metals
Article
Effect of Al2O3 on Microstructure and Corrosion Characteristics
of Al/Al2O3 Composite Coatings Prepared by Cold Spraying
Wei Jiang * , Xin Shen, Zhiyuan Wang, Yang Liu, Xiaohua Zhang, Enhao Wang and Junxin Zhang
Citation: Jiang, W.; Shen, X.; Wang, Z.;
Liu, Y.; Zhang, X.; Wang, E.; Zhang, J.
Effect of Al2 O3 on Microstructure and
Corrosion Characteristics of Al/Al2 O3
Composite Coatings Prepared by
Cold Spraying. Metals 2024, 14, 179.
https://doi.org/10.3390/met14020179
Academic Editor: Hannu Hänninen
Received: 7 January 2024
Revised: 22 January 2024
Accepted: 28 January 2024
Published: 1 February 2024
Copyright: © 2024 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Metals 2024, 14, 179. https://doi.org/10.3390/met14020179
School of Materials Science and Chemical Engineering, Harbin University of Science and
Technology, Harbin 150040, China; shenxinbwjl@163.com (X.S.); wangzhiyuan@hrbust.edu.cn (Z.W.);
yang_liu@hrbust.edu.cn (Y.L.); zxhhrbu@hrbust.edu.cn (X.Z.); enhaowang@hrbeu.edu.cn (E.W.);
junxin_zhang2020@163.com (J.Z.)
* Correspondence: jiangwei@hrbust.edu.cn
Abstract: Cold spraying was used to prepare Al/Al2 O3 composite coatings. The Al2 O3 content was
controlled to increase the mechanical property and corrosion resistance of the composite coating.
The inclusion of Al2 O3 particles results in considerable plastic deformation of Al particles and
grain size refinement in the coating. Additionally, the coating’s surface roughness decreased from
24.63 µm to 9.02 µm, and the porosity decreased from 6.34% to 2.07%. The increase in microhardness
of the composite coatings was attributed to the combined effect of residual compressive stress,
second phase strengthening of Al2 O3 , and plastic hardening of Al particles. The electrochemical
test results indicate that the mass fractions of Al2 O3 significantly affected the corrosion resistance
of the Al/Al2 O3 composite coating. Compared to the Al coating, the composite coating exhibited
improved corrosion resistance, with a reduction in corrosion current density from 1.09 × 10−3 A/cm2
to 2.67 × 10−6 A/cm2 and an increase in corrosion potential from −1.57 V to −1.14 V. However, when
the alumina particle content exceeded 17.7%, it led to more Al2 O3 particle breakage, increasing the
weak bonding interfaces in the composite coating, and consequently reducing its corrosion resistance.
Keywords: composite coating; cold spraying; microstructure; corrosion resistance
1. Introduction
Among the coating materials, aluminum coating is extensively utilized in aviation
and space, transportation, marine engineering equipment, and electronics owing to its
excellent anti-corrosion properties, and its electrical and thermal conductivity [1,2]. How-
ever, the application of aluminum coatings was limited due to its relatively low hardness
and insufficient wear resistance. Therefore, the current research focus is on how to modify
the Al coating to improve its overall performance. Aluminum metal matrix composite
(Al-MMC) coatings containing ceramic reinforcements are a type of high-performance
surface-modified coating [3,4]. Ceramic particles in Al-MMC materials can influence the
degree of deformation of Al particles [5], resulting in a decrease in porosity [6] and rough-
ness, and an increase in hardness [7], abrasion resistance [8], and corrosion resistance [9]
of the coating, and it can also change the physical properties of the coating such as the
strength-to-density ratio and high-temperature performance [10].
Cold spraying is a common method for preparing composite coatings [11]. Cold
spraying technology is a surface coating technology developed based on the principles
of gas dynamics and high-speed collision dynamics [12–14]. Cold spraying technology
has the characteristics of high spraying rate, the high strength of the sprayed bonding
layer, dense coating, and low temperature compared to preparation methods such as ther-
mal spraying [15], electroplating [16], laser cladding [17], and chemical vapor deposition
(CVD) [18]. In recent years, scholars have investigated the properties of cold-sprayed
Al-MMC coatings. For instance, in their study, Wang et al. [19] investigated the corrosion
characteristics of Al-MMC coatings and determined their anticorrosion mechanism. They
https://www.mdpi.com/journal/metals
 the corrosion characteristics of Al-MMC coatings and determined their anticorrosion
mechanism. They found that the ceramic particle content and porosity of composite
coatings have a great influence on corrosion resistance. However, the deposition effi-
ciency and coating porosity of ceramic particles are related to the sizes of ceramic parti-
Metals 2024, 14, 179 cles. Yang et al. [20] prepared an Al/Al2O3 composite coating by spraying the raw mate- 2 of 14
rial containing Al2O3 particles onto the surface of the substrate using the cold spraying
technique. The results show that the composite coating had the best corrosion resistance
when that
found the Al the2Oceramic
3 content was 20content
particle vol. %.and Xie porosity
et al. [21]ofprepared
compositeTiB 2 particle
coatings reinforced
have a great
influence on corrosion
7075Al composite resistance.
coatings usingHowever, the deposition
the cold spraying efficiency
technique, and and coating
reduced porosity
coating po-
of ceramic
rosity while particles are related
simultaneously to the sizes
improving theofcorrosion
ceramic particles.
resistanceYangof theetcoating.
al. [20] prepared
Qiu et al.
an
[22]Al/Al
mixed 2 O3spherical,
compositeirregular,
coating by andspraying the raw material
spherical–irregular Al2Ocontaining
3 particles Al 2 Ocold
into 3 particles
spray
onto the surface of the substrate using the cold spraying
powder materials and studied the influence of Al2O3 morphology on coating perfor- technique. The results show
that
mance.the composite
The research coating had the
indicates thatbest corrosion
spherical resistance
particles have when
the the
bestAlmechanical
2 O3 contentinter-was
20 vol. %.
locking Xie et al.with
connection [21]the
prepared
substrateTiBand2 particle reinforced
the lowest surface 7075Al
porosity.composite
Wang et coatings
al. [23]
using
utilizedthethecoldcoldspraying
spraying technique,
techniqueand reduced Al/Al
to prepare coating2O3porosity
composite while simultaneously
coatings and inves-
improving
tigated thethe corrosion resistance
microstructure of the coating. Qiu
and nanomechanical et al. [22]
properties of mixed spherical,
the composite irregular,
coatings in
and spherical–irregular Al O particles into cold spray powder
orthogonal and normal planes. The experimental results show that the degree of plastic
2 3 materials and studied
the influence of
deformation of Al
the2 OAl
3 morphology on coating
particles increases dueperformance.
to the tamping Theeffect
researchof theindicates
high-speedthat
spherical particles have the best mechanical interlocking connection
Al2O3 particles, leading to grain refinement along the grain boundaries of the composite with the substrate and
the lowest surface porosity. Wang et al. [23] utilized the cold spraying
coating, resulting in increased hardness and reduced friction coefficient. Many research- technique to prepare
Al/Al
ers have2 O3 composite
investigated coatings and investigated
the mechanical the microstructure
characteristics and nanomechanical
and corrosion resistance of
properties of the composite coatings in orthogonal and normal
cold-sprayed Al-MMC coatings [24,25], but comparatively little work has been done on planes. The experimental
results
the effect show of that
the the degree of plastic
microstructure deformation
of Al-MMC of the
coatings onAlthe particles
corrosion increases due to and
mechanism the
tamping
process. effect of the high-speed Al 2 O 3 particles, leading to grain refinement along the
grainThisboundaries
paper aims of theto composite
further explorecoating, andresulting
elucidateinthe increased
effect of hardness
doping Aland reduced
2O3 particles
friction coefficient. Many researchers have investigated the
on the microstructure evolution and performance improvement of Al/Al2O3 composite mechanical characteristics and
corrosion resistance of cold-sprayed Al-MMC coatings [24,25], but comparatively little
coatings, building upon previous studies. The fabrication of Al/Al2O3 composite coatings
work has been done on the effect of the microstructure of Al-MMC coatings on the corrosion
on the surface of No. 45 steel was carried out using the cold spraying technique, with
mechanism and process.
varying Al2O3 contents (mass fractions of 0%, 17.7%, 25.5%, 33.3%). A characterization of
This paper aims to further explore and elucidate the effect of doping Al2 O3 particles
the microhardness and electrochemical corrosion behavior of the Al/Al2O 3 composite
on the microstructure evolution and performance improvement of Al/Al2 O3 composite
coatings was conducted, along with an analysis of microstructure evolution.
coatings, building upon previous studies. The fabrication of Al/Al2 O3 composite coatings
on the surface of No. 45 steel was carried out using the cold spraying technique, with
2. Materials and Methods
varying Al2 O3 contents (mass fractions of 0%, 17.7%, 25.5%, 33.3%). A characterization
2.1.
of theExperimental
microhardness Materials
and electrochemical corrosion behavior of the Al/Al2 O3 composite
coatingsCommercial
was conducted,spherical Al powder
along (diameter
with an analysis of20 µm) and Al2O
microstructure 3 powder (diameter 20
evolution.
µm) were used in the cold spray experiment, as illustrated in Figure 1a,b. The substrate
2. Materials
material and Methods
selected was No. 45 steel, the composition of which is detailed in Table 1. The
2.1. Experimental
dimensions of the Materials
substrate were 30 mm × 30 mm × 5 mm.
The carrier gas
Commercial for coldAl
spherical spraying
powderwas compressed
(diameter 20 µm) air and
at a Al
pressure
2 O3 powderof 1.0 MPa and a
(diameter
temperature
20 µm) were used of 500 in°C.
theThe
coldspray
spraygun outlet was
experiment, positionedin10Figure
as illustrated mm away 1a,b. from the sub-
The substrate
material selected
strate, while was No. 45
the traveling steel,
speed wastheset composition
at 60 mm/s.ofThe which is detailed
coating thickness in Table 1. The
obtained by
dimensions
cold spraying of the
wassubstrate were 30
about 400–500 µm.mm × 30 mm × 5 mm.

