the FCC phase of the HEA coating are the substrate (247.67 ± 15.7 HV0.3). Meanwhile, there is obvious work
lower than those of the powder. The content of the FCC phase in the hardening at the region of the substrate close to the coating, which is
coating is reduced by the remelting of the powder. It may be caused by caused by the sandblasting.
the high cooling rate during the HVOF spraying process. Meanwhile, the Cavitation erosion damage is mainly caused by the repeated impact
grain refinement caused by the high cooling rate also leads the diffrac­ of micro-jet [26]. It is necessary to evaluate the local plastic deformation
tion peaks of the coating to become wider than that of the powder resistance of the FCC phase and BCC phase by nanoindentation.
[20,25]. Although the effect of defects on the local mechanical properties of the
Cross-section morphologies and elemental mappings of the HEA coating can’t be well reflected, the results of nanoindentation can be
coating are shown in Fig. 4. The average thickness and porosity of the used to predict the cavitation resistance of each phase in the coating
coating are 250 ± 10.7 μm and 0.36 ± 0.11%, respectively. The HEA [27]. The nanoindentation curves are shown in the Fig. 6. Table 4 lists
coating is closely attached to the substrate and well filled in the craters the nanoindentation experimental results of the BCC phase, FCC phase
caused by sand blasting, as shown in Fig. 4(a). At high magnification, it and 06Cr13Ni5Mo steel. The work of plastic deformation (Wdeformation)
can be found that the HEA coating is mainly consisted of the dark gray of the FCC phase is higher than that of the BCC phase. It indicates that
phase and light gray phase (Fig. 4(b)). The dark gray phase is the main the FCC phase absorbed more energy under the same stress condition.
phase. In Fig. 4(c–g), the results of elemental mapping on the HEA The BCC phase has higher work of elastic deformation (Welastic) than that

Fig. 2. Schematic diagram of the cavitation erosion test apparatus (a) and sample (b).

3
Z. Wei et al. Surface & Coatings Technology 409 (2021) 126899

Fig. 4. Cross-section morphologies of the HEA coatings: (a) Microstructure of the HEA coating-substrate bonding; (b–g) the cross-section morphologies and
elemental mapping of the HEA coating.

Table 3
The EDS results of the coatings.
Area Element at.%

Al Co Cr Fe Ni

A 18.50 20.78 20.54 20.13 20.01

B – 24.50 23.47 25.89 26.14

Fig. 6. Load-depth nanoindentation curves of the BCC phase, FCC phase and
06Cr13Ni5Mo steel.

Fig. 5. Variation of microhardness across the coating and the substrate.
of FCC phase, which indicates the BCC phase has the larger elastic
recovery after deformation. In addition, the H/E and H3/E2 of the BCC
phase are higher than those of the FCC phase, which indicates that the
elastic strain failure resistance and plastic deformation resistance of the
BCC phase are better than those of the FCC phase [28,29]. Under the
same load, the Wdeformation of the 06Cr13Ni5Mo steel is the largest (Fig. 6
and Table 4). It is shown that the 06Cr13Ni5Mo steel is more likely to
deform and absorb a lot of energy under the same load. At high
magnification, one can see some small pop-in events in the curve of BCC
phase (Fig. 6), which also appears in the Al0.3CoCrFeNi. It may be caused

