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ORIGINAL RESEARCH ARTICLE

Mechanical, Tribological, and Electrochemical Evaluation

of NiCrAlMoFe Thermally Sprayed Coatings Subject
to Post-treatments
Sarra Boudjit, Rassim Younes, Mohand Amokrane Bradai, Issam Bouklouche, Lidia Baiamonte, and Giuseppe Pintaude

Submitted: 25 June 2023 / Revised: 13 February 2024 / Accepted: 15 February 2024

Herein, two Ni-based coatings, namely NiAlFeMo (P21) and NiAlFeCrMo (P31), were deposited on E335
steel using the flame spraying technique. The coatings were subjected to post-treatments at three different
temperatures (450, 550, and 650 °C) for one hour. Microstructural analysis revealed that the heat treat-
ments reduced porosities, resulting in more homogeneous and denser microstructures. Additionally, the
formation of carbides and alumina was observed. The 550 and 650 °C treatments significantly enhanced
the mechanical properties (hardness and indentation modulus) and tribological behavior (wear resistance
and friction coefficient) of the studied coatings. Moreover, open-circuit potential (OCP), potentiodynamic
polarization, and electrochemical impedance spectroscopy (EIS) were performed to assess the electro-
chemical characteristics of coatings. They revealed that the coatings treated at 550 and 650 °C exhibited
excellent corrosion resistance that can be attributed to the reduction of open pores and the presence of
alumina, which enhances the passivity of the surface. Such results underscore the significance of heat
treatment in optimizing the microstructural, mechanical, and electrochemical properties of nickel-based
coatings, by offering promising prospects for their application in various fields.

Nickel superalloys are considered superior materials because

Keywords corrosion, heat treatment, NiCrAlMoFe, thermal
spraying, tribological behavior
1. Introduction
The constituent parts of machines or equipment of increas-
ingly reduced dimensions must resist numerous stresses such as
mechanical stress, fatigue, wear, corrosion, and chemical
attack. The field of surface treatments of metal alloys is vast,
giving them essential properties for their use and making it
possible to obtain excellent protective coatings with excellent
efficiency, immediately addressing the issues of corrosion
resistance, wear, and changes in appearance (Ref 1). Various
surface treatment processes are available for surface stresses,
including thermal spraying, which allows the formation of
protective coatings against wear, high temperatures, and
corrosion. In this context, it is possible to extend the life of
parts while improving their performance. This fascinating
technique can restore worn mechanical parts by providing
desirable surface properties such as wear resistance (Ref 2, 3).
Sarra Boudjit, Rassim Younes, Mohand Amokrane Bradai, and
Issam Bouklouche, Laboratoire de Mécanique, Matériaux et
énergétique (L2ME). Faculté de Technologie, Université de Bejaia,
06000 Bejaia, Algeria; Lidia Baiamonte, Department of Chemical
Engineering, Materials and Environment, Sapienza University of
Rome - INSTM Reference Laboratory for Engineering of Surface
Treatments, Via Eudossiana 18, 00184 Rome, RM, Italy; and
Giuseppe Pintaude, Universidade Tecnológica Federal do Paraná,
Curitiba, Brazil. Contact e-mail: pintaude@utfpr.edu.br.
they can withstand high temperatures and possess greater
mechanical strength (Ref 4-6). As a result, they exhibit a
combination of properties that make them suitable for various
applications where both wear resistance and oxidation or hot
corrosion resistance are necessary (Ref 7). Therefore, the
industry and scientists are drawn to using nickel in coatings to
enhance magnetic, mechanical, and electrochemical properties
of parts.
The microstructure of Ni-based alloys is usually balanced to
contain intermetallic phases (Ref 8). Some fabrication routes
for obtaining these phases are complex (Ref 9), and using
thermally sprayed coatings is an excellent alternative (Ref 10).
However, exposure to service temperatures can precipitate
deleterious phases, reducing the coatingsÕ performances (Ref
11). Other beneficial effects can appear by applying thermal
cycles on Ni-based coatings. Prashar and Vasudev (Ref 12)
summarized these benefits in their review, particularly the
increase of ultimate tensile strength and the adhesive strength of
Inconel 718 coating, for example.
Daram and Banjongprasert (Ref 13) investigated the effect
of post-treatments on the corrosion behavior of the NiCrMoAl
coating. They revealed that modifying the microstructure after
post-treatment reduced the corrosion rate. A reduction in open
pores and an increase in oxide phases in the interlamellar bands
contributed significantly to the improved corrosion resistance of
the NiCrMoAl coating. Another study of NiCrMoAl arc-
sprayed coating was conducted by Srichen et al. (Ref 14). They
applied heat treatments in the range of 500-700 C for 10 and
30 days. The corrosion resistance tested with 20 vol.% H2SO4
solution was better after the exposure at 500 C, compared with
the other temperatures.