Figure 1. Morphologies of Al powder (a) and Al2 O3 particles (b).

Table 1. Chemical composition of No. 45 steel.

C Mn Si Cr Ni Cu
0.42–0.50% 0.50–0.80% 0.17–0.37% ≤0.25% ≤0.30% ≤0.25%
Metals 2024, 14, 179 3 of 14

The carrier gas for cold spraying was compressed air at a pressure of 1.0 MPa and a
temperature of 500 ◦ C. The spray gun outlet was positioned 10 mm away from the substrate,
while the traveling speed was set at 60 mm/s. The coating thickness obtained by cold
spraying was about 400–500 µm.

2.2. Test Methods

The surface cross-section morphology of the cold-sprayed coatings was observed
using a scanning electron microscope (SEM, Hitachi, Tokyo, Japan, SU5000). The chemical
composition of the coatings was analyzed using an energy dispersive spectrometer (EDS,
Ultimately Max40, Oxford Instruments, Abingdon, UK), and the microstructural evolution
of the coatings was characterized using electron backscatter diffraction (EBSD, Symmetry,
Oxford Instruments, Abingdon, UK). Porosity statistics of the coatings were obtained from
SEM images of five different areas of the coating cross-section using Image J software
(v1.52a, NIH, Rockville, MD, USA). The phase composition of the coatings was analyzed
using an X-ray diffractometer (XRD, X’Pert PRO, Panalytical, Almelo, The Netherlands).
Microhardness measurements of the samples were conducted using a Vickers hardness
tester (HVS-1000Z, Shangcai, Shanghai, China) with a load of 50 g and a holding time of
15 s. Measurements were taken three times at 20 µm intervals along the depth direction.
The surface roughness of the coating was measured using an ultra-depth-of-field three-
dimensional microscope (OLYMPUS, Tokyo, Japan, DSX1000).
The electrochemical properties of the Al/Al2 O3 composite coating were determined us-
ing an electrochemical workstation (VMP3, BioLogic, Seyssinet-Pariset, France) at 25 ± 1 ◦ C
in a 3.5 wt. % NaCl solution. In a three-electrode system, the working electrode (WE)
was the coating, the reference electrode (SCE) was an Ag/AgCl electrode, and the counter
electrode (CPE) was a platinum electrode. The reference electrode was positioned within
3 mm of the sample surface, and the counter electrode was placed at an equal distance
from the other two electrodes. The open circuit potential (OCP) of the sample was mea-
sured. The electrochemical impedance spectroscopy (EIS) of the composite coating was
evaluated at frequencies ranging from 10 mHz to 100 kHz, with the voltage amplitude
was OCP ± 10 mV. Subsequently, potentiodynamic polarization curves of the samples
were obtained. The electrochemical data of the cold-sprayed coatings were determined
by fitting the potentiodynamic polarization curves by Tafel extrapolation. The tested area
of the samples was 1 cm2 . All electrochemical tests were repeated at least three times for
better accuracy.

3. Results
3.1. XRD Analysis
The XRD test results of the coating are shown in Figure 2. The results show that in
the Al coating, the diffraction peaks were located at 38.5◦ , 44.7◦ , 65.1◦ , and 78.2◦ , which
correspond to the (111), (200), (220), and (311) crystal planes, respectively. In addition, in
the Al/Al2 O3 composite coatings with three different Al2 O3 contents, typical characteristic
peaks of Al2 O3 appeared at 52.6◦ , 57.5◦ , and 68.2◦ . These correspond to crystal planes
(024), (116) and (300), respectively. As can be seen from the Figure 2, no new phases
appeared during the composite coating-manufacturing process. The right side of Figure 2
shows a magnified partial XRD spectrum from 37◦ to 40◦ , indicating a shift of characteristic
peaks toward higher angles. This phenomenon was due to stress changes within the
coating. The compressive residual stress was caused by the shot peening effect of Al2 O3
particles on Al coating. The presence of compressive residual stresses induced a reduction
in the interplanar crystal spacing, accompanied by a shift in the characteristic peaks of Al
phase to higher angles. Residual compressive stress is beneficial to the improvement of
the mechanical and electrochemical properties of the composite coating by reducing the
porosity of the coating and preventing microcrack propagation.
FOR PEER REVIEW 4 of 15
Metals 2024, 14, 179 4 of 14

Figure 2. XRD patterns

Figureof
2. the
XRDcold spraying
patterns coatings.
of the cold spraying coatings.

