coatings
Article
Effect of Temperature on the Corrosion Resistance of Ni5Al
Coating Deposited by Electric Arc in 3.5% NaCl Solution
Cinthya Dinorah Arrieta-González 1 , Francisco Javier Perez-Arizmendi 2 , Milagros Alejandra Dorta-Leon 2
and Jesús Porcayo-Calderón 3, *
Citation: Arrieta-González, C.D.;
Perez-Arizmendi, F.J.; Dorta-Leon,
M.A.; Porcayo-Calderón, J. Effect of
Temperature on the Corrosion
Resistance of Ni5Al Coating
Deposited by Electric Arc in 3.5%
NaCl Solution. Coatings 2023, 13,
1349. https://doi.org/10.3390/
coatings13081349
Academic Editor: Peter Rodič
Received: 16 June 2023
Revised: 18 July 2023
Accepted: 21 July 2023
Published: 1 August 2023
Copyright: © 2023 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/).
Coatings 2023, 13, 1349. https://doi.org/10.3390/coatings13081349
1 National Technologic of Mexico, Technological Institute of Zacatepec, Calzada Instituto Tecnológico 27,
Zacatepec 62780, Mexico; cdaglez@gmail.com
2 DIPROCAT, Economos 6719, Zapopan 45037, Mexico; francisco@diprocat.com (F.J.P.-A.);
milagros.dorta@diprocat.com (M.A.D.-L.)
3 Department of Chemical Engineering and Metallurgy, University of Sonora, Hermosillo 83000, Mexico
* Correspondence: jporcayoc@gmail.com
Abstract: The electrochemical behavior of the Ni5Al coating deposited by an electric arc was evalu-
ated. Its behavior was evaluated in a saline solution as a function of temperature (20 ◦ C, 40 ◦ C, and
60 ◦ C). The variation as a function of time of the Ni5Al coating’s values of open circuit potential, linear
polarization resistance, and the evolution of its electrochemical impedance spectra were analyzed.
With this deposition technique, the rapid formation of thick coatings is achieved, which reduces the
presence of interconnected porosity. Even though the microstructural characteristics showed the
presence of trapped oxides, the electrochemical measurements carried out showed excellent corrosion
resistance of the coating. The coating quickly develops a passive layer that allows it to rapidly reach
thermodynamic equilibrium with the corrosive medium.
Keywords: Ni5Al coatings; corrosion; passive layer; RPL; EIS; electrochemical corrosion
1. Introduction
In aqueous media, the degradation of materials and alloys occurs through electro-
chemical processes that involve the oxidation of one species and the reduction of another,
that is, an electron transfer process. This degradation process is widely known as corro-
sion, and it is one of the main problems that cause significant economic losses in different
industrial processes. [1–6]. The corrosive nature of an electrolyte depends on the dissolved
species it contains as well as environmental conditions such as temperature. These degra-
dation processes contribute to the deterioration of material properties and their premature
failures [7–9].
In order to counteract these thermodynamically spontaneous processes, corrosion
prevention and control techniques have been implemented. Some of them can be corrosion
inhibitors, cathodic protection, selection of materials, and surface modification through
the application of coatings, among others. With the implementation of these actions, it
has been possible to increase the useful life of the materials. However, the choice of
prevention techniques depends on the location and environmental conditions of the surface
to be protected. In particular, the use of metallic coatings is a way of modifying the
chemical composition of a substrate with poor resistance to corrosion. In this way, a coated
system achieves high chemical stability in a corrosive environment. Coatings applied by
thermal spray can be a technical solution for corrosion problems at both low and high
temperatures [2,9–18].
Through thermal spraying, it is possible to modify the chemical composition of the
surface of a substrate. The deposited layers can be made of both metallic and non-metallic
materials (ceramics and polymers). For it, materials in powder or wire form are heated to
or near their melting point and projected at high velocity onto the substrate to produce
https://www.mdpi.com/journal/coatings
Coatings 2023, 13, 1349 2 of 16

satisfactory bond strength without changing the metallurgical characteristics of the base
metal [9]. These characteristics make thermal spraying one of the most versatile tools for
protecting materials [14].
The protective properties of a coating are also dependent on the thermal spray method
used for its deposition (plasma spray, electric arc spray, cold spray, flame spray, high velocity
oxy-fuel spray, etc.), since it influences the coating’s microstructural characteristics [14,15,17].
To guarantee good corrosion protection, in addition to excellent chemical stability, it is
necessary to minimize defects such as interconnected porosity. This reduces the risk of
diffusion of the electrolyte to the substrate.
Due to its high speeds of spraying, the electric arc thermal projection technique is a
good alternative to carry out the surface modification of a substrate to increase its resistance
to corrosion, recover dimensions, increase its resistance to wear, etc., without affecting the
microstructural properties of the substrate [16].
Regarding corrosion resistance, various studies have shown that Ni-based alloys
deposited as protective coatings show greater chemical stability than those based on
Fe [2,9–21]. Ni5Al coatings are generally used as an anchor layer for the deposition of a top
coating with low bond strength towards the substrate; however, according to their chemical
composition, they may also present excellent corrosion resistance in certain corrosive
environments. Therefore, the objective of this study is to evaluate the electrochemical
performance of the Ni5Al coating deposited by an electric arc. Its evaluation was carried
out in a NaCl solution (3.5 wt.%) at temperatures of 20 ◦ C, 40 ◦ C, and 60 ◦ C, and its
electrochemical performance was obtained through measurements of open circuit potential,
linear polarization resistance, and electrochemical impedance.