4
Z. Wei et al.
Table 4
Nanoindentation results of the HEA coating and 06Cr13Ni5Mo steel.
Material H (GPa) E (GPa)
BCC 9.514 208.27
FCC 5.948 249.69
06Cr13Ni5Mo steel 4.552 367.21
by the lattice distortion, dislocation tangle and local structural insta­
bility [30–32].
3.3. Corrosion behavior
The cyclic polarization curves of the HEA coating and 06Cr13Ni5Mo
steel are shown in the Fig. 7. The pitting corrosion resistances of the HEA
coating and 06Cr13Ni5Mo steel are assessed based on the difference
between repassivation potential (Erep) and corrosion potential (Ecorr), as
shown in Fig. 7(a) and Table 5. One can note that Erep − Ecorr of the HEA
coating is significantly higher than that of the 06Cr13Ni5Mo steel. It
exhibits that the pitting corrosion resistance of the HEA coating is better
than that of the 06Cr13Ni5Mo steel, which makes the coating more
efficiently in preventing the extension of corrosion pits [33,34]. Mean­
while, the larger hysteresis loop represents the worse pitting corrosion
resistance [35,36]. The hysteresis loop of the 06Cr13Ni5Mo steel is
larger than that of the HEA coating, as shown in Fig. 7(b). Therefore, the
pitting corrosion is considered to be more prone to occur on the surface
of the 06Cr13Ni5Mo steel.
The Nyquist plots and Bode plots of the HEA coating and
06Cr13Ni5Mo steel are shown in Fig. 8. The diameter of the semi-arc of
the 06Cr13Ni5Mo steel is larger than that of the HEA coatings (Fig. 8
(a)), implying the better corrosion resistance of the 06Cr13Ni5Mo steel
[37,38]. Compared with the coating, the 06Cr13Ni5Mo steel displays
higher angle θ, as shown in Fig. 8(b). It also shows that the corrosion
resistance of the 06Cr13Ni5Mo steel is higher than that of the HEA
coating. The Nyquist plots are fitted by the equivalent circuit. The cor­
responding fitting results are listed in Table 6. The RL is the solution
resistance. The R1 is the resistance of passive film and corrosion prod­
ucts. The R2 represents the charge transfer resistance. The R1 and R2 of
the 06Cr13Ni5Mo steel are higher than those of the HEA coating, which
can be deduced that the corrosion film of the 06Cr13Ni5Mo steel ex­
hibits better protective effect. It also reveals that the corrosion resistance
of the 06Cr13Ni5Mo steel is higher than that of the HEA coating. In
previous reports, Muangtong et al. [38] used vacuum arc melting
method to prepare the CoCrFeNi (FCC phase) and AlCoCrFeNi (BCC
phase) high entropy alloys, then investigated the corrosion behaviors of
them. They found that the AlCoCrFeNi showed lower corrosion resis­
tance, which was mainly caused by the selective dissolution of Al-rich
phase and Ni-rich phase. In multiphase high entropy alloys, the
Fig. 7. The electrochemical cyclic polarization curves (a) and hysteresis loops (b) of the coating and 06Cr13Ni5Mo steel.
Surface & Coatings Technology 409 (2021) 126899
H/E H3/E2 (GPa) Wdeformation (nJ) Welastic (nJ)
0.0457 0.0198 0.570 0.239
0.0238 0.00338 0.798 0.191
0.0124 0.000699 0.996 0.132
Table 5
Corrosion parameters of the HEA coating and 06Cr13Ni5Mo steel.
Sample Ecorr(V) Erep(V) Erep − Ecorr (V)
06Cr13Ni5Mo steel − 0.13605 − 0.12297 0.01308
HEA coating − 0.24193 − 0.18437 0.05756
galvanic corrosion of Al0.5CoCrFeNi (FCC + BCC phases), Al0.7CoCrFeNi
(FCC + BCC phases), CoCrFeNiCu (FCC (CoCrFeNi) + FCC (Cu-rich)
phases) and AlCoCrFeNi (FCC + BCC phases, heat treatment at 1200 ◦ C)
were reported and the galvanic corrosion was the main corrosion
mechanism of these HEAs [39,40]. Combined with the data obtained in
this paper, the HEA coating is consisted of the BCC phase and FCC phase
and the higher corrosion resistance of the FCC phase leads to the
galvanic corrosion driven by the different potential of two phases
[16,41]. It indicates the main corrosion type of the HEA coating is the
galvanic corrosion rather than pitting corrosion.
3.4. Cavitation erosion behavior and mechanism
Fig. 9 shows the cumulative mass losses and cumulative mass loss
rates of the HEA coating and 06Cr13Ni5Mo steel in different solutions.
After eroded for 24 h in distilled water, the mass losses of the HEA
coating and 06Cr13Ni5Mo steel are 6.1 mg and 22.7 mg (Fig. 9(a)),
respectively. When the cavitation erosion environment changes to 3.5
wt% NaCl solution, the mass losses of the HEA coating and
06Cr13Ni5Mo steel increase to 6.8 mg and 24.4 mg (Fig. 9(a)), respec­
tively. It indicates that the corrosion damage aggravated cavitation
erosion damage. However, the slight differences between cumulative
mass losses in 3.5 wt% NaCl solution and those in distilled water reveal
that the enhancement effect of corrosion on cavitation erosion is limited.
After eroded for 24 h in distilled water, the mass loss rates of the HEA
coating and 06Cr13Ni5Mo steel are 0.254 mg/h and 0.946 mg/h,
respectively. In 3.5 wt% NaCl solution, the mass loss rates of the HEA
coating and 06Cr13Ni5Mo steel are 0.280 mg/h and 1.017 mg/h,
respectively. The cumulative mass loss rates of all samples firstly
decrease with the increase of the time, and then gradually reach the
stable stage (Fig. 9(b)). This phenomenon has also been reported in
previous studies [16,42,43], but the reasons for this phenomenon are
5
Z. Wei et al. Surface & Coatings Technology 409 (2021) 126899

Fig. 8. Nyquist plots (a) and Bode plots (b) of the 06Cr13Ni5Mo steel and HEA coating in 3.5 wt% NaCl solution.