3.2. Surface Morphology of the Coating

3.2. Surface Morphology of the Coating
Figure 3 presents the micro-morphology of the Al coating and the Al/Al2 O3 composite
Figure 3 presents
coatings.theInmicro-morphology of the Al coating
Figure 3a, the surface morphology of the Aland the reveals
coating Al/Al2shallow
O3 compo-craters
and spherical Al particles. This occurrence is attributed
site coatings. In Figure 3a, the surface morphology of the Al coating reveals shallow cra- to the relatively small plastic
deformation experienced by the aluminum particles, allowing
ters and spherical Al particles. This occurrence is attributed to the relatively small plastic some particles to maintain
their spherical shape. In contrast, the Al/Al2 O3 composite coating does not exhibit a
deformation experienced by the aluminum particles, allowing some particles to maintain
similar phenomenon. The peening action of the Al2 O3 particles leads to the significant
their spherical shape. In contrast,
secondary the Al/Alof2O
plastic deformation 3 composite
the co-depositedcoating
Al particles,does not exhibit
resulting a sim-
in the flattening
ilar phenomenon. of The peening
the spherical Al action
particles.ofFigure
the Al 3c2O 3 particles
illustrates that leads to the
the coating significant
surface sec-
displays deeper
ondary plastic deformation of the co-deposited Al particles, resulting in the flattening of3e
craters due to the presence of embedded spherical Al 2 O 3 particles. Furthermore, Figure
demonstrates that an increase in the percentage of Al2 O3 particles leads to the fragmentation
the spherical Al particles. Figure 3c illustrates that the coating surface displays deeper
of the embedded particles. Lastly, Figure 3g depicts the collision-induced breakage of
craters due to the presence of embedded spherical Al 2 O 3 particles.
some Al2 O3 particles, causing the detachment of certain embedded Furthermore, Figure
Al2 O3 particles from
3e demonstrates thethat an increase in the percentage of Al2O3 particles leads to the frag-
coating.
As can be seen
mentation of the embedded from Figure
particles. 3b,d,f,h,
Lastly, a small3g
Figure number
depictsof micropores developed between
the collision-induced
the particles. The process characteristics of cold
breakage of some Al2O3 particles, causing the detachment of certain embedded spraying resulted in the formation
Al2O3 of
micropores in the deposited coating. In Figure 3h, it can be observed that with the increase
particles from theincoating.
Al2 O3 content in the raw material, the Al2 O3 particles in the composite coating tended
As can be seen fromfrom
to change Figure 3b,d,f,h,
internal cracks toa fracture
small number
separation, ofwhich
micropores developed
is consistent be-
with the results
tween the particles. The process characteristics of cold spraying resulted
observed in the surface microstructure. This indicates that the Al2 3 in the formation in
O particles deposited
the coating are more susceptible to being broken
of micropores in the deposited coating. In Figure 3h, it can be observed by the impact of the
thatsubsequent
with theAl 2 O3
in-
particles with the increase in the Al2 O3 content in the raw material in the spraying process.
crease in Al2O3 content in the raw material, the Al2O3 particles in the composite coating
The porosity of the coatings was calculated from the cross-sectional images using
tended to changeImage
fromJ internal cracks
software, and to fracture
the porosity dataseparation,
are shown in which Table 2. isTheconsistent
Al coating with
showed thethe
results observedhighest
in theporosity
surface microstructure.
at around This indicates
6.34%. The composite that the
coating’s porosity Al2O3 toparticles
decreased 2.07% with
an increase in
deposited in the coating are more Al O content to 17.7%. This decrease can be
2 3 susceptible to being broken by the impact of the sub-attributed to the compaction
effect of the alumina particles. The hardness and density of Al2 O3 particles are higher
sequent Al2O3 particles with the increase in the Al2O3 content in the raw material in the
than those of Al particles. Including Al2 O3 particles in the spraying process enhances the
spraying process.
The porosity of the coatings was calculated from the cross-sectional images using
Image J software, and the porosity data are shown in Table 2. The Al coating showed the
highest porosity at around 6.34%. The composite coating’s porosity decreased to 2.07%
with an increase in Al2O3 content to 17.7%. This decrease can be attributed to the com-
Metals 2024, 14,2024,
Metals x FOR PEER REVIEW
14, 179 5 of 14

deformation of the Al particles, resulting in the sealing of micropores and cracks in the
Al 2O3 composite
coatings. However, thecoatings were
porosity of the 3.39%
composite and increased
coatings 3.59%, slightly
respectively. With incr
with increasing
Al 2 O 3 content. The porosity values of the Al/25.5% Al 2 O 3 and Al/33.3%
concentration in the composite coating, the probability of collision betwe Al 2 O 3 composite
coatings were 3.39% and 3.59%, respectively. With increasing Al2 O3 concentration in
particles
the compositeincreases, resulting
coating, the probabilityinof more
collisionalumina
between the particles beingincreases,
Al2 O3 particles broken. Fra
particles
resulting inincrease
more aluminamicroporosity
particles being and microcracking
broken. Fractured Al2 O3 in Al/Alincrease
particles 2O3 compos
microporosity and microcracking
causing coating porosity to increase. in Al/Al 2 O 3 composite coatings, causing coating porosity
to increase.

Figure 3. Surface and cross-section microstructures of Al coatings (a,b), Al/17.7% Al2 O3 com-
Figure 3. Surface and cross-section microstructures of Al coatings (a,b), Al/17.7% Al
posite coatings (c,d), Al/25.5% Al2 O3 composite coatings (e,f) and Al/33.3% Al2 O3 composite
coatings (c,d), Al/25.5% Al2O3 composite coatings (e,f) and Al/33.3% Al2O3 comp
coatings (g,h).
(g,h).
Table 2. Porosity of the cold spraying coatings.
TableSpecimen
2. Porosity of theAl
cold spraying coatings.
Al/17.7% Al O Al/25.5% Al2 O3 Al/33.3% Al2 O3
2 3

Specimen 6.34 ± 0.08 Al 2.07 ± 0.12

Porosity (%)
Al/17.7% 3.39 ± 0.07 3.59 ± 0.10
Al2O3 Al/25.5% Al2O3 Al/3
Porosity (%) 6.34 ± 0.08 2.07 ± 0.12 3.39 ± 0.07 3

3.3. Coating Hardness and Roughness

The microhardness distribution of coatings with different Al2O3 conte
 Metals 2024, 14, 179 6 of 14

3.3. Coating Hardness and Roughness

The microhardness distribution of coatings with different Al2 O3 contents is shown
in Figure 4. With the increase in depth, the microhardness of the coating did not show
a significant difference. This phenomenon is an indication that the Al2 O3 particles are
Metals 2024, 14, x FOR PEER REVIEW
uniform throughout the coating. The average hardness of the Al coating is 21.62 HV,
and the average hardness of the Al/17.7% Al2 O3 , Al/25.5% Al2 O3 , and Al/33.3% Al2 O3
composite coatings are 47.25 HV, 48.54 HV, and 49.55 HV, respectively. The average
hardness of the sprayed coating significantly increased when ceramic particles of Al2 O3
grainadded.
were morphology, consequently
This phenomenon enhancing
can be attributed theirreasons.
to three hardness. Lastly,
Firstly, the Althe
2 O3
additio
particles
particles refined
enhanced thethe
secondAlphase-strengthening
grain and increased effect ofthe
the number of grain
aluminum-based boundaries
composite
coating, thereby increasing its hardness. Secondly, the presence of
ence of grain boundaries inhibited dislocation movement, increasing the yieceramic particles created
residual stress in the coatings, leading to changes in the crystal microstructure and grain
the composite and consequently the average coating hardness. The increase
morphology, consequently enhancing their hardness. Lastly, the addition of Al2 O3 particles
hardness
refined the Al was relatively
grain and increasedlowtheafter
numbertheofAl 2O3boundaries.
grain content exceeded
The presence 17.7%.
of grainThis w
when a certain amount of reinforcement by ceramic particles occurred,
boundaries inhibited dislocation movement, increasing the yield stress in the composite and the
consequently the average coating hardness. The increase in coating
density significantly increased, leading to dislocation entanglement during hardness was relatively
low after the Al2 O3 content exceeded 17.7%. This was because, when a certain amount of
movement.byAs
reinforcement a result,
ceramic further
particles dislocation
occurred, the dislocationmovement is hindered,
density significantly increased,resulting
tively low
leading increaseentanglement
to dislocation in coating hardness.
during dislocation movement. As a result, further
dislocation movement is hindered, resulting in a relatively low increase in coating hardness.