2. Materials and Methods

Ni5Al coating. The coatings were generated with a Ni5Al alloy in the form of a wire,
which was deposited by the electric arc spray technique on 304 stainless steel plates. Prior
to the deposition of the coating, the stainless-steel plates were cleaned with acetone, and
their surface was shotblasted with alumina particles in accordance with the recommended
practice of NACE No. 1/SSPC-SP 5. After surface preparation, the metal plates were
cleaned again with dry air and acetone, and the coatings were deposited in that condition.
A copper wire was soldered to each coated plate on the uncoated rear face, and in that
condition, they were encapsulated in epoxy resin. The surface of the coatings was roughed
with abrasive paper from grade 120 to grade 600, and in that surface condition, the corrosion
tests were carried out.
Electrochemical tests. As corrosive medium, a 3.5% NaCl solution (% by weight)
was used, and the corrosion tests were carried out at 20 ◦ C, 40 ◦ C, and 60 ◦ C for 24 h.
An electrochemical cell with three electrodes was used, where the working electrode was
Ni5Al coatings encapsulated in epoxy resin, a saturated calomel electrode (SHE) was
used as a reference electrode, and a graphite rod was used as an auxiliary electrode.
Open circuit potential (OCP), linear polarization resistance (LPR), and electrochemical
impedance spectroscopy (EIS) measurements were performed. OCP values were recorded
as a function of time, and LPR measurements were performed by polarizing the working
electrode ± 10 mV with respect to the corrosion potential at a sweep rate of 10 mV/min.
EIS measurements were evaluated under open circuit conditions by applying a sinusoidal
AC signal with an amplitude of ± 10 mV in the frequency range of 100 kHz to 0.01 Hz.

3. Results and Discussion

3.1. Structural Aspects of the Coating
Figure 1 shows the cross-sectional appearance of the Ni5Al coating. The morphological
aspects observed are consistent with the typical characteristics associated with coatings
deposited by the thermal spray technique, that is, a heterogeneous structure, the formation
of the coating by the overlapping of layers, segregation of phases, the presence of trapped
oxides, and porosity [9–18]. A great advantage of the electric arc coating deposition
Coatings 2023, 13, x FOR PEER REVIEW

Coatings 2023, 13, 1349 formation of the coating by the overlapping of layers, segregation of phases, 3 of 16 the p
of
Coatings 2023, 13, x FOR PEER REVIEW trapped oxides, and porosity [9–18]. A great advantage of the electric arc coatin 3 of 15

sition technique is the rapid formation of thick coatings. The thickness of a coati
technique
important is the rapid formation
parameter of thick
because thecoatings.
greaterThethethickness of a coating
thickness, is an the
the lower important
probability
parameter
formation because the greater
of the coating by thethe thickness,of
overlapping the lowersegregation
layers, the probability of interconnected
of phases, the presence
connected porosity [9,15]. According to the measurements made, the average thic
porosity
of trapped[9,15]. According
oxides, to the measurements
and porosity [9–18]. A great made, the average
advantage thickness
of the electric arc of the coating
coating depo-
the
after coating
sitionthe
after
grinding
technique
the grinding
isprocess 1 mmprocess
wasformation
the rapid ± 50
of µm.
was 1 mm ± 50 µm.
thick coatings. The thickness of a coating is an
important parameter because the greater the thickness, the lower the probability of inter-
connected porosity [9,15]. According to the measurements made, the average thickness of
the coating after the grinding process was 1 mm ± 50 µm.

Figure1.1.1.
Figure
Figure Cross-sectional aspect
Cross-sectional
Cross-sectional ofthe
aspect
aspect of theNi5Al
Ni5Al
of coatings.
thecoatings.
Ni5Al coatings.
Figure
Figure22shows
showsan anapproach
approachtotothe
thecross
crosssection
sectionof ofthe
theNi5Al
Ni5Alcoating
coatingand
andits
itselement
element
Figure
mapping. It 2 shows
shows an approach
details of the to the
structure of cross
the section
coating of thebyNi5Al
formed the coating
impact andand its
mapping. It shows details of the structure of the coating formed by the impact and defor-
mapping.
deformation
mation of the Itofdrops
shows of details
the dropsliquid of the
of liquid
metal andstructure
metal and
the of the
the presence
presence coating formed
of trapped
of trapped oxides.oxides.byThe
The dark the impact an
dark
phases
mation
phases
correspondof the
correspond drops
to trapped of liquid
to trapped metaloxides,
aluminum
aluminum oxides, and the
and theand presence
the gray
clear of trapped
clear phases
gray phases oxides.
to thetoNi5Al
the Ni5AlThe dark
alloy
alloy [15,17].
correspond to trapped aluminum oxides, and the clear gray phases to the Ni5
[15,17].
[15,17].

Figure2.2.Details
Figure Detailsand
andmapping
mappingof
ofelements
elementsto
tothe
thecross
crosssection
sectionof
ofthe
theNi5Al
Ni5Alcoatings.
coatings.
Coatings 2023, 13, x FOR PEER REVIEW 4

Coatings 2023, 13, 1349 4 of 16

3.2. Open Circuit Potential Curves

3.2. Open Circuit
Figure Potential
3 shows theCurves
evolution of the open circuit potential as a function of time fo
Ni5Al coating
Figure immersed
3 shows in saline
the evolution solution
of the at thepotential
open circuit differentastest temperatures.
a function The obser
of time for
the Ni5Al
trend coatingthat
indicates immersed
as the in saline solution
temperature at the different
increases, test temperatures.
the coating tends to show The
a more ac
observed trend indicates that as the temperature increases, the coating tends to show a
behavior.
more active behavior.

Figure3.3.OCP
Figure OCP values
values versus
versus timetime forNi5Al
for the the Ni5Al
coating.coating.