Table 6
The fitted results for EIS of the coating and the 06Cr13Ni5Mo steel in 3.5 wt% NaCl.
Sample RL (Ω⋅cm2) Q1 n1 R1 (Ω⋅cm2) Q2 n2 R2 (Ω⋅cm2)
− 5 4 − 5
HEA coating 15.93 3.973 × 10 0.8867 6.06 × 10 1.827 × 10 0.6209 3.123 × 104
5
06Cr13Ni5Mo steel 13.65 3.962 × 10− 0.9445 1.35 × 105 3.129 × 10− 5
0.9975 6.29 × 105

Fig. 9. Cumulative mass loss (a), cumulative mass loss rate (b) as a function of exposure time of the 06Cr13Ni5Mo steel and HEA coating.

complex. The ASTM G32-10 [22] pointed out that the rate of mass loss
varied with exposure time and there was a maximum cavitation loss
rate. Combined our team’s studies and related researches
[16,17,19–21], the maximum erosion rate may be related to the damage
of the initial smooth surface. In the early stage of cavitation erosion test,
the cavitation erosion damage expands from the pores on the eroded
surface to the surrounding area, then the smooth surface of the sample is
completely destroyed. In this process, pressure perturbation on the pit
surface leads the bubble to collapse at the edge of the existed pit, which
result in a severe damage at the edge of the pit [44]. The cavitation

Fig. 10. Cavitation erosion morphologies of the HEA coatings in distilled water: (a) the boundary of cavitation erosion area; (b) the center of cavitation erosion area.