Figure4. 4.
Figure Microhardness
Microhardness profilesprofiles of coldcoatings
of cold spraying spraying coatings
along along
the coating the coating
cross-section. cross-sect
Figure 5 shows the 3D surface morphology and surface root-mean-square roughness
(Sq) ofFigure 5 shows
the Al coating, the
as well 3DAl/17.7%
as the surfaceAlmorphology and surface root-mean-squ
2 O3 , Al/25.5% Al2 O3 and Al/33.3% Al2 O3
ness (Sq)coatings,
composite of the respectively.
Al coating, Asas
thewell
Al2 O3as the Al/17.7%
concentration Al2Othe
increased, 3, Al/25.5%
surface rough- Al2O3 an
ness of the composite coatings tended to decrease and then increase.
Al2O3 composite coatings, respectively. As the Al2O3 concentration increased, The Al coating showed
a surface roughness of 24.63 µm. The Al/17.7% Al2 O3 composite coating was 9.02 µm,
roughness
the Al/25.5% Al of O
the composite coatings tended to decrease and then increase. T
2 3 composite coating was 15.63 µm, and the Al/33.3% Al2 O3 composite
ing showed
coating a surface
was 16.94 µm. The roughness
incorporationof of 24.63 µm. The
Al2 O3 particles Al/17.7%
resulted Al2O3 composite
in a smoother com- c
posite coating surface. The 3D morphology of the coatings
9.02 µm, the Al/25.5% Al2O3 composite coating was 15.63 µm, and the Al/3 shows that the surface of the
Al coating was very rough and wavy and the Al/Al2 O3 composite coating’s surface was
composite coating was 16.94 µm. The incorporation of Al2O3 particles res
relatively flat. The addition of Al2 O3 particles caused the deformation of already coated
smoother
Al composite
particulates, gradually coating
flattening surface. The 3D
the Al particles, andmorphology of the coatings
reducing the roughness of the sho
surfaceHowever,
coating. of the Al coating
as the addition was
of Alvery roughincreased,
2 O3 particles and wavy the and the Al/Al
cooperative 2O3 composi
deformation
ability of Al particles decreased, and the probability of a mutual
surface was relatively flat. The addition of Al2O3 particles caused the deformimpact of Al 2 O 3 particles
rose, causing the Al2 O3 particles to fracture. The broken Al2 O3 particles were embedded in
ready coated Al particulates, gradually flattening the Al particles, and re
the coating surface, leading to a slight increase in the surface roughness of the coating.
roughness of the coating. However, as the addition of Al2O3 particles increas
operative deformation ability of Al particles decreased, and the probability o
impact of Al2O3 particles rose, causing the Al2O3 particles to fracture. The br
particles were embedded in the coating surface, leading to a slight increase in
roughness of the coating.
Metals 2024, 14, x FOR PEER REVIEW 7 of 15
Metals 2024, 14, 179 7 of 14

Figure
Figure5.5.The
The3D3Dmorphology
morphologyofofAlAlcoatings
coatings(a),
(a),Al/17.7%
Al/17.7%Al
Al2OO
2 3 composite
3 compositecoatings
coatings(b),
(b),Al/25.5%
Al/25.5%
AlAl
2O3Ocomposite coatings (c) and Al/33.3% Al2 O 3 composite coatings (d), and the roughness
2 3 composite coatings (c) and Al/33.3% Al2 O3 composite coatings (d), and the roughness of the
of the
cold spray coating (e).
cold spray coating (e).

3.4.Corrosion
3.4. CorrosionExperiment
Experiment
3.4.1. Coating ElectrochemicalCorrosion
3.4.1. Coating Electrochemical CorrosionBehavior
Behavior
TheThepotentiodynamic
potentiodynamicpolarization
polarizationcurves
curvesofofthe
thecoldcoldspray
spraycoating
coatingmeasured
measuredinina a
3.5 wt. % NaCl solution are shown in Figure 6a. The open
3.5 wt. % NaCl solution are shown in Figure 6a. The open circuit potentials (OCP)circuit potentials (OCP)ofofthe
the
pure Al coating, and the Al/17.7% Al O ,
pure Al coating, and the Al/17.7% Al22O33, Al/25.5% Al2OAl/25.5% Al O , and Al/33.3%
2 3,3and Al/33.3% Al2O Al O composite
2 3 composite
3
coatings, were −1.46 V, −1.08 V, −1.25 V, and −1.20 V, respectively. The OCP values of
coatings, were −1.46 V, −1.08 V, −1.25 V, and −1.20 V, respectively. The OCP values of the
the Al coatings were more negative compared to the Al/Al2 O3 composite coatings, which
Al coatings were more negative compared to the Al/Al2O3 composite coatings, which can
can be a preliminary indication that the incorporation of Al2 O3 particles improved the
be a preliminary indication that the incorporation of Al2O3 particles improved the corro-
corrosion resistance of the coating. The corrosion potential (E ) and corrosion current
sion resistance of the coating. The corrosion potential (Ecorr) andcorr corrosion current densi-
density (I ) for different samples are presented in Table 3. The Ecorr and Icorr of the
ty (Icorr) for corr
different samples are presented−in Table 3. The Ecorr and Icorr of the Al coating
Al coating were −1.58 V−3 and 1.09 × 10 3 A/cm2 . For the Al/17.7% Al2 O3 , Al/25.5%
were −1.58 V and 1.09 × 10 A/cm . For the Al/17.7% Al2O3, Al/25.5% Al2O3, and Al/33.3%
2
Al O3 , and Al/33.3% Al2 O3 composite coatings, the Ecorr and Icorr were −1.14 V and
Al2O2 3 composite coatings, the Ecorr and Icorr were −1.14 V and 2.67 × 10−6 A/cm2,−−1.25 V
2.67 × 10−6−5A/cm22, −1.25 V and 2.12 × 10−5 A/cm 2 , and − 1.22 V and 1.54 × 10 5 A/cm2 ,
and 2.12 × 10 A/cm , and −1.22 V and 1.54 × 10−5 A/cm2, respectively. Notably, the Ecorr of
respectively. Notably, the Ecorr of the Al/Al2 O3 composite coating exhibited an increase
the Al/Al2O3 composite coating exhibited an increase compared to that of the Al coating,
compared to that of the Al coating, concomitant with a decrease in Icorr . The Ecorr serves as
concomitant with a decrease in Icorr. The Ecorr serves as an indicator of corrosion difficulty,
an indicator of corrosion difficulty, while Icorr mirrors the rate of corrosion. The increase in
while
Ecorr Iand
corr mirrors the rate of corrosion. The increase in Ecorr and the decrease in Icorr indi-
the decrease in Icorr indicate an improvement in the corrosion resistance of the
cate an
compositeimprovement
coating. Thein Ethe corrosion resistance of the composite coating. The Ecorr val-
corr values of the Al/25.5% Al2 O3 and Al/33.3% Al2 O3 composite
ues of the Al/25.5% Al 2O3 and Al/33.3% Al2O3 composite coatings were higher than that
coatings were higher than that of the Al coating but lower than that of the Al/17.7% Al2 O3
ofcomposite
the Al coating butThe
coating. lower Icorrthan
wasthat of than
lower the Al/17.7%
that of the AlAl2O3 composite coating. The Icorr
coating but higher than that of
was lower than that of the Al coating but higher
the Al/17.7% Al2 O3 composite coating. The corrosion behavior than that of theofAl/17.7%
the coating Al2isO3influenced
compo-
site
by coating.
the content The of
corrosion behaviorThe
Al2 O3 particles. of the coatingofisAlinfluenced
addition by the content of Al2O3
2 O3 particles can make the coating
particles. The addition of Al 2O3 particles can make the coating denser and improve the
denser and improve the corrosion resistance. However, the particle boundary between
Metals 2024,
Metals 14,14,
2024, 179x FOR PEER REVIEW 9 of 15 8 of 14

Al particles
order and Al/17.7%
as follows: Al2 O3 particles
Al2O3 > provides
Al/33.3% Ala channel for theAlentry
2O3 > Al/25.5% of NaCl
2O3 > Al. Thesesolution.
results Al2 O3
particles
align withundergo fragmentation
the potentiodynamic due to excessive
polarization addition
curves. The mechanismformofmore particle boundaries.
the improvement
Therefore, the corrosion
in the corrosion resistance
resistance of compositeofcoatings
the coating increases
is explained and then
in detail in thedecreases
discussion with the
section. in alumina content.
increase