Even though the grinding process reduced the heterogeneity of the surface and with
Even though the grinding process reduced the heterogeneity of the surface and w
it the presence of active sites, it is observed that at 20 ◦ C and 40 ◦ C, the coating showed a
it the presenceinoftheactive
stable behavior sites,
first two it isofobserved
hours immersion,that
andatsubsequently
20 °C and 40 an °C, thedrop
abrupt coating
in show
stable behavior
potential values wasin observed.
the first twoAfterhours of immersion,
the abrupt and values,
drop in potential subsequently
a steady an abrupt dro
decline
potential
was values
observed untilwas observed.
the end After
of the test. Thethe abrupt of
magnitude drop in potential
the potential dropvalues, a steady
was lower at dec
60 ◦
wasC,observed
as was its until
variationtheafter
end5–6 h of test.
of the immersion, possibly dueoftothe
The magnitude the potential
rapid formation
dropofwas low
a60passive
°C, aslayer
was on
its the coating after
variation surface.
5–6 h of immersion, possibly due to the rapid formatio
The trend of the open circuit potential values provides a clear trend of the active-
a passive layer on the coating surface.
passive behavior of the surface under study. In this case, the greatest active behavior was
observedThe intrend of the
the first hoursopen circuit potential
of immersion. values
After that, provides awere
the fluctuations clear trend or
minimal of the ac
passive behavior
insignificant, of the surface
which suggests under study.
the establishment In this case,
or development of athe greatest
protective active
layer behavior
on the
observed
coating in the first hours of immersion. After that, the fluctuations were minimal o
surface.
It has been
significant, suggested
which suggeststhat the
the establishment
observed behavior may be associated
or development of aboth with thelayer on
protective
presence of surface defects (pores and oxides) [10,22–24] and with the absence of a passive
coating surface.
layer [10,13,25]. Both situations activate the metallic dissolution process since they allow
It has been suggested that the observed behavior may be associated both with
the infiltration of the electrolyte through the superficial defects as well as the direct contact
presence
of of surface
the metallic surface defects
with the (pores andenvironment
aggressive oxides) [10,22–24]
due to theand withofthe
absence absence of a pas
a protective
layer[10,12,13,22,23,25]
layer [10,13,25]. Both or situations
the presenceactivate the metallic
of superficial defectsdissolution process
such as porosity, since
voids, or they a
oxides trapped [22–24].
the infiltration of the electrolyte through the superficial defects as well as the direct con
of the metallic surface with the aggressive environment due to the absence of a protec
3.3. Linear Polarization Resistance Curves
layer [10,12,13,22,23,25] or the presence of superficial defects such as porosity, void
Figure 4 shows the evolution of the resistance values to linear polarization as a function
oxides
of trapped
time for [22–24].
the Ni5Al coating immersed in saline solution at the different test temperatures.
The figure shows a clear effect of temperature on the corrosion rate; that is, the increase in
3.3. Linear Polarization
temperature Resistance
reduces the resistance to Curves
polarization of the coating.
Figure 4 shows the evolution of the resistance values to linear polarization as a f
tion of time for the Ni5Al coating immersed in saline solution at the different test tem
atures. The figure shows a clear effect of temperature on the corrosion rate; that is
increase in temperature reduces the resistance to polarization of the coating.
Coatings 2023, 13, x FOR PEER REVIEW 5
Coatings 2023, 13, 1349 5 of 16

Figure4.4.Change
Figure Changein Rp
in values over over
Rp values time for thefor
time Ni5Al
thecoating.
Ni5Al coating.

At 20 ◦ C, at the beginning of the test, in the first three hours of immersion, an increase
At 20 °C, at the beginning of the test, in the first three hours of immersion, an incr
in the Rp values was observed, followed immediately by a sharp drop, and after that,
ainquasi-stationary
the Rp valuesbehavior
was observed,
where thefollowed
Rp values immediately by a sharp
oscillated around drop, and
3000 ohm-cm 2 . A after th

quasi-stationary
similar behavior was behavior
observedwhere ◦
at 40 C, thewith
Rp avalues oscillated
slight increase around
in the 3000followed
Rp values ohm-cm2. A sim
by a decrease
behavior was and a subsequent
observed at 40increase,
°C, with anda after
slightthree hours in
increase of immersion,
the Rp values a quasi-
followed
stable behavior with Rp values around 2000 ohm-cm 2 during the rest of the test. On the
decrease and a subsequent increase, and after three hours of immersion, a quasi-s
other hand, at 60 ◦ C, only a decrease in Rp values was2observed during the first hour of
behavior with Rp values around 2000 ohm-cm during the rest of the test. On the o
immersion, followed by a quasi-stable behavior with Rp values around 1600 ohm-cm2
hand, the
during at 60
rest°C, only
of the a decrease
test. in Rp
The evolution values
of the was observed
Rp values is consistentduring theoffirst
with that hour of im
the OCP
sion, followed
values by a quasi-stable
shown in Figure 3. Despite thebehavior with Rp
lower corrosion valuesobserved
resistance around at 1600
60 ◦ohm-cm
C, at this during
2

rest of the the

temperature test.coating
The evolution
showed theofmost thestable
Rp values is consistent
behavior, which may be with
duethat ofrapid
to the the OCP va
development
shown in Figureof a protective
3. Despitelayer on lower
the the surface of the coating.
corrosion resistance observed at 60 °C, at this
The evolution
perature the coatingof both the OCP
showed theandmostRp stable
values is due to the
behavior, anodicmay
which and becathodic
due to the r
processes that occur on the surface of the coating. In general, it can be said that the anodic
development of a protective layer on the surface of the coating.
dissolution is due to the occurrence of the following reactions [10,26–30]:
The evolution of both the OCP and Rp values is due to the anodic and cathodic
cesses that occur on the Ni
surface
+ H2 Oof↔the + H+ +
coating.
NiOH Ine−general, it can be said that
(1) the an
dissolution is due to the occurrence of the following reactions [10,26–30]:

𝑁𝑖 +
NiOH +H𝐻+ ↔
𝑂↔Ni+𝑁𝑖𝑂𝐻
+ H2 O + 𝐻 +𝑒 (2)

𝑁𝑖𝑂𝐻
Ni +
+2+𝐻+ e−↔
↔ Ni 𝑁𝑖 + 𝐻 𝑂 (3)

Al + 3H2 O ↔ Al (𝑁𝑖 ↔ +𝑁𝑖3H + +

OH )3,ads +3e𝑒− , (4)

𝐴𝑙
Al (+
OH3𝐻
)3,ads𝑂↔
↔Al𝐴𝑙
(OH(𝑂𝐻
)33+)+ ,3e− , + 3𝐻 + 3𝑒 , (5)

𝐴𝑙)33(+𝑂𝐻
Al (OH ) +, ↔ Al
+ 3H +(3H
↔3+𝐴𝑙 𝑂𝐻 )
2 O, + 3𝑒 , (6)

𝐴𝑙 (𝑂𝐻 ) + 3𝐻 ↔ 𝐴𝑙 + 3𝐻 𝑂,
It has been reported that the formation and accumulation of hydroxides, as we
oxyhydroxides, can retard the metal dissolution process because their presence limit
diffusion of aggressive species towards the metal surface [10,31].
However, in the presence of chloride ions, the following side reactions are also
Coatings 2023, 13, 1349 6 of 16

It has been reported that the formation and accumulation of hydroxides, as well as
oxyhydroxides, can retard the metal dissolution process because their presence limits the
diffusion of aggressive species towards the metal surface [10,31].
However, in the presence of chloride ions, the following side reactions are also possi-
ble [10,32,33]:
Al (OH )3,ads + Cl − ↔ Al (OH )2 Clads + OH − , (7)

Al (OH )2 Clads + Cl − ↔ Al (OH )Cl2,ads + OH − , (8)

Al (OH )Cl2,ads + Cl − ↔ AlCl3 + OH − , (9)

Similar reactions are possible for Ni hydroxides. Since these reactions occur on the
metal surface, they affect the adhesion of the layer of protective corrosion products, thereby
enhancing the corrosion process [10].

3.4. Electrochemical Impedance Spectroscopy

Figure 5 shows the evolution of the electrochemical impedance spectra as a function of
time for the Ni5Al coating immersed in the saline solution at 20 ◦ C. The Nyquist diagram
shows the presence of at least two overlapping depressed capacitive semicircles, whose
diameters vary as a function of immersion time. The Bode diagram in its impedance
modulus format, |Z|, in the high frequency region (>1000 Hz) shows the presence of the
high frequency plateau, and in the intermediate and low frequency regions, the presence of
several slopes in the linear relationship (log f -log |Z|). Each observed slope is associated
with a capacitive semicircle observed in the Nyquist diagram. The presence of the low
frequency plateau is not observed, which suggests that the impedance modulus is greater
than the last recorded value (>3 kHz). From the Bode plot in its phase angle (◦ ) format,
there is a clear presence of three time constants, each associated with each slope of the
linear relationship, log f -log |Z|, as well as with each capacitive semicircle present in
the Nyquist diagram. The first time constant is observed between 10 and 100 Hz, the
second around 1 Hz, and the third at frequencies less than 0.1 Hz. The first time constant
shows the highest value of the maximum phase angle and may be associated with the
capacitive response of the coating surface. It is observed that at the beginning of the test,
the maximum phase angle decreased until 6 h of immersion (57◦ → 50◦ ) and subsequently
showed a constant increase until reaching a value of 60◦ at the end of the test. The other
time constants showed a decreasing behavior in their maximum value of phase angle, and
these may be associated either with processes of adsorption or diffusion of species due to
the presence of films of adsorbed metal hydroxides according to the corrosion mechanism
indicated in the previous section.
Figure 6 shows the evolution of the electrochemical impedance spectra as a function of
time at 40 ◦ C. From the Nyquist diagram, it is possible to observe the presence of several
depressed capacitive semicircles, which apparently overlap. The Bode plot, in its impedance
modulus format, |Z|, in the high frequency region (>1000 Hz) also shows the presence
of the high frequency plateau, and again in the intermediate and low frequency regions,
several slopes of the linear relationship (log f -log |Z|) are observed. The presence of the low
frequency plateau is not observed, which suggests that the impedance modulus is greater
than the last recorded value (>2.1 kHz). From the Bode plot in its phase angle (◦ ) format, it
is also possible to observe the presence of three time constants. As observed at 20 ◦ C, the
first is located between 10 and 100 Hz, the second around 1 Hz, and the third at frequencies
less than 0.1 Hz. The meaning of the time constants can be the same as that described below.
Unlike what was observed at 20 ◦ C, in this case, for the first time constant, it is observed
that the maximum of the phase angle increased constantly throughout the test (46◦ → 57◦ ).
The other time constants showed a behavior similar to that observed at 20 ◦ C.

Coatings 2023, 13, 1349
capacitive response of the coating surface. It is observed that at the beginning of the test,
the maximum phase angle decreased until 6 h of immersion (57° → 50°) and subsequently
showed a constant increase until reaching a value of 60° at the end of the test. The other
time constants showed a decreasing behavior in their maximum value of phase angle, and
these may be associated either with processes of adsorption or diffusion of species due to
the presence of films of adsorbed metal hydroxides according to the corrosion mechanism 7 of 16
indicated in the previous section.