6
Z. Wei et al.
erosion rate increases rapidly and reaches a peak value. When the
original surface is completely destroyed, the segregation of bubble de­
creases and the cavitation loss rate decreases to a stable level. In addi­
tion, one can note that the cavitation erosion loss rate of 06Cr13Ni5Mo
steel rises again after falling, which may be caused by the plastic
deformation of the steel at the bottom of craters [20,45]. After the
spalling of eroded surface, the plastic deformation ability of exposed
part is better. With the impact of micro-jet, the brittleness of eroded
surface increases and the cavitation loss rate increases again.
The typical cavitation erosion morphologies of the HEA coating in
distilled water are shown in Fig. 10. In the boundary of the cavitation
erosion area, the coating surface consists of the undamaged areas and
shallow cavitation craters (Fig. 10(a)), which are caused by the low
cavitation erosion intensity [46]. In the center of cavitation erosion area,
the eroded surface is covered by a lot of craters. At high magnification,
the bottoms of the craters are very smooth. The lamellar structure and
fatigue fracture morphologies are obvious on the side of the craters, as
shown in Fig. 10(b). The region A shows that micro-cracks extended
along the lamellar structure. During spraying process, the high speed
molten and semi-molten particles impact on the substrate, and then
rapid cooling. On the one hand, the lower thermal expansion coefficient
of the HEA coating leads to the residual compressive stress and pre­
venting crack propagation [47,48]. On the other hand, the metal coat­
ings prepared by thermal spraying usually show lamellar structure,
which leads to the fact that the cracks are more prone to develop along
the lamellar structure [49]. In conclusion, the main cavitation erosion
mechanism of the HEA coating is lamellar spalling.
Fig. 11 shows the cavitation erosion morphologies of the
06Cr13Ni5Mo steel in distilled water. The boundary of cavitation
erosion area exhibits obvious plastic deformation and pits, as shown in
Fig. 11(a). From the previous analysis, one can see that the
06Cr13Ni5Mo steel shows excellent plastic deformation capability,
which can reduce the mass loss of the 06Cr13Ni5Mo steel in the initial
stage of cavitation. With the aggravation of cavitation erosion damage,
Fig. 11. Cavitation erosion morphologies of 06Cr13Ni5Mo steel in distilled water: (a) the boundary of cavitation erosion area; (b) the center of cavitation erosion
area; (c) groove; (d) deep crater.
7
Surface & Coatings Technology 409 (2021) 126899
the repeated impact of micro-jets causes the rapid initiation and prop­
agation of fatigue cracks, which lead to the surface spalling as shown in
Fig. 11(b). In addition, some grooves appear on the eroded surface, as
shown in Fig. 11(c). Under the impact of micro-jet and shock waves, the
small spalling pits expand and form larger craters, then the craters
connect to each other to form the grooves. Fig. 11(d) illustrates the
morphology of the deep crater. It may be caused by the following two
reasons: (1) The mechanical properties of some regions with more de­
fects are poor, which leads to severe cavitation erosion damage in local
areas [50]; (2) The cavitation intensity on the center of the eroded
surface is higher than that on other areas. According to the above
analysis, the main cavitation erosion mechanism of the 06Cr13Ni5Mo
steel is material spalling caused by plastic deformation and fatigue
fracture.
After eroded for 24 h in 3.5 wt% NaCl solution, the morphologies of
the HEA coatings are shown in Fig. 12. The cavitation erosion mor­
phologies of the boundary area are similar to that in distilled water, as
shown in Figs. 10(a) and 12(a). The pits on the surface of the original
coating aggravate the cavitation erosion damage. At high magnification,
it can be found that there are three kinds of cavitation erosion damage
morphologies from slight to sever. Under the impact of cavitation
erosion, the cracks initiate at the surface defects (pits, cracks, interfaces)
and develop along the defects (Fig. 12(a)), then form small and shallow
pits, as shown in region B. With the further aggravation of cavitation
erosion damage, the cavitation erosion pits are further expanded, as
shown in region C. Finally, the spalling pits increase and connect with
each other to form the cavitation craters, as shown in region D. In
addition, there are two kinds of shapes on the boundary of the crater,
which are smooth and rough, as shown in Fig. 12(b). In the process of
cavitation erosion, the cracks extending along the interlaminar surface