Figure 6.6.Potentiodynamic
Figure Potentiodynamic polarization curves
polarization (a), Nyquist
curves plots (b),
(a), Nyquist Bode
plots modulus
(b), (c) and phase
Bode modulus (c) and phase
angle (d) spectra for cold-sprayed Al coatings and Al/Al2O3 composite coatings.
angle (d) spectra for cold-sprayed Al coatings and Al/Al2 O3 composite coatings.
3.4.2. Surface Morphology after Electrochemical Corrosion
Table 3. Results of Tafel extrapolation of potentiodynamic polarization curves and electrochemical
Figure 7 depicts the surface morphology and chemical element composition of the
data obtained via equivalent circuit fitting for cold-sprayed coatings.
Al coating and Al/Al2O3 composite coating after undergoing a corrosion test. The specific
Icorr
content Rp of each element Rs
is presented
RI
in TableQc
4. Upon examinationRof Figure 7a,e,i,m, Qdl
it
ct
Specimen Ecorr (V) nc ndl
(A/cm2 )was observed
(Ω·cm2 ) that
(kΩthe
·cm2 )Al coating
(kΩ·cm2 )displayed
(µF·cm−significant
2) corrosion
(kΩ·cmholes,
2
) whereas
(µF·cm−2 ) the
Al −1.57 1.09 × 10−Al/Al
3 2O 3 composite
139.4 coating
1.72 × 10−2 exhibited
0.071 smaller
229.7corrosion0.71
holes, which is mainly 596.9
2.20 attributed 0.62
Al/17.7%Al2 O3 −1.14 2.67 × 10−to6
pitting
21,447.7 10−2
1.58 ×Additionally,
corrosion. 7.82 the pure35.1Al coating demonstrated
0.87 3.41the highest Cl con- 0.92
487.4
Al/25.5%Al2 O3 −1.26 2.12 × 10−5 2579.6 1.82 × 10−2 2.04 50.4 0.70 2.91 25.9 0.98
Al/33.3%Al2 O3 −1.22 1.54 × 10
tent
− 5 at 2.66
6967.8
wt. %. On
1.84 × 10
the
− 2 other hand,
3.49
the composite
45.6
coatings,
0.83
namely,
3.01
Al/17.7%
164.2
Al2O3, 0.61
Al/25.5% Al2O3, and Al/33.3% Al2O3, showcased lower Cl contents at 0.40 wt. %, 1.18 wt.
%, and 1.86 wt. %, respectively. The combination of morphology and data leads to the
The corrosion
conclusion that the Al resistance
coating isofmore Al/Al 2 O3 composite
susceptible coatings
to corrosion. ThewasCl- inevaluated using electro-
the electrolyte
reacted with the passivation film on the surface of the coating in
chemical impedance spectroscopy (EIS). Figure 6b depicts the Nyquist plots generated froma nucleophilic substitu-
tion reaction,
tests conducted resulting in the destruction
on cold-sprayed of the passivation
composite film. The reaction
coatings immersed in a 3.5% is NaCl
as fol- solution.
lows:
The diameter of the capacitive arc in the high-frequency region of the Nyquist diagram has
a significant correlation withAl the
2Ocorrosion resistance
3 + 8Cl− = 2AlCl 4− + 3O2−of the coatings. By adding
(1) ceramic
particles, the arc diameter of the Al/Al2 O3 composite coating is made considerably larger
than that of the pure aluminum O coating
2− + H2Oat a high
= 2OH − frequency. This disparity(2)signifies a
noteworthy enhancement in corrosion resistance for the composite coating featuring added
alumina, as opposed to its pure AlCl4− + 3OH− = Al(OH)
aluminum 3 + 4Cl− Among the Al/Al O (3)
counterpart. 2 3 composite
coatings, the Al/17.7%
The whole reaction isAlequivalent
2 O3 coating
to Clhas the largest
− catalyzing thecapacitive
following arc diameter. The capacitive
reactions:
arc diameter of the Al/33.3% Al2 O3 coating is slightly larger than the Al/25.5% Al2 O3
Al2O3 + 3H2O = 2 Al(OH)3 (4)
coating. Figure 6c,d shows the Bode plot obtained after impedance testing. According
to previous studies [26], the magnitude of low-frequency impedance |Z| is positively
correlated with corrosion resistance. From Figure 6c, we see that the |Z| of the Al/17.7%
Al2 O3 composite coating was the largest, which also proves its best corrosion resistance.
Figure 6d illustrates a phase diagram used for calculating the interfacial processes involved
in impedance data. As shown in the figure, the phase diagrams of almost all coatings have
Metals 2024, 14, 179 9 of 14

two peaks throughout the test, i.e., two time constants (TC). One is in the mid-frequency
region (MF), indicating the presence of an oxide film on the coating surface. The other
is in the low-frequency region (LF). The low-frequency region is characterized by pitting
formation, which is due to the relaxation process of adsorbed substances (e.g., Cl− ) ac-
quired in the vulnerable region [27], and the diffusion resistance in the system decreases
with increasing Al2 O3 content, which corresponds to the porosity of the composite coating
in Table 2.
The obtained electrochemical impedance spectroscopy can be fitted using the ZSim-
pWin software (v3.60, AMETEK Scientific Instruments, Berwyn, IL, USA), which helps
in reflecting the electrochemical processes at the interface between the sample and the
electrolyte. Figure 6b shows the fitted equivalent circuit, which indicates that the oxide film
on the coating surface is not uniform [28]. In the figure, Rs is the solution resistance, Rct
is the charge transfer resistance of the aluminum coating, and RI is the added resistance
of the electrolyte within the localized corrosion site. Considering the non-ideal nature of
the system, we used a constant phase element CPE (abbreviated as Q) instead of a pure
capacitor [29,30]. QC is an oxide film capacitor and Qdl is a double-layer capacitor. The RI
and Rct values derived from the fitting results are shown in Table 3. At low frequencies,
the current cannot flow through the oxide film, only through the corrosion site. At high
frequencies, the current can pass through the oxide film. The combined values of RI and
Rct in the fitting results determine the corrosion resistance of the coating. A larger value
of RI + Rct indicates the better corrosion resistance of the coating. The RI + Rct values of
the coatings were 2.27 kΩ·cm2 , 11.23 kΩ·cm2 , 4.95 kΩ·cm2 and 6.50 kΩ·cm2 , respectively.
The coatings’ corrosion resistance were ranked, in descending, order as follows: Al/17.7%
Al2 O3 > Al/33.3% Al2 O3 > Al/25.5% Al2 O3 > Al. These results align with the potentiody-
namic polarization curves. The mechanism of the improvement in the corrosion resistance
of composite coatings is explained in detail in the discussion section.

3.4.2. Surface Morphology after Electrochemical Corrosion

Figure 7 depicts the surface morphology and chemical element composition of the Al
coating and Al/Al2 O3 composite coating after undergoing a corrosion test. The specific
content of each element is presented in Table 4. Upon examination of Figure 7a,e,i,m, it was
observed that the Al coating displayed significant corrosion holes, whereas the Al/Al2 O3
composite coating exhibited smaller corrosion holes, which is mainly attributed to pit-
ting corrosion. Additionally, the pure Al coating demonstrated the highest Cl content at
2.66 wt. %. On the other hand, the composite coatings, namely, Al/17.7% Al2 O3 , Al/25.5%
Al2 O3 , and Al/33.3% Al2 O3 , showcased lower Cl contents at 0.40 wt. %, 1.18 wt. %, and
1.86 wt. %, respectively. The combination of morphology and data leads to the conclusion
that the Al coating is more susceptible to corrosion. The Cl− in the electrolyte reacted with
the passivation film on the surface of the coating in a nucleophilic substitution reaction,
resulting in the destruction of the passivation film. The reaction is as follows:

Al2 O3 + 8Cl− = 2AlCl4− + 3O2− (1)

O2− + H2 O = 2OH− (2)

4− − −
AlCl + 3OH = Al(OH)3 + 4Cl (3)

Table 4. EDS analysis results of the coating surface after corrosion.