Journal of Materials Engineering and Performance

 Other investigations have shown that thermal post-treatment
effectively reduces the superficial and sub-superficial defects,
resulting in highly homogeneous microstructure, and improves
coatingsÕ tribological performances (Ref 15, 16). However,
these cases were dedicated to NiCrAl compositions without the
addition of iron or molybdenum. In this fashion, Srichen et al.
(Ref 17) studied the dry sliding wear of post-treated NiCrMoAl
coating after heat treatments at 300-700 C for 10 and 30 days.
They found that the heat treatment conducted at 600 C was the
best option within those investigated. In our vision, a post-
treatment longer than hours is not effective economically,
although their findings can help from the scientific point of
view.
The objective of this work is to study the effect of thermal
post-treatments on the microstructure and the tribological and
electrochemical behavior of nickel-based alloy coatings
(NiAlMoFe) and (NiAlCrMoFe) produced by the thermal
flame spray process. They were submitted at different temper-
atures (450, 550, and 650 C) for one hour, avoiding the
formation of deleterious phases (Ref 13).
2. Experimental details
2.1 Materials and Thermal Spraying Process
The substrate used in this investigation is an unalloyed E335
steel. The steel samples were machined in the shape of
cylinders (D = 10 mm, L = 20 mm). The E335 steel contains
the following elements: Fe as bal, Ni 0.724 wt.%, Mn
0.438 wt.%, Cr 0.085 wt.%, C 0.1 wt.%, and Mo
0.021 wt.%. Metavision-1008i (Metal Power, India)
Before the deposition process, the substrate was grit blasted
with 0.5 mm corundum particles of 99.50 wt.%, using com-
pressed air of 0.4 MPa, an incidence angle of 90, and a gun-to-
substrate distance of 150 mm. The surface was subsequently
cleansed and defatted with acetone in an ultrasonic bath. Then,
the following Ni-base powders were applied: Proxon 21021
(P21) and Proxon 21031 (P31), fueled with acetylene gas, using
a flame-powder gun-type CastoDyn DS8000. The P21 mainly
comprises Ni, Al, Fe, and Mo, whereas the P31 mainly
comprises Ni, Fe, Al, Mo, and Cr. The particle size distribution
of powders ranges from 44 to 125 lm. These powders were
obtained by melting and grinding and present a spread-out
distribution in size and grain shape, which gives them an
angular morphology observed by scanning electron microscopy
Fig. 1 SEM micrograph of the powder based on nickel: (a) Proxon P21, and (b) Proxon P31
(Fig. 1). The chemical composition (wt.%) of the powders has
been determined by EDS and contains the following elements:
Ni (bal), Al 12.63 wt.%, Mo 6.33 wt.%, Fe 11.74 wt.%, Si 2.27
wt.% for the P21 and Ni (bal), Al 10.55 wt.%, Cr 9.06 wt.%,
Mo 4.94 wt.%, Fe 7.61 wt.%, and Si 1.31 wt.% for the P31.
The spray parameters are given in Table 1. After the Ni-
based powder coatings were produced, post-treatments were
performed, heating to temperatures of 450, 550, and 650 C for
one hour, followed by air cooling. These treatments were
performed in a C1228 Cress single-chamber furnace.
2.2 Microstructural Analyses and Mechanical Properties
CoatingsÕ microstructural observations were carried out
using the FEI Quanta 200 PHILIPS scanning electron micro-
scope (SEM). X-ray diffraction (XRD) spectra were recorded
using a PANalytical X’PERT PRO MRD diffractometer with a
copper anode x-ray tube. A recording time of 40 seconds per
angular step of 0.04 C was used over the interval between 10
and 120 (2H). The crystalline phases are identified by
comparing the observed lines with those of the appropriate
phases in the PDF2 database.
The microhardness measurements are made on polished
surfaces with a Vickers indenter by applying a load of 2N for
15 s, and the average values result from a series of 10
measurements. The equipment used is a Zwick ZHV10
equipped with a CCD camera. From the instrumented inden-
tation tests, the indentation modulus was calculated using the
procedures described in section X4 of E2546–15 ASTM
Table 1 Parameters of the thermal flame spraying
process
Parameter Setting
Powder flow rate, Kg/h 1.25
Air pressure, bar 4.5
Gas pressure, bar 4
Oxygen pressure, bar 1.2
Oxygen ball height, mm 70
Gas ball height, mm 60
Projection distance, mm 70-80
Projection angle,  90
Coating thickness, mm 6
Journal of Materials Engineering and Performance
Fig. 2 SEM micrographs of Ni-based alloy coatings (P21): (a) as-sprayed; (b) treated at 450 C; (c) treated at 550 C; (d) treated at 650 C,
and (e) EDS analysis of different areas