are smooth. In the contrary, the cracks formed under repeated impact
are coarse. Compared with the cavitation erosion morphologies in
distilled water, some deep craters appear on the eroded surface (Fig. 12
(c)). At the same time, the craters tend to extend outwards. At the edge
Z. Wei et al.
Fig. 12. Cavitation erosion morphologies of the HEA coatings in 3.5 wt% NaCl solution: (a, b) the boundary of cavitation erosion area; (c, d) the center of cavitation
erosion area.
of the crater, it can be found the obvious lamellar morphologies and
rough fracture surface, as shown in the Fig. 12(d). Chen et al. [44] used
numerical simulation to investigate the development of cavitation
erosion pits on solid surface and found the collapse probability of bubble
at the edge of craters was higher than undamaged surface. It indicates
that the craters tend to expand around during cavitation erosion process.
In addition, the lamellar structure (Fig. 12(d)) of the coating also pro­
motes this trend. The corrosion damage aggravates the cavitation
erosion, which accelerates the craters propagating along depth direc­
tion. However, it can be determined from the cavitation erosion mor­
phologies that the cavitation erosion mechanism is unchanged. The
main mechanism of cavitation erosion damage is lamellar spalling.
The cavitation erosion morphologies of the 06Cr13Ni5Mo steel in
3.5 wt% NaCl solution are shown in Fig. 13. At low magnification, one
can note a large number of cavitation craters and grooves, as shown in
Fig. 13(a). At the edge of the deep crater, there is obvious material
spalling, as shown in Fig. 13(b). Compared with the Fig. 11, the typical
morphologies in 3.5 wt% NaCl solution and distilled water are similar.
Fig. 13. Cavitation erosion morphologies of 06Cr13Ni5Mo steel in 3.5 wt% NaCl solution: (a) the center of cavitation erosion area; (b) deep crater.
8
Surface & Coatings Technology 409 (2021) 126899
However, it can be seen from the area of the grooves and craters that the
cavitation erosion damage in 3.5 wt% NaCl solution is more severe.
Fig. 14 illustrates the schematic diagram of cavitation erosion
mechanism of the HEA coating in 3.5 wt% NaCl solution. The cavitation
erosion damage is prone to appear on the pits and interfaces, as shown in
Fig. 14(a). From the cavitation erosion morphologies of the HEA
coating, it can be seen that the deep craters are appeared on the eroded
surface in 3.5 wt% NaCl solution, as shown in Figs. 12 and 14(d). In the
previous analysis, the main cavitation erosion mechanism of the HEA
coating is lamellar spalling. The appearance of the deep crater indicates
the increase of cracks perpendicular to the lamellae and the acceleration
of local spalling, during cavitation erosion process. Under the impact of
micro-jet, the surface of the HEA coating is deformed to tear the passive
film and the accumulation layer of corrosion products, as shown in
Fig. 14(b). The corrosion pits would be formed on the surface of the
coating without the protection of the passive film and the accumulation
layer of corrosion products, which causes stress concentration and ac­
celerates the crack growth perpendicular to the lamellae. The galvanic
Z. Wei et al.
Fig. 14. Schematic diagram of cavitation erosion mechanism of the HEA coating in 3.5 wt% NaCl solution: (a) original coating; (b) initial stage of cavitation erosion;
(c) lamellar spalling; (d) deep crater.
corrosion aggravates the corrosion damage of the interface between the
FCC phase and BCC phase. Under the same load, the differences of the
mechanical properties between the FCC phase and BCC phase lead the
difference of deformation between them, which can accelerate the
interlaminar cracks extending and the lamellar spalling in the area
around the FCC phase, as shown in Fig. 14(b) and (c). The galvanic
corrosion and difference of deformation are the main reasons for the
deep cavitation erosion craters appearing in some areas of the eroded
surface. With the cavitation erosion going on, the eroded surface of the
coating becomes rougher, the area exposed to the corrosion solution is
larger and the micro-jet increases the flow speed of the corrosion solu­
tion [44]. Those lead the corrosion damage in cavitation erosion process
more serious than that of immersion corrosion. The corrosion damage
and cavitation erosion damage reinforce each other, which causes the
increase of mass loss and the deep craters (Fig. 14(d)) appearing on the
eroded surface of HEA coating in 3.5 wt% NaCl solution. For the
06Cr13Ni5Mo steel, the pitting corrosion is more prone to occur on the
eroded surface of the 06Cr13Ni5Mo steel, which is convenient for the