Coatings 2023, 13, x FOR PEER REVIEW 7 of 15

(a)

(b)

(c)
Figure
Figure5.5.Evolution
Evolutionofofthe
theNyquist
Nyquistand Bode
and diagrams
Bode diagramsforfor
thethe
Ni5Al coating
Ni5Al immersed
coating in saline
immersed in saline
solution at 20 °C.
◦ (a) is Nyquist diagram; (b) is Bode plot, impedance modulus; (c) is Bode plot,
solution at 20 C. (a) is Nyquist diagram; (b) is Bode plot, impedance modulus; (c) is Bode plot,
phase angle.
phase angle.
Figure 6 shows the evolution of the electrochemical impedance spectra as a function
of time at 40 °C. From the Nyquist diagram, it is possible to observe the presence of several
depressed capacitive semicircles, which apparently overlap. The Bode plot, in its imped-
ance modulus format, |Z|, in the high frequency region (>1000 Hz) also shows the pres-
Coatings 2023,
Coatings 2023, 13,
13, x1349
FOR PEER REVIEW 8 of 15
8 of 16

(a)

(b)

(c)

Figure 6. Evolution of the Nyquist and Bode diagrams for the Ni5Al coating immersed in saline
solution at 40 ◦ C. (a) is Nyquist diagram; (b) is Bode plot, impedance modulus; (c) is Bode plot,
phase angle.
 Figure 6. Evolution of the Nyquist and Bode diagrams for the Ni5Al coating immersed in sa
solution at 40 °C. (a) is Nyquist diagram; (b) is Bode plot, impedance modulus; (c) is Bode p
phase angle.
Coatings 2023, 13, 1349 9 of 16
Figure 7 shows the evolution of the electrochemical impedance spectra as a funct
of time at 60 °C. The Nyquist diagram suggests the apparent presence of two depres
capacitive
Figure semicircles, which apparently
7 shows the evolution overlap.impedance
of the electrochemical Their diameters
spectra asshow little variat
a function
◦
with
of timeimmersion
at 60 C. The time. The Bode
Nyquist diagramplot, in its the
suggests impedance
apparent modulus
presence offormat, |Z|, shows ch
two depressed
capacitive semicircles, which apparently overlap. Their diameters show
acteristics similar to those described at lower temperatures. That is, in the high freque little variation
with immersion time. The Bode plot, in its impedance modulus format, |Z|, shows
region (>1000 Hz), the presence of the high frequency plateau is observed, and in the
characteristics similar to those described at lower temperatures. That is, in the high
termediate and (>1000
frequency region low frequency regions,
Hz), the presence of several
the high slopes
frequencyareplateau
observed in the linear
is observed, and relati
ship
in the(log f-log |Z|).
intermediate Once
and lowagain, the regions,
frequency presence of theslopes
several low-frequency
are observed plateau is not observ
in the linear
indicating
relationshipthat(log the
f -logimpedance
|Z|). Once modulus is greater
again, the presence of than the last recorded
the low-frequency plateauvalue
is not (>1.2 kH
observed,
The Bode indicating
plot in itsthatphasethe angle
impedance modulus
(°) format is shows
also greater than the last recorded
the presence of threevalue
time consta
(>1.2 kHz). The Bode plot in its phase angle ( ◦ ) format also shows the presence of three
in the same frequency regions noted above. The maximum of the phase angle of the fi
time constants in the same frequency regions noted above. The maximum of the phase
time constant tends to increase with the immersion time (43° → 50°),◦ and that of the seco
angle of the first time constant tends to increase with the immersion time (43 → 50◦ ), and
and third time constants showed the opposite behavior.
that of the second and third time constants showed the opposite behavior.

(a)

(b)
Figure 7. Cont.
Coatings 2023, 13, x FOR PEER REVIEW 10 o
Coatings 2023, 13, 1349 10 of 16

Coatings 2023, 13, x FOR PEER REVIEW 10 of 15

(c) (c)
Figure7.7. Evolution
Evolution of
of the
Figure
Figure Evolution ofthe Nyquist and
the and Bode
Nyquist
Nyquist Bode diagrams
and diagrams for
Bode for the
diagrams theNi5Al
Ni5Alcoating
for the coating immersed in
Ni5Alimmersed insaline
saline
coating immersed in sa
solution at 60 ◦°C. (a) is Nyquist diagram; (b) is Bode plot, impedance modulus; (c) is Bode plot,
solution
solution at 60
phase angle.
60 °C. (a)
C. (a) is is Nyquist
Nyquist diagram;
diagram; (b) is(b) is
Bode Bode
plot, plot, impedance
impedance modulus;modulus;
(c) is Bode(c) is
plot, Bode p
phase angle.
phase angle.