Specimen Al (wt. %) Cl (wt. %) O (wt. %)

Al 79.22 2.66 18.12
Al/17.7%Al2 O3 80.26 0.40 19.33
Al/25.5%Al2 O3 73.01 1.18 25.82
Al/33.3%Al2 O3 69.08 1.86 37.16
Metals 2024, 14, 179 Metals 2024, 14, x FOR PEER REVIEW 10 of 14 11 of

Figure
Figure 7. Surface 7. Surface
morphology morphology
and elementaland elemental
maps maps after electrochemical
after electrochemical corrosion ofcorrosion
(a–d) Al of (a–d)
coating, (e–h) Al/17.7%Al 2O3 composite coating, (i–l) Al/25.5% Al2O3 composite coating, and (m–
coating, (e–h) Al/17.7%Al2 O3 composite coating, (i–l) Al/25.5% Al2 O3 composite coating, and
Al/33.3% Al2O3 composite coating.
(m–p) Al/33.3% Al2 O3 composite coating.
Table 4. EDS analysis results of the coating surface after corrosion.
The whole reaction is equivalent to Cl− catalyzing the following reactions:
Specimen Al (wt. %) Cl (wt. %) O (wt. %)
Al Al 2 O 3 + 3H 2 O =
79.22 2 Al(OH) 3 2.66 (4)
18.12
Al/17.7%Al2O3 80.26 0.40 19.33
At the same time, the surface of the coating constituted a galvanic cell as the NaCl
Al/25.5%Al2O3 73.01 1.18 25.82
solution acts as an electrolyte. The cathode generated OH− , which led to a decrease in
Al/33.3%Al2O3 69.08 1.86 37.16
the PH value of the electrolyte, and the anode generated Al3+ . The anode and cathode
reacted as:
4. Discussion
O2 + H2 O + 3e− → 4OH− (5)
To further investigate the microstructural evolution of coatings with different al
mina contents, EBSD analysisAl → Alwas 3+
3e−
+performed on Al coatings and Al/17.7% Al (6)2O3 comp
site coatings. Figure 8a,d shows the IPF maps of the Al
The corrosion resistance of the coating is negatively correlated with the content of coating and Al/17.7% Al2
composite coatings, respectively, illustrating the grain orientation and microstructu
Cl element. Cl− tended to accumulate in corrosive areas. From Figure 7m,o, we see that
within the coatings. The coatings underwent severe plastic deformation due to the hig
the Cl element was mainly concentrated at the bonding interface between the Al matrix
velocity impact. The surfaces were characterized by small grains surrounding lar
and Al2 O3 particles. The bonding between Al particles and Al2 O3 particles was weak,
grains. The appearance of this structure is attributed to the localized distortion of par
and a weak bonding surface was present. The weak binding surface provided a channel
cles concentrated at the particle interface during rapid collisions. In other words, a lar
for the electrolyte to enter the coating. When the amount of alumina particles added
amount of energy from particle impact was taken up by the particle surface, leading
exceeded 17.7%, more alumina broke due to collisions. The broken alumina particles
particle refinement. High-speed particle impacts led to the accumulation of high disloc
created additional weak bonding surfaces in the coating, resulting in reduced corrosion
tion densities, which further caused dynamic recrystallization, resulting in grain refin
resistance. Thement.
O contents
Crystalof the Aliscoating
rotation evidentand fromthetheAl/17.7% Al2 Ovariations
color gradient 3 , Al/25.5% Al2 O38a,d,
in Figure , whe
and Al/33.3% the Al2assorted
O3 composite coatings were 18.12 wt. %, 19.33 wt. %, 25.82 wt.
color gradients represent different grain orientations. Furthermore, it can %,
and 37.16 wt. %, respectively.
observed that theThe surface oxygen
introduction of Al2contents of the
O3 particles ledcoatings increased
to a greater degreewith
of deformatio
the increase in of
AlAl2 O3particles
content.inThe main sources of O on the surface of the
the coating, accompanied by an increase in the number coating were
of small-siz
(1) Al2 O3 particles containing
grains. the element
Figure 8c,f displays O; thealso,
grain(2)size
Al reacts with O2ofinthe
distribution theAl
electrolyte
coating andto Al/17.7
form Al2 O3 ; (3)Al
OH − generated by the cathodic reaction reacts with Al3+ to form Al(OH) ,
2O3 composite coating. The average grain size of the coating decreased from 3 1.68 µ
and (4) Al(OH)to3 1.47
is further converted
µm after to insoluble
the addition Al2 O3 ·3HFigure
of Al2O3 particles. 2 O [31].
8b,eThe
showsreactions
the KAM areplots of t
as follows:
4Al + 3O2 = 2Al2 O3 (7)
 Metals 2024, 14, 179 11 of 14

Al3+ + 3OH− → Al(OH)3 (8)

2Al(OH)3 → Al2 O3 ·3H2 O (9)
These reaction products covered the surface of the coating, making it more difficult
for the coating to corrode further.

4. Discussion
To further investigate the microstructural evolution of coatings with different alumina
contents, EBSD analysis was performed on Al coatings and Al/17.7% Al2 O3 composite
coatings. Figure 8a,d shows the IPF maps of the Al coating and Al/17.7% Al2 O3 composite
coatings, respectively, illustrating the grain orientation and microstructure within the
coatings. The coatings underwent severe plastic deformation due to the high velocity
impact. The surfaces were characterized by small grains surrounding large grains. The
appearance of this structure is attributed to the localized distortion of particles concentrated
at the particle interface during rapid collisions. In other words, a large amount of energy
from particle impact was taken up by the particle surface, leading to particle refinement.
High-speed particle impacts led to the accumulation of high dislocation densities, which
further caused dynamic recrystallization, resulting in grain refinement. Crystal rotation is
evident from the color gradient variations in Figure 8a,d, where the assorted color gradients
represent different grain orientations. Furthermore, it can be observed that the introduction
Metals 2024, 14, x FOR PEER REVIEW of Al O particles led to a greater degree of deformation of Al particles in the12coating, of 15
2 3
accompanied by an increase in the number of small-sized grains. Figure 8c,f displays
the grain size distribution of the Al coating and Al/17.7% Al2 O3 composite coating. The
Alaverage
coatinggrain
and size of the coating
the Al/17.7% Al2Odecreased
3 composite from 1.68 µm
coating, to 1.47 µm which
respectively, after the
areaddition
used toof
Al
check O
2 the
3 particles.
residual compressive stress in the grains. It is evident from the plots thatAl
Figure 8b,e shows the KAM plots of the Al coating and the Al/17.7% 2 O3
the
composite coating, respectively, which are used to check the residual
residual compressive stress generated inside the grains of the Al/17.7% Al2O3 composite compressive stress
in the grains.
coating It is evident
was higher than thatfrom theAl
of the plots that the
coating. residual in
Moreover, compressive
Figure 2, we stress
see generated
that the
inside
XRD the shifted
peaks grains of the Al/17.7%
towards higher Al 2 O3 composite
angles, indicatingcoating was higher
a reduction than thatspacing,
in interplanar of the Al
coating. Moreover, in Figure 2, we see that the XRD peaks shifted
in accordance with Bragg’s law. This confirms the presence of residual compressivetowards higher angles,
indicating a reduction in interplanar spacing, in accordance with Bragg’s
stress in the coating which induced crystal rotation and led to the creation of substruc-law. This confirms
the presence
tures of residual
in the coating. The compressive stress in compressive
presence of residual the coating which induced
stresses crystal rotation
also contributed to
and led to the creation of substructures
the enhanced hardness of the composite coating.in the coating. The presence of residual compressive
stresses also contributed to the enhanced hardness of the composite coating.

EBSDinverse
Figure8.8.EBSD
Figure inversepole
pole figure
figure (IPF) maps,
maps, kernel
kernelaverage
averagemisorientation
misorientation(KAM)
(KAM)and
andgrain size
grain
distribution
size forfor
distribution different coatings:
different (a–c)
coatings: Al Al
(a–c) coating, (d–f)
coating, Al/17.7%
(d–f) AlAl
Al/17.7% 2O 3 3composite
2O compositecoating.
coating.