appearance of crack sources and stress concentration. Compared with
the HEA coating, the poor deformation resistance and dense cracks
cause that the area exposed to corrosive solution increases. It aggravates
the material spalling and mass loss.
In a word, corrosion aggravates cavitation erosion damage. The
enhancement of corrosion damage on cavitation erosion damage is
related to the microstructures, mechanical properties, corrosion be­
haviors and cavitation erosion mechanisms of the materials, rather than
only controlled by the corrosion resistance of the materials. The me­
chanical effect of cavitation erosion is the main factor causing cavitation
erosion damage in 3.5 wt% NaCl solution. The main cavitation erosion
mechanism of the coating is lamellar spalling due to the interlaminar
cracks extending. The main cavitation erosion mechanism of the
06Cr13Ni5Mo steel is material spalling caused by plastic deformation
9
Surface & Coatings Technology 409 (2021) 126899
and fatigue fracture.
4. Conclusion
The AlCoCrFeNi (HEA) coating was successfully fabricated by HVOF
spraying process and the microstructure of the coating was character­
ized. The mechanical properties, corrosion resistance and cavitation
corrosion resistance of the coating and 06Cr13Ni5Mo martensitic
stainless steel were tested. The effects of mechanical properties and
corrosion resistance on cavitation corrosion resistance of the two ma­
terials in different solutions were studied. The main conclusions could
be drawn as follows:
1. The HEA coating was consisted of the BCC phase (Al-rich phase) and
FCC phase (Al-poor phase). The BCC phase was main phase. The
thickness and porosity of the coating were 250 ± 10.7 μm and 0.36 ±
0.11%, respectively.
2. The average microhardness of the HEA coating (552.12 ± 23.3
HV0.3) was 2 times that of the 06Cr13Ni5Mo steel (247.67 ± 15.7
HV0.3). The plastic deformation resistance of the BCC phase was
better than that of the FCC phase. The plastic deformation resistance
of the 06Cr13Ni5Mo steel was the worst. The corrosion resistance of
the HEA coating was lower than that of the 06Cr13Ni5Mo steel. The
main corrosion types of the HEA coating were the galvanic corrosion.
3. The cumulative mass loss of the 06Cr13Ni5Mo steel was about 3.5
times that of the HEA coating after eroded for 24 h in different so­
lutions. The superior cavitation erosion resistance was attributed to
the excellent mechanical property of the coating. In 3.5 wt% NaCl
solution, the corrosion damage and cavitation erosion damage
reinforced each other. The corrosion environment did not change the
cavitation erosion mechanism of the two materials. The main cavi­
tation erosion mechanism of the coating was lamellar spalling due to
Z. Wei et al.
the interlaminar cracks extending. The main cavitation erosion
mechanism of the 06Cr13Ni5Mo steel was material spalling caused
by plastic deformation and fatigue fracture.
CRediT authorship contribution statement
Zheng Wei: Investigation, Conceptualization, Methodology, Data
curation, Writing – original draft. Yuping Wu: Formal analysis, Inves­
tigation, Writing – review & editing, Supervision. Sheng Hong: Formal
analysis, Investigation, Writing – review & editing, Supervision.
Jiangbo Cheng: Writing – review & editing. Lei Qiao: Conceptualiza­
tion. Jie Cheng: Data curation, Investigation. Shuaishuai Zhu: Data
curation, Investigation.
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.
Acknowledgments
This work was supported by the National Natural Science Foundation
of China (Grant Nos. 51579087, 51979083 and 51975183), Natural
Science Foundation of Jiangsu Province, China (Grant No. BK20201316)
and the Opening Project of Jiangsu Key Laboratory of Advanced Struc­
tural Materials and Application Technology (Grant No. ASMA201902).
References
[1] Y. Wang, J. Stella, G. Darut, T. Poirier, H.L. Liao, M.P. Planche, APS prepared
NiCrBSi-YSZ composite coatings for protection against cavitation erosion, J. Alloy
Compd. 699 (2017) 1095–1103.
[2] V. Matikainen, H. Koivuluoto, P. Vuoristo, A study of Cr3C2-based HVOF- and
HVAF- sprayed coatings: abrasion, dry particle erosion and cavitation erosion
resistance, Wear 446 (2020) 203188.
[3] Y. Wang, B. Lebon, I. Tzanakis, Y.L. Zhao, K.S. Wang, J. Stella, T. Poirier, G. Darut,
H.L. Liao, M.P. Planche, Experimental and numerical investigation of cavitation-
induced erosion in thermal sprayed single splats, Ultrason. Sonochem. 52 (2019)
336–343.
[4] V. Matikainen, S.R. Peregrina, N. Ojala, H. Koivuluoto, J. Schubert, S. Houdkova,
P. Vuoristo, Erosion wear performance of WC-10Co4Cr and Cr3C2-25NiCr coatings
sprayed with high-velocity thermal spray processes, Surf. Coat. Tech. 370 (2019)