Standard (Ref 18). A value of 0.3 was used for the PoissonÕs
ratio of the tested materials.
2.3 Electrochemical Analysis
The corrosion behavior of the coatings was evaluated at
room temperature of 25 C in solutions of 3.5 wt.% NaCl. An
electrochemical system composed of three-electrode cells was
connected to an electrochemical workstation (VoltaLab, Elec-
trochemical research equipment). Platinum was used as a
counter electrode, and a saturated calomel electrode (SCE,
0.242 V relative to the standard hydrogen electrode) was
employed as a reference electrode. The working electrode,
whose area was 0.785 cm2, was our coating. Each sample was
submerged in the electrolyte for one hour before all the
experiments until the open-circuit potential (OCP) reached an

Journal of Materials Engineering and Performance

Fig. 3 SEM micrographs of Ni-based alloy coatings (P31): (a) as-sprayed; (b) treated at 450 C; (c) treated at 550 C; (d) treated at 650 C,
and (e) EDS analysis of different areas

almost stable state. A potential range between  1 V and 1 V potential between the substrate and the coating, and ba is the
was used for potentiodynamic polarization with a scan speed of anodic Tafel slope of the substrate:
2 mV/s. Electrochemical impedance spectroscopy (EIS) tests
Rpm DEcorr
were carried out at a sinusoidal amplitude of 10 mV, ranging P% ¼ 10j ba j  100 ðEq 1Þ
from 100 KHz to 10 mHz. Rp
The porosity rate (pore connectivity) was calculated using
electrochemical data measurements. For all conditions, the 2.4 Tribological Tests
following Equation is applicable (Ref 19), where Rpm is the
polarization resistance of the substrate, Rp is the polarization Tribological tests under room temperature were performed
resistance of the coating, DEcorr is the difference in corrosion using a pin on disk. The coatings slid against the disks under