Electrochemicaltests
Electrochemical testsshowed
showedthatthatthe
theincorporation
incorporationofofAlAl
2O2O 3 particles
3 particles significantly
significantly
reducedthe
reduced thedegree
degreeofofcorrosion
corrosionofofthethecomposite
compositecoating.
coating.Several
Severalfactors
factorscontributed
contributedtoto
theincrease
the increaseinincorrosion
corrosionresistance.
resistance.Firstly,
Firstly,the
theinherent
inherentdisadvantages
disadvantages ofof thecold
the coldspray
spray
technique resulted in a high porosity in the coating. The entry of electrolyte solution into
these pores increases the specific surface area of the corrosion reaction. The addition of
hard alumina particles can compact the coating, making the surface denser, reducing
porosity. This makes it more difficult for the electrolyte to penetrate the interior of the
coating, thereby enhancing the corrosion resistance of the composite coating. Secondly,
 Metals 2024, 14, 179 12 of 14

technique resulted in a high porosity in the coating. The entry of electrolyte solution
into these pores increases the specific surface area of the corrosion reaction. The addition
of hard alumina particles can compact the coating, making the surface denser, reducing
porosity. This makes it more difficult for the electrolyte to penetrate the interior of the
coating, thereby enhancing the corrosion resistance of the composite coating. Secondly,
after adding Al2 O3 particles, the grains of the composite coating are refined, the grain
size is reduced, and the grain boundary densities of the composite coatings are increased.
The oxidation reactions preferentially occur at the grain boundaries due to their higher
energy, and the increased density of these boundaries promotes the formation of Al2 O3
from Al and O2 . This results in the formation of a barrier layer of Al2 O3 on the coating
surface, which improves its corrosion resistance. Thirdly the addition of Al2 O3 particles
improves the corrosion resistance of the composite coating. This is due to the reduction in
the exposed area of the Al matrix after the addition. The corrosion resistances of Al/25.5%
Al2 O3 and Al/33.3% Al2 O3 composite coatings are weaker than that of the Al/17.7% Al2 O3
composite coating. This is because more Al2 O3 particles will be broken due to collision
when the amount of Al2 O3 particles added exceeds 17.7%. The broken Al2 O3 particles will
create additional weak bonding surfaces in the coating, and the electrolyte solution can
more easily enter the coating’s interior through the weak bonding surfaces. Figure 9 shows
Metals 2024, 14, x FOR PEER REVIEW a schematic diagram of the corrosion principle of the coating before and after the 13 of 15
addition
of Al2 O3 particles, depicting the grain refinement caused by the addition of Al2 O3 particles
as well as the fragmentation of Al2 O3 particles. The addition of Al2 O3 particles led to a
large
the plastic
coating. Atdeformation
the same time,of the
theAl particles,
grains of theresulting
compositein the closure
coating of refined.
were the micropores
The cor-in
the composite coating and the densification of the coating. At the same
rosion resistance of the composite coating was improved by the combined effect of time, the grains
theseof
the composite
changes. coating were refined. The corrosion resistance of the composite coating was
improved by the combined effect of these changes.

Figure 9. Schematic representation of the effect of Al2 O3 particle addition on coating.

Figure 9. Schematic representation of the effect of Al2O3 particle addition on coating.
5. Conclusions
5. Conclusions
The Al/Al2 O3 composite coatings were deposited on No. 45 steel by cold spraying.
TheThe Al/Al2and
structure O3 composite coatings
characteristics of thewere
Al/Al deposited
2 O3 coatingson No.
were45 steel by coldinvestigated.
systematically spraying.
The structure and characteristics of the Al/Al
The inclusion of Al2 O3 particles led to a more significant plastic transformation ofinvesti-
2 O 3 coatings were systematically the pre-
gated.
viouslyThe inclusionAlofparticles,
deposited Al2O3 particles
resulting ledinto a morecoating.
a denser significant plastic transformation
Compared to the cold-sprayed of
the
Al previously
coating, thedeposited
grains in theAl Al/Al
particles,
O
2 3 resulting
composite in a denser
coatings coating.
were refined,Compared
and the to the
residual
cold-sprayed
compressiveAl coating,
stress andthe grains in
hardness the increased.
were Al/Al2O3 composite
The porositycoatings
and were refined,
surface and
roughness
the
of residual
composite compressive stress and
coatings initially hardness
decreased andwere
thenincreased.
increased The withporosity and of
the amount surface
Al2 O3
roughness of composite
particles. The compositecoatings initially
coating with decreased
Al/17.7% Al2 Oand
3 hadthen
theincreased with the
lowest porosity andamount
showed
ofthe
Albest corrosion The
2O3 particles. resistance. The promotion
composite coating with of aAl/17.7%
corrosion-resistant
Al2O3 had layer on the porosity
the lowest surface of
theshowed
and Al/A2 Othe 3 composite coatingresistance.
best corrosion was facilitated by the refinement
The promotion of grains. The corrosion
of a corrosion-resistant layer
−6 A/cm2 , which is significantly
× 10facilitated
oncurrent density
the surface ofofthetheAl/A
composite coating was
2O3 composite coating2.67was by the refinement of
lower The
grains. thancorrosion
the corrosion current
current density
density of the
of the pure Al coating,
composite coating wasat 1.092.67 ×−
× 10 103−6A/cm
A/cm2 .2,If
the amount
which of addedlower
is significantly Al2 Othan
3 particles exceedscurrent
the corrosion 17.7%, some
density of of
thethe
Alpure
2 O3 will break. The
Al coating, at
broken Al
1.09 × 10 A/cm
−3 2 3 . If the amount of added Al2O3 particles exceeds 17.7%, some ofofthe
O particles
2 result in a slight increase in the porosity and roughness the
composite coating, and will create more weak bonding surfaces in
Al2O3 will break. The broken Al2O3 particles result in a slight increase in the porosity and the composite coating.
These weak
roughness bonding
of the surfaces
composite provide
coating, and channels
will create formore
the electrolyte
weak bonding to enter the interior
surfaces in the
of the coating,
composite coating. leading
Thesetoweak
a decrease
bonding in the corrosion
surfaces resistance
provide channels of the
for composite coating.
the electrolyte to
enter the interior of the coating, leading to a decrease in the corrosion resistance of the
composite coating. The addition of Al2O3 particles to the cold spray Al coating will sig-
nificantly impact the microstructure of the resulting Al/Al2O3 composite coating, affect-
ing both its mechanical properties and corrosion behavior.
Metals 2024, 14, 179 13 of 14

The addition of Al2 O3 particles to the cold spray Al coating will significantly impact the
microstructure of the resulting Al/Al2 O3 composite coating, affecting both its mechanical
properties and corrosion behavior.

Author Contributions: W.J. contributed to the conceptualization, methodology, data curation,