196–212.
[5] T. Varis, T. Suhonen, M. Jokipii, P. Vuoristo, Influence of powder properties on
residual stresses formed in high-pressure liquid fuel HVOF sprayed WC-CoCr
coatings, Surf. Coat. Tech. 388 (2020) 125604.
[6] Y. Wang, J.W. Liu, N. Kang, G. Darut, T. Poirier, J. Stella, H.L. Liao, M.P. Planche,
Cavitation erosion of plasma-sprayed CoMoCrSi coatings, Tribol. Int. 102 (2016)
429–435.
[7] H.S. Grewal, R.B. Nair, H.S. Arora, Complex concentrated alloy bimodal composite
claddings with enhanced cavitation erosion resistance, Surf. Coat. Tech. 392
(2020) 125751.
[8] A. Babu, H.S. Arora, H. Singh, H.S. Grewal, Microwave synthesized composite
claddings with enhanced cavitation erosion resistance, Wear 422 (2019) 242–251.
[9] H.S. Arora, S. Pradhan, A. Kumar, G. Perumal, R. Salloom, S. Mukherjee, H.
S. Grewal, Cavitation erosion-corrosion resilient surfaces through reciprocating
friction processing, Wear 456-457 (2020) 203385.
[10] J.W. Yeh, Alloy design strategies and future trends in high-entropy alloys, Jom 65
(12) (2013) 1759–1771.
[11] B.X. Cao, C. Wang, T. Yang, C.T. Liu, Cocktail effects in understanding the stability
and properties of face-centered-cubic high-entropy alloys at ambient and cryogenic
temperatures, Scripta Mater. 187 (2020) 250–255.
[12] T.F. Yang, S.Q. Xia, S. Liu, C.X. Wang, S.S. Liu, Y. Zhang, J.M. Xue, S. Yan, Y.
G. Wang, Effects of AL addition on microstructure and mechanical properties of
AlxCoCrFeNi high-entropy alloy, Mater. Sci. Eng. A 648 (2015) 15–22.
[13] W.R. Wang, W.L. Wang, S.C. Wang, Y.C. Tsai, C.H. Lai, J.W. Yeh, Effects of Al
addition on the microstructure and mechanical property of AlxCoCrFeNi high-
entropy alloys, Intermetallics 26 (2012) 44–51.
[14] V. Hasannaeimi, S. Mukherjee, Galvanic corrosion in a eutectic high entropy alloy,
J. Electroanal. Chem. 848 (2019) 113331.
[15] Z. Tang, T. Yuan, C.-W. Tsai, J.-W. Yeh, C.D. Lundin, P.K. Liaw, Fatigue behavior of
a wrought Al0.5CoCrCuFeNi two-phase high-entropy alloy, Acta Mater. 99 (2015)
247–258.
[16] R.B. Nair, H.S. Arora, H.S. Grewal, Microwave synthesized complex concentrated
alloy coatings: plausible solution to cavitation induced erosion-corrosion, Ultrason.
Sonochem. 50 (2019) 114–125.
10
Surface & Coatings Technology 409 (2021) 126899
[17] S. Hong, Y.P. Wu, J.H. Wu, Y.Q. Zhang, Y. Zheng, J.H. Li, J.R. Lin, Microstructure
and cavitation erosion behavior of HVOF sprayed ceramic-metal composite
coatings for application in hydro-turbines, Renew. Energy 164 (2021) 1089–1099,
https://doi.org/10.1016/j.renene.2020.08.099.
[18] S. Hong, Z.Y. Wei, K.L. Wang, W.W. Gao, Y.P. Wu, J.R. Lin, The optimization of
microbial influenced corrosion resistance of HVOF sprayed nanostructured WC-
10Co-4Cr coatings by ultrasound-assisted sealing, Ultrason. Sonochem. 72 (2021)
105438.
[19] S. Hong, J.R. Lin, Y.P. Wu, J.H. Wu, Y. Zheng, Y.Q. Zhang, J.B. Cheng, W. Sun,
Cavitation erosion characteristics at various flow velocities in NaCl medium of
carbide-based cermet coatings prepared by HVOF spraying, Ceram. Int. 47 (2021)
1929–1939, https://doi.org/10.1016/j.ceramint.2020.09.022.
[20] S. Hong, Y.P. Wu, J.H. Wu, Y. Zheng, Y.Q. Zhang, J.B. Cheng, J.H. Li, J.R. Lin,
Effect of flow velocity on cavitation erosion behavior of HVOF sprayed WC-10Ni
and WC-20Cr3C2-7Ni coatings, Int. J. Refract. Met. Hard Mater. 92 (2020) 105330.
[21] Y.G. Zheng, S.Z. Luo, W. Ke, Cavitation erosion-corrosion behaviour of CrMnB
stainless overlay and 0Cr13Ni5Mo stainless steel in 0.5 M NaCl and 0.5 M HCL
solutions, Tribol. Int. 41(12) (2008) 1181–1189.
[22] Astm G32-10, Standard Test Method for Cavitation Erosion Using Vibratory
Apparatus, ASTM, Philadelphia, 2010.
[23] S. Uporov, V. Bykov, S. Pryanichnikov, A. Shubin, N. Uporova, Effect of synthesis
route on structure and properties of AlCoCrFeNi high-entropy alloy, Intermetallics
83 (2017) 1–8.
[24] C. Chattopadhyay, A. Prasad, B.S. Murty, Phase prediction in high entropy alloys -
a kinetic approach, Acta Mater. 153 (2018) 214–225.
[25] A. Munitz, S. Salhov, S. Hayun, N. Frage, Heat treatment impacts the micro-
structure and mechanical properties of AlCoCrFeNi high entropy alloy, J. Alloys
Compd. 683 (2016) 221–230.
[26] H. Wu, C. Zhou, Z.H. Pu, H.X. Yu, D.C. Li, Effect of low-frequency ultrasonic field at
different power on the dynamics of a single bubble near a rigid wall, Ultrason.
Sonochem. 58 (2019) 104704.
[27] P. Niederhofer, F. Pohl, K. Geenen, S. Huth, W. Theisen, Influence of
crystallographic orientation on cavitation erosion resistance of high interstitial
CrMnCN austenitic stainless steels, Tribol. Int. 95 (2016) 66–75.
[28] X.L. Ji, C.C. Ji, J.B. Cheng, Y.P. Shan, S.Y. Tian, Erosive wear resistance evaluation