ItIt is
is interesting
interesting to
toobserve
observethat
thatatat
thethe
end of the
end testtest
of the (24 h),
(24the
h),maximum of theof
the maximum phase
the
angle
phase
It angle
is
of interesting
theof first
thetime
totime
observe
first constant
that
tended
constant
at
to the
tended
end of
decrease with
to decrease
thewith
testincrease
the (24 h),inthe
the increase
maximum(61°
temperature
in temperature
of the ph
→ ◦57°
angle
(61 → of→
57the →first
◦50°) 50◦ )time
and also constant
and experienced
also experienced tended to decrease
a displacement
a displacement at higherwith
at thefrequencies
frequencies
higher increase(25 Hz in →
(25 temperature
40 Hz
Hz → (
→ →
4057°Hz →
50 Hz).
→ 50°) It has been
and Italso
50 Hz). reported
hasexperienced that the
been reporteda that decrease in
displacement the phase
the decreaseatinhigher angle
the phase is due to
frequencies the
angle is due decrease
(25 Hz to → 40
→ in50
the both
Hz). theItcorrosion
decrease has
in both been resistance
the reported
corrosion andthatthethe
resistance capacitive
decrease
and the properties ofproperties
in the phase
capacitive the passive
angleofisfilm due
the formed,
to the decre
passive
in addition tointhe compactnessto the of the passive of film [34–37], and that the displacement of
infilm
both formed,
the corrosion addition resistance compactness
and the capacitive the passive film
properties [34–37],
of theand passivethat the film form
the phase angle at higher
phase frequencies has frequencies
been associated with associated
an increasewith in the thickness
indisplacement
ofaddition
the thickness
protectivetoofthe
the angle at higher
compactness of thehand, passive has been
film [34–37], that an
and second theincrease
displacement
in the oflayer [37]. On the
the protective other
layer [37]. Onat thethe end hand,
other of the at test,
thetheend of thetime test,con-
the
the phase
stant did angle
not show at higher
significant frequencies
changes in has
eitherbeenthe associated
maximum
second time constant did not show significant changes in either the maximum phase angle with
phase an
angle increase
or its in
position, the thickn
ofor the
and protective
itsthe third time
position, andlayer constant
the [37].
third Onconstant
tended
time the other
to decrease hand,
tended with at the end
increasing
to decrease with ofincreasing
the test,temperature.
temperature. the second
This may be time c
due
stant
This didto the
maynot permanent
show
be due presence
to significant
the permanent of an
changes adsorbed
presence film
in either of metal
the maximum
of an adsorbed hydroxides
film of phase that is formed
angle or its positi
metal hydroxides
andduring
that the the metal
is formed
third during
time dissolution
the metal
constant process
dissolution
tended and the fact that,
process
to decrease and
with with an that,
theincreasing
fact increase with inantemperature,
increase in
temperature. This may
the diffusion the
temperature, ratediffusion
of aggressive rate species
of aggressiveincreases [10].
species increases [10].
due to the permanent presence of an adsorbed film of metal hydroxides that is form
Basedon
Based onthetheabove,
above,the theimpedance
impedance spectra
spectra were
were analyzed
analyzed usingusing thethe equivalent
equivalent cir-
circuit
during
cuit shown
the metalin Figure
dissolution
8. The
process and the fact that,with with an increaseprocess in temperatu
shown in Figure 8. The first first
timetime constant
constant is associated
is associated with the the adsorption
adsorption process of
theof diffusion
the the metal
metal rate offilm
hydroxide
hydroxide aggressive
filmandand is is species increases
represented
represented bybythe [10]. phase
theconstant
constant phaseelementelement(CPEads)
(CPEads)in in
Based
parallelwith
parallel on
withthe the above,
theresistance
resistanceof the
ofthe impedance
theadsorption
adsorptionprocess spectra
process(Rads). were
(Rads).The analyzed
Thesecond
secondtime using the
timeconstant equivalent
constantisis
cuit shownwith
associated
associated in Figure
with thepresence
the 8. The
presence ofofafirst
alayer
layertime
ofof constant
adsorbed
adsorbed is associated
metal
metal hydroxides
hydroxides with
and and the adsorption
is represented
is represented by proc
by
the the constant
constant phase phase element
element (CPEf)(CPEf) in in parallel
parallel with with
of the metal hydroxide film and is represented by the constant phase element (CPEadsthe the resistance
resistance of the of the
adsorbedadsorbedfilm film
(Rf).
The
(Rf).third
parallel Thewithtimethe
third constant
time resistanceis represented
constant isof
represented by the
the adsorption byconstant
the constantphase
process element
phase
(Rads). element (CPEdl)
The (CPEdl)
second in parallel
in
timepar-constan
with
allel the
with charge transfer
the charge resistance
transfer (Rct). (Rct).
resistance
associated with the presence of a layer of adsorbed metal hydroxides and is represen
by the constant phase element (CPEf) in parallel with the resistance of the adsorbed fi
(Rf). The third time constant is represented by the constant phase element (CPEdl) in p
allel with the charge transfer resistance (Rct).

Figure8.8.Equivalent
Figure Equivalentcircuit
circuitused
usedto
tofit
fitthe
theimpedance
impedancespectra.
spectra.

The impedance of the CPE is defined by the expression [38]:

Coatings 2023, 13, 1349 11 of 16

The impedance of the CPE is defined by the expression [38]:

 
1
ZCPE = ( jω )−n , (10)
Y0

CPE is commonly used instead of capacitance when the capacitive semicircles are
depressed, and this is mainly attributed to surface imperfections. In this case, Y0 , also
known as admittance, is a constant whose magnitude is proportional to the active area
√
in contact with the electrolyte, j = −1, ω = angular frequency (rad/s), and n = α/(π/2),
where α is the phase angle of the CPE [39].
Tables 1–3 show the value and evolution of the electrochemical parameters as a
function of time.

Table 1. Electrochemical parameters of the electrochemical impedance spectroscopy (EIS) at 20 ◦ C.