writing—original draft preparation, funding acquisition, writing—reviewing and editing. X.S. per-
formed visualization, data curation, writing—original draft preparation and formal analysis. Z.W.
and Y.L. performed conceptualization, formal analysis, validation. X.Z. and J.Z. contributed to the
validation. E.W. helped with the methodology, and the writing—reviewing and editing. All authors
have read and agreed to the published version of the manuscript.
Funding: This work was supported by Heilongjiang Provincial Natural Science Foundation of
China (LH2020E084), the Key Research and Development Program of Heilongjiang (Grant No.
2022ZX01A01), and the National Natural Science Foundation of China (51901058).
Data Availability Statement: The original contributions presented in the study are included in the
article, further inquiries can be directed to the corresponding author/s.
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Trueba, M.; Trasatti, S.P. Study of Al alloy corrosion in neutral NaCl by the pitting scan technique. Mater. Chem. Phys. 2010,
121, 523–533. [CrossRef]
2. Diab, M.; Pang, X.; Jahed, H. The effect of pure aluminum cold spray coating on corrosion and corrosion fatigue of magnesium
(3% Al-1% Zn) extrusion. Surf. Coat. Technol. 2017, 309, 423–435. [CrossRef]
3. Fernandez, R.; Jodoin, B. Cold Spray Aluminum-Alumina Cermet Coatings: Effect of Alumina Content. J. Therm. Spray Technol.
2018, 27, 603–623. [CrossRef]
4. Bu, H.Y.; Yandouzi, M.; Lu, C.; MacDonald, D.; Jodoin, B. Cold spray blended Al+Mg17 Al12 coating for corrosion protection of
AZ91D magnesium alloy. Surf. Coat. Technol. 2012, 207, 155–162. [CrossRef]
5. Liu, H.H.; Tariq, N.U.; Ren, Y.P.; Zhao, L.J.; Yang, Y.; Cui, X.Y.; Wang, J.Q.; Xiong, T.Y. Influence of Al2 O3 content on microstructure,
electrical conductivity and adhesion strength of cold sprayed Al-Al2 O3 coatings on PEEK substrate. Surf. Coat. Technol. 2022,
446, 128752. [CrossRef]
6. Li, Q.L.; Yuan, S.M.; Li, Z.; Gao, X.X.; Chen, B.C. Mechanical response and microstructure evolution of SiC particle-reinforced
Al-MMCs under ultrasonic loading. Compos. Part A Appl. Sci. Manuf. 2023, 173, 107657. [CrossRef]
7. Zhao, L.J.; Tariq, N.U.; Ren, Y.P.; Liu, H.H.; Han, R.F.; Cui, X.Y.; Wang, J.Q.; Xiong, T.Y. Effect of Particle Size on Ceramic Particle
Content in Cold Sprayed Al-Based Metal Matrix Composite Coating. J. Therm. Spray Technol. 2022, 31, 2505–2516. [CrossRef]
8. Liu, H.J.; Fu, M.K.; Pang, S.Z.; Zhu, H.Q.; Zhang, C.; Ming, L.J.; Liu, X.Y.; Ding, M.H.; Fu, Y.D. Effect of Ball-Milled Feedstock
Powder on Microstructure and Mechanical Properties of Cu-Ni-Al-Al2 O3 Composite Coatings by Cold Spraying. Coatings 2023,
13, 948. [CrossRef]
9. Witharamage, C.S.; Alrizqi, M.A.; Chirstudasjustus, J.; Darwish, A.A.; Ansell, T.; Nieto, A.; Gupta, R.K. Corrosion-resistant
metallic coatings for aluminum alloys by cold spray. Corros. Sci. 2022, 209, 110720. [CrossRef]
10. Sayahlatifi, S.; Zaiemyekeh, Z.; Shao, C.W.; McDonald, A.; Hogan, J.D. Micromechanical damage analysis of Al-Al2 O3 composites
via cold-spray additive manufacturing. Int. J. Mech. Sci. 2023, 259, 108573. [CrossRef]
11. Chen, H.; Liu, C.; Chu, X.; Zhang, T.; Zheng, J. Corrosion Behavior and Microstructure of Cu-Based Composite Coatings Deposited
by Cold Spraying. Metals 2022, 12, 955. [CrossRef]
12. Aubanel, L.; Delloro, F. Tribological behavior of steel-based composite coatings produced by cold spray. Surf. Coat. Technol. 2023,
470, 129815. [CrossRef]
13. Bakar, I.A.A.; Omar, N.I.; Yusuf, Y.; Rahim, T.A. Reflection and Future Perspectives in Cold Spray Technology: A Bibliometric
Analysis. J. Therm. Spray Technol. 2023, 32, 1576–1595. [CrossRef]
14. Huang, C.J.; List, A.; Wiehler, L.; Schulze, M.; Gärtner, F.; Klassen, T. Cold spray deposition of graded Al-SiC composites. Addit.
Manuf. 2022, 59, 17. [CrossRef]
15. Ilyushchanka, A.P.; Baray, S.G.; Letsko, A.I.; Talako, T.L.; Manoila, Y.D.; Janu, Y.; Chauhan, V.S.; Patra, M.K.; Saini, L. High-
Temperature-Resistant, Mechanically Stable FeCrNiAl/Al2 O3 Thermally Sprayed Thick Ceramic Coatings for Stealth Applications
over X-Band. Adv. Eng. Mater. 2022, 24, 103116. [CrossRef]
16. Gül, H.; Kiliç, F.; Aslan, S.; Alp, A.; Akbulut, H. Characteristics of electro-co-deposited Ni-Al2 O3 nano-particle reinforced metal
matrix composite (MMC) coatings. Wear 2009, 267, 976–990. [CrossRef]
17. Jue, J.B.; Gu, D.D.; Chang, K.; Dai, D.H. Microstructure evolution and mechanical properties of Al-Al2 O3 composites fabricated
by selective laser melting. Powder Technol. 2017, 310, 80–91. [CrossRef]
18. Konstantiniuk, F.; Tkadletz, M.; Czettl, C.; Schalk, N. Fracture Properties of α– and κ–Al2 O3 Hard Coatings Deposited by
Chemical Vapor Deposition. Coatings 2021, 11, 1359. [CrossRef]
Metals 2024, 14, 179 14 of 14

19. Wang, Y.Y.; Normand, B.; Mary, N.; Yu, M.; Liao, H.L. Effects of ceramic particle size on microstructure and the corrosion behavior
of cold sprayed SiC P /Al5056 composite coatings. Surf. Coat. Technol. 2017, 315, 314–325. [CrossRef]
20. Yang, X.; Li, W.; Yu, S.; Xu, Y.; Hu, K.; Zhao, Y. Electrochemical characterization and microstructure of cold sprayed AA5083/Al2 O3
composite coatings. J. Mater. Sci. Technol. 2020, 59, 117–128. [CrossRef]
21. Xie, X.L.; Hosni, B.; Chen, C.Y.; Wu, H.J.; Li, Y.L.; Chen, Z.; Verdy, C.; Kedim, O.E.I.; Zhong, Q.D.; Addad, A.; et al. Corrosion
behavior of cold sprayed 7075Al composite coating reinforced with TiB2 nanoparticles. Surf. Coat. Technol. 2020, 404, 126460.
[CrossRef]
22. Qiu, X.; Tariq, N.U.; Qi, L.; Tang, J.R.; Cui, X.Y.; Du, H.; Wang, J.Q.; Xiong, T.Y. Effects of Dissimilar Alumina Particulates
on Microstructure and Properties of Cold-Sprayed Alumina/A380 Composite Coatings. Acta Metall. Sin. Engl. Lett. 2019,
32, 1449–1458. [CrossRef]
23. Wang, Q.; Birbilis, N.; Huang, H.; Zhang, M.X. Microstructure characterization and nanomechanics of cold-sprayed pure Al and
Al-Al2 O3 composite coatings. Surf. Coat. Technol. 2013, 232, 216–223. [CrossRef]
24. Zhang, Z.C.; Liu, F.C.; Han, E.H.; Xu, L. Mechanical and corrosion properties in 3.5% NaCl solution of cold sprayed Al-based
coatings. Surf. Coat. Technol. 2020, 385, 125372. [CrossRef]
25. Qiu, X.; Tariq, N.U.; Wang, J.Q.; Tang, J.R.; Gyansah, L.; Zhao, Z.P.; Xiong, T.Y. Microstructure, microhardness and tribological
behavior of Al2 O3 reinforced A380 aluminum alloy composite coatings prepared by cold spray technique. Surf. Coat. Technol.
2018, 350, 391–400. [CrossRef]
26. Lu, F.F.; Ma, K.; Li, C.X.; Yasir, M.; Luo, X.T.; Li, C.J. Enhanced corrosion resistance of cold-sprayed and shot-peened aluminum
coatings on LA43M magnesium alloy. Surf. Coat. Technol. 2020, 394, 125865. [CrossRef]
27. Liu, F.; Han, E.H.; Xu, L.; Uzoma, P.C. Effects of Al2 O3 on the microstructures and corrosion behavior of low-pressure cold gas
sprayed Al 2024-Al2 O3 composite coatings on AA 2024-T3 substrate. Surf. Coat. Technol. 2019, 9, 735–742.
28. Mansfeld, F.; Jeanjaquet, S.L.; Kendig, M.W. An electrochemical impedance spectroscopy study of reactions at the metal/coating
interface. Corros. Sci. 1986, 26, 735–742. [CrossRef]
29. da Silva, F.S.; Bedoya, J.; Dosta, S.; Cinca, N.; Cano, I.G.; Guilemany, J.M.; Benedetti, A.V. Corrosion characteristics of cold gas
spray coatings of reinforced aluminum deposited onto carbon steel. Corros. Sci. 2017, 114, 57–71. [CrossRef]
30. Conde, A.; de Damborenea, J.J. Electrochemical impedance spectroscopy for studying the degradation of enamel coatings. Corros.
Sci. 2002, 44, 1555–1567. [CrossRef]
31. Chen, H.X.; Kong, D.J. Comparison on electrochemical corrosion performances of arc and laser thermal sprayed Al–Ti–Ni coatings
in marine environment. Mater. Chem. Phys. 2020, 251, 123200.

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.