with the hardness after strain-hardening and its application for a high-entropy
alloy, Wear 398 (2018) 178–182.
[29] S.P. Wen, R.L. Zong, F. Zeng, S. Guo, F. Pan, Nanoindentation and nanoscratch
behaviors of Ag/Ni multilayers, Appl. Surf. Sci. 255 (8) (2009) 4558–4562.
[30] J. Qiang, K. Tsuchiya, H.Y. Diao, P.K. Liaw, Vanishing of room-temperature slip
avalanches in a face-centered-cubic high-entropy alloy by ultrafine grain
formation, Scripta Mater. 155 (2018) 99–103.
[31] X.L. Bian, G. Wang, K.C. Chan, J.L. Ren, Y.L. Gao, Q.J. Zhai, Shear avalanches in
metallic glasses under nanoindentation: deformation units and rate dependent
strain burst cut-off, Appl. Phys. Lett. 103 (10) (2013) 101907.
[32] J.I. Lee, J.W. Kim, H.S. Oh, J.S. Park, E.S. Park, Abnormal devitrification behavior
and mechanical response of cold-rolled Mg-rich Mg-Cu-Gd metallic glasses, Acta
Mater. 116 (2016) 238–249.
[33] M.A. Almomani, W.R. Tyfour, M.H. Nemrat, Effect of silicon carbide addition on
the corrosion behavior of powder metallurgy Cu-30Zn brass in a 3.5 wt% NaCl
solution, J. Alloys Compd. 679 (2016) 104–114.
[34] J.L. Wu, X.Z. Li, H.B. Cao, Y. Pan, Y.T. Zhu, Ultraviolet light irradiation on pitting
corrosion of Cu-based bulk metallic glasses, J. Alloys Compd. 661 (2016) 345–348.
[35] R. Chelariu, L.C. Trinca, C. Munteanu, G. Bolat, D. Sutiman, D. Mareci, R.M. Souto,
Corrosion behavior of new quaternary ZrNbTiAl alloys in simulated physiological
solution using electrochemical techniques and surface analysis methods,
Electrochim. Acta 248 (2017) 368–375.
[36] M.M. Pariona, V. Teleginski, K. dos Santos, A.A.O.C. de Lima, A.J. Zara, K.
T. Micene, R. Riva, Influence of laser surface treated on the characterization and
corrosion behavior of Al-Fe aerospace alloys, Appl. Surf. Sci. 276 (2013) 76–85.
[37] D.D. Gu, H. Zhang, D.H. Dai, C.L. Ma, H.M. Zhang, Y.X. Li, S.H. Li, Anisotropic
corrosion behavior of Sc and Zr modified Al-Mg alloy produced by selective laser
melting, Corrosion Sci. 170 (2020) 108657.
[38] P. Muangtong, A. Rodchanarowan, D. Chaysuwan, N. Chanlek, R. Goodall, The
corrosion behaviour of CoCrFeNi-x (x = Cu, Al, Sn) high entropy alloy systems in
chloride solution, Corrosion Sci. 172 (2020) 108740.
[39] R. Wang, K. Zhang, C. Davies, X.H. Wu, Evolution of microstructure, mechanical
and corrosion properties of AlCoCrFeNi high-entropy alloy prepared by direct laser
fabrication, J. Alloy Compd. 694 (2017) 971–981.
[40] Y. Qiu, S. Thomas, D. Fabijanic, A.J. Barlow, H.L. Fraser, N. Birbilis,
Microstructural evolution, electrochemical and corrosion properties of
AlxCoCrFeNiTiy high entropy alloys, Mater. Des. 170 (2019) 107698.
[41] Y.Z. Shi, B. Yang, X. Xie, J. Brechtl, K.A. Dahmen, P.K. Liaw, Corrosion of
AlxCoCrFeNi high-entropy alloys: Al-content and potential scan-rate dependent
pitting behavior, Corrosion Sci. 119 (2017) 33–45.
[42] S. Hong, Y.P. Wu, J.F. Zhang, Y.G. Zheng, Y. Zheng, J.R. Lin, Synergistic effect of
ultrasonic cavitation erosion and corrosion of WC-CoCr and FeCrSiBMn coatings
prepared by HVOF spraying, Ultrason. Sonochem. 31 (2016) 563–569.
[43] F. Cheng, S.Y. Jiang, J. Liang, Cavitation erosion resistance of microarc oxidation
coating on aluminium alloy, Appl. Surf. Sci. 280 (2013) 287–296.
[44] H.S. Chen, Y.J. Li, D.R. Chen, J.D. Wang, Experimental and numerical
investigations on development of cavitation erosion pits on solid surface, Tribol.
Lett. 26 (2) (2007) 153–159.
[45] D.G. Li, D.R. Chen, P. Liang, Enhancement of cavitation erosion resistance of 316 L
stainless steel by adding molybdenum, Ultrason. Sonochem. 35 (2017) 375–381.
Z. Wei et al.
[46] S. Hong, Y.P. Wu, J.F. Zhang, Y.G. Zheng, Y.J. Qin, J.R. Lin, Ultrasonic cavitation
erosion of high-velocity oxygen-fuel (HVOF) sprayed near-nanostructured WC-
10Co-4Cr coating in NaCl solution, Ultrason. Sonochem. 26 (2015) 87–92.
[47] M. Jadhav, S. Singh, M. Srivastava, G.S.V. Kumar, An investigation on high entropy
alloy for bond coat application in thermal barrier coating system, J Alloy Compd
783 (2019) 662–673.
[48] H.H. Mao, H.L. Chen, Q. Chen, TCHEA1: a thermodynamic database not limited for
“high entropy” alloys, J Phase Equilib Diff 38 (4) (2017) 353–368.
11
Surface & Coatings Technology 409 (2021) 126899
[49] P. Sassatelli, G. Bolelli, M.L. Gualtieri, E. Heinonen, M. Honkanen, L. Lusvarghi,
T. Manfredini, R. Rigon, M. Vippola, Properties of HVOF-sprayed Stellite-6
coatings, Surf. Coat. Tech. 338 (2018) 45–62.
[50] X. Ding, Y. Huang, C.Q. Yuan, Z.X. Ding, Deposition and cavitation erosion
behavior of multimodal WC-10Co4Cr coatings sprayed by HVOF, Surf. Coat. Tech.
392 (2020) 125604.