Time RCT Yodl Rf Yof Yads

ndl nf Rads nads
(h) (Ω·cm2 ) (Ω−1 ·cm−2 ·sn ) (Ω·cm2 ) (Ω−1 ·cm−2 ·sn ) (Ω−1 ·cm−2 ·sn )
(Ω·cm2 )
0 5230 3.4271 × 10−3 0.62 1185 3.4707 × 10−4 0.7 79.2 6.8921 × 10−5 0.86
3 4787 1.6161 × 10−3 0.58 820.3 4.5659 × 10−4 0.75 236.7 8.7879 × 10−5 0.87
6 4197 1.7331 × 10−3 0.6 783.9 4.8316 × 10−4 0.76 226.9 8.9884 × 10−5 0.87
9 3944 1.9496 × 10−3 0.64 827.5 4.5329 × 10−4 0.76 252.9 8.402 × 10−5 0.89
12 3743 2.112 × 10−3 0.65 863.8 4.3681 × 10−4 0.78 321.8 8.2458 × 10−5 0.89
18 3194 2.1309 × 10−3 0.65 867.1 4.107 × 10−4 0.81 492.4 7.8769 × 10−5 0.89
24 2939 2.0608 × 10−3 0.64 872.8 3.728 × 10−4 0.84 635.5 7.6915 × 10−5 0.9

Table 2. Electrochemical parameters of the electrochemical impedance spectroscopy (EIS) at 40 ◦ C.

Time RCT Yodl Rf Yof Yads

ndl nf Rads nads
(h) (Ω·cm2 ) (Ω−1 ·cm−2 ·sn ) (Ω·cm2 ) (Ω−1 ·cm−2 ·sn ) (Ω−1 ·cm−2 ·sn )
(Ω·cm2 )
0 2230 1.1607 × 10−3 0.66 481 5.4595 × 10−4 0.75 108.1 1.1827 × 10−4 0.85
3 2174 2.791 × 10−3 0.69 749 5.7519 × 10−5 0.74 166.5 1.1339 × 10−4 0.86
6 1991 2.7736 × 10−3 0.7 725.9 5.5912 × 10−4 0.77 242.6 1.0027 × 10−4 0.87
9 1878 2.8209 × 10−3 0.7 722 5.6178 × 10−4 0.78 294.9 9.553 × 10−5 0.87
12 1804 2.8838 × 10−3 0.7 716.3 5.6666 × 10−5 0.79 338.7 9.3554 × 10−5 0.86
18 1788 3.1535 × 10−3 0.69 722.9 5.8251 × 10−4 0.79 404.4 9.1253 × 10−5 0.87
24 1790 3.669 × 10−3 0.68 756.8 6.2464 × 10−4 0.78 459.6 9.1898 × 10−5 0.86

Analysis of Yodl values shows that they increase with increasing temperature. At 20 ◦ C,
these show an increase in the first three hours of immersion and then tend to decrease
slightly as a function of time. However, at 40 ◦ C and 60 ◦ C, these tend to increase as a
function of time. This suggests that the increase in temperature reduces the corrosion
resistance through an increase in the active reaction surface.
This is in accordance with the trend observed in the ndl values. At 20 ◦ C, a decrease is
observed in the first three hours of immersion, followed by an increase that remains practi-
cally constant after 9 h. However, at 40 ◦ C and 60 ◦ C, the general trend is that ndl values
tend to decrease as a function of time. Since Yo is associated with the effective reaction
area and n with the irregularity and/or surface roughness, this indicates the presence of a
parallel process that is causing the observed changes (see Section 3.5 SEM analysis).
 Coatings 2023, 13, 1349 12 of 16

Coatings 2023, 13, x FOR PEER REVIEW

Table 3. Electrochemical parameters of the electrochemical impedance spectroscopy (EIS) at 60 ◦ C.

Time RCT Yodl Rf Yof Yads

ndl nf Rads nads
(h) (Ω·cm2 ) (Ω−1 ·cm−2 ·sn ) (Ω·cm2 ) (Ω−1 ·cm−2 ·sn ) (Ω−1 ·cm−2 ·sn )
(Ω·cm2 )
This is in accordance with−4the trend observed in the ndl −values. At 20 °C, a dec
0 1354 6.2125 × 10−3 0.7 931.5 4.8139 × 10 0.7 44.89 2.0732 × 10 4 0.87
observed in the first three hours of immersion, followed by an increase that remai
3 702.6 6.5276 × 10−3 0.69 738.1 5.9689 × 10−4 0.74 91.34 1.8407 × 10−4 0.85
tically constant after 9 h. However, at 40 °C and 60 °C, the general trend is that n
6 667.1 6.8598 × 10−3 × 10−4 × 10−4
tend to0.68 decrease753.6
as a 5.961
function of time.0.74 127.8
Since Yo is 1.6344
associated with 0.84
the effective
9 641.9 9.1178 × 10−3 0.67 792.6 5.901 × 10−4 0.73 150.2 1.4968 × 10−4 0.84
area and n with the irregularity and/or surface roughness, this indicates the prese
−2
1.2367 × 10parallel × 10−the4 10−4
12 674.2 0.66
process 812.4
that is5.9086
causing 0.73
observed 171.1
changes (see× Section
5.9086 3.50.73
SEM analysi
18 693 1.1406 × 10 − 2 − 4
× 10 the films × 10 − 4
On0.53 778 hand,
the other 5.9459since 0.73 formed
183.9 on 1.6432
the surface act as0.82insulators b
24 649 −2
1.0918 × 10the 0.43 720.2 5.9675the −3
× 10electrolyte,0.74 their
184.4Yof values 10−4 be less
1.7161 × must 0.82 than thos
metallic surface and
metallic surface, and their nf values must tend towards unity. The analysis of both
shows thatother
On the indeed,
hand, thesincepresence of oxy-hydroxide
the films formed films
on the surface act tends tobetween
as insulators decrease the the act
metallic surface and the electrolyte, their Yo values must be less
and reduce the surface roughness. This is because even when this active area ex
f than those of the metallic
surface, and their nf values must tend towards unity. The analysis of both values shows
film formed hides it. It has been reported that this is associated with film thicknes
that indeed, the presence of oxy-hydroxide films tends to decrease the active area and
low electrical
reduce the surfacepermittivity
roughness. This [40].is because even when this active area exists, the film
formed Considering
hides it. It hasthat
beenthe sumthat
reported of the
this resistances of the
is associated with filmtime constants
thickness and/orislowsimilar to
electrical
values, permittivity
Figure 9 shows [40]. these results. When comparing the results obtained with
Considering that the sum of the resistances of the time constants is similar to the
values (Figure 4), it is observed that the trend of the values is similar; however, th
Rp values, Figure 9 shows these results. When comparing the results obtained with the
at 20
Rp °C and
values 40 4),
(Figure °Citare higher than
is observed those
that the trendcorresponding with the
of the values is similar; Rp measuremen
however, the
is consistent
values ◦
at 20 C andwith40the◦ EIShigher
C are measurements since in none
than those corresponding of the
with theRpcases was it possible t
measurements.
the formation
This is consistentof thethe
with low-frequency
EIS measurements plateau,
since inand
nonethe
of adjustment
the cases was of the data
it possible towith th
define the formation of the low-frequency plateau, and the adjustment
alent circuit allows us to predict the value of the impedance module where this of the data with
the equivalent circuit allows us to predict the value of the impedance module where this
occur. Nevertheless, the electrochemical behavior is much better than that rep
would occur. Nevertheless, the electrochemical behavior is much better than that reported
other
in otherstudies
studies that usemore
that use morecomplex
complex deposition
deposition techniques,
techniques, such as such as thermal
thermal plasma plasm
ing [41].[41].
spraying

Figure9.9.
Figure Graphical
Graphical representation
representation of the
of the sum sum
of Rct + Rfof+ Rct +
Rads. Rf + Rads.

3.5. SEM Analysis

Figure 10 shows the morphological aspects after the corrosion test of the Ni5
ing in saline solution at the different test temperatures. Even though the surfac
 Coatings 2023, 13, 1349 13 of 16

3.5. SEM Analysis

Figure 10 shows the morphological aspects after the corrosion test of the Ni5Al coat-
ing in saline solution at the different test temperatures. Even though the surface of the
coating was roughened to obtain a homogeneous surface, it is evident that the dark phases
corresponding to the aluminum oxides that were trapped during the formation of the
coating are observed on it. It is worth noting that it is still possible to see the marks of
the surface preparation process, which suggests that despite the increase in temperature,
Coatings 2023, 13, x FOR PEER REVIEW
the rate of corrosion experienced by the coating was negligible. The only visible signs
of degradation are in the dark phases that correspond to the trapped aluminum oxides.
This is understandable since these aluminum oxides do not correspond to the formation
of protective films but to trapped oxides. It has been reported that even Al-based passive
are susceptible to failure in aqueous halide solutions [10,42,43]. The degradation
films are susceptible to failure in aqueous halide solutions [10,42,43]. The degradation of
phases
these caused
phases causedananincrease
increase ininthe
theeffective
effective reaction
reaction area, could
area, which which could
have have
caused the caused
iations ininthe
variations Yodldland
the Yo andndlndlvalues
values discussed
discussed previously.
previously.

Figure
Figure 10.10. Surface
Surface morphology
morphology of thecoating
of the Ni5Al Ni5Alafter
coating after
exposure exposure
to the to the NaCl
NaCl solution. solution.

The results obtained suggest that the Ni5Al coatings deposited by the electric arc
The results obtained suggest that the Ni5Al coatings deposited by the ele
technique have a high resistance to corrosion in saline solutions at a wide range of tempera-
technique
tures. The OCP,have
Rp, a high
and resistance toshowed
EIS measurements corrosion in saline
that the surface solutions at reaches
of the coating a wide range
peratures. The
thermodynamic OCP, Rp,
equilibrium and
with EIS measurements
its environment showed
in a short time that the surface
since quasi-stable values of the
of potential, resistance to polarization, and impedance modulus are reached.
reaches thermodynamic equilibrium with its environment in a short time since q
ble values of potential, resistance to polarization, and impedance modulus are re

4. Conclusions
The electric arc thermal spray technique is a suitable process for the depo
thick coatings. The OCP and Rp measurements indicated that the coating rapidly
Coatings 2023, 13, 1349 14 of 16

4. Conclusions
The electric arc thermal spray technique is a suitable process for the deposition of thick
coatings. The OCP and Rp measurements indicated that the coating rapidly reaches its
thermodynamic equilibrium with the corrosive medium due to the formation of a passive
layer. The EIS measurements showed that the corrosion process can be represented by
three time constants. The first one is the capacitive-resistive response of the metal surface,
while the other two are relaxation processes due to the adsorption of metal hydroxides
formed during the anodic process and the adsorption process of these species. The in-
crease in temperature (as well as the immersion time) causes a decrease in the maximum
phase angle (61◦ → 57◦ → 50◦ ) and its displacement towards the high frequency region
(25 Hz → 40 Hz → 50 Hz). The relaxation process associated with the metal hydroxide
layer (Ni and/or Al) does not undergo changes since it is an intermediate step of the anodic
process, and that associated with the adsorption process decreases its influence with the
increase in temperature, possibly due to the increase in the diffusion rate of the species.

Author Contributions: Conceptualization, M.A.D.-L. and J.P.-C.; Data curation, F.J.P.-A.; Formal
analysis, C.D.A.-G. and M.A.D.-L.; Investigation, C.D.A.-G., M.A.D.-L. and J.P.-C.; Methodology,
C.D.A.-G. and J.P.-C.; Resources, F.J.P.-A. and M.A.D.-L.; Supervision, J.P.-C.; Validation, F.J.P.-A.;
Writing—original draft, F.J.P.-A.; Writing—review and editing, C.D.A.-G. and J.P.-C. All authors have
read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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