Journal of Materials Engineering and Performance

Fig. 4 SEM micrographs of P31 coating post-treated at 550 C
Fig. 5 X-ray diffraction spectrum of Ni-based alloy coatings (P21):
(a) as-sprayed (ST); (b) treated at 450 C; treated at 550 C; treated
at 650 C
dry conditions using loads of 5, 15, and 25 N, over 1000 m in
30 minutes at a speed of 0.5 m/s, corresponding to a wear track
diameter of 30 mm. The counterbody is a Z200CR13 marten-
sitic steel with 63-65 HRC, ground to 0.3 lm of Ra. All
samples were cleaned with ethanol and air-dried prior to and
following testing. The mass losses were determined by
weighing samples before and after each test using a TG328B
balance having an accuracy of 0.01 mg. Friction coefficients
were recorded by the software attached to the tribometer. The
wear rate is presented as the ratio between mass loss and the
sliding distance.
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Fig. 6 X-ray diffraction spectrum of Ni-based alloy coatings (P31):
(a) as-sprayed (ST); (b) treated at 450 C; treated at 550 C; treated
at 650 C
3. Results and Discussions
3.1 Microstructures of Processed Coatings
SEM observations of the polished longitudinal section of
P21 and P31 coatings, both as-sprayed and heat-treated at 450,
550, and 650 C, are presented in Figure 2 and 3, and the
corresponding EDS analyses. According to the micrographs,
the microstructure of the as-sprayed coatings has more
porosities (see Fig. 2a and 3a) than those obtained after heat
treatment. Porosities on the as-sprayed microstructures proba-
bly come from the imprisonment of the air between the various
Fig. 7 Quantification of phases of Ni-based alloy coatings: (a) P21 and (b) P31 coatings

each liquid particle of the alloy is enveloped by a film of air

throughout its flight and will continue its oxidation with the
trapping of oxygen after it has crashed into the target.
The micrographs presented in Figure 4 illustrate the
morphologies of the P31 coating post-treated at 550 C, at
different magnifications. It presents a microstructure of micro-
metric particles of different sizes, with microcracks and pores
on its surface, displaying a classic lamellar morphology that is
wider, more compact, and denser. These coatings exhibit a
compact microstructure with lower porosity, oxide content, and
unmelted particles.

3.2 X-ray Diffraction (XRD)

The XRD spectra of the as-sprayed coatings revealed the
presence of a primary phase, which is identified as a solid
solution of face-centered cubic FCC structure (Al, Fe)Ni3
(Fig. 5), with a lattice parameter of 2.8666 A (JCPDS No. 00-
044-1187) and a relative content of 71wt.% (Fig. 7a). Figure 4
Fig. 8 Crystallite size of the Ni-based coatings used before and
after heat treatments: (a) P21 and (b) P31 coatings
also revealed the presence of an iron carbide with Fe5C2
stoichiometry, having a monoclinic structure and a relative
quantity of about 29 wt.% (Fig. 7a). The peaks of the coatings
deposited layers; some unmelted particles (spherical shape) and
heat-treated at 450, 550, and 650 C revealed the appearance of
microcracks are also visible (Fig. 2a and 3a). On the other hand,
a new Ni phase as the primary phase, with relative contents of
the different post-heat treatments reduced the porosities,
64, 91, and 80 wt.%, respectively. At the same time, the
making the coatings more homogeneous and denser through
volume fraction of monoclinic carbide was reduced (Fig. 7a).
the phenomenon of clogging (Fig. 2b, c, d and 3b, c, d). It is
The post-treatment at 550 C induced an evident change, where
also worth noting that the coating treated at 550 C exhibits
the disappearance of the fraction of the solid solution FCC, the
more extensive and tightly packed lamellae, giving it a denser
appearance of a new peak relative to a molybdenum carbide
and more compact microstructure than the as-sprayed coatings.
type Mo2C of orthorhombic structure, with a low composition
During the heat treatment process, the liberation of residual
of 1 wt.%.
stresses and the deformation of the projected particles favored
The x-ray diffraction spectra of the as-sprayed P31 coating
the compacting of the coating (Ref 20).
and heat-treated coatings at 450, 550, and 650 C (Fig. 6)
The microstructure of both compositions after heat treat-
revealed the presence of typical phases, differing one from the
ments at different temperatures revealed three regions: the light
other just in terms of mass quantity (Fig. 7b). The primary
gray area 1, the dark gray area 2, and the white area 3. The EDS
phase is identified as a solid solution of face-centered cubic
results indicated that Region 1 is rich in Ni, with small and
FCC structure (Fe-Ni-Cr) with a lattice parameter of 3.5537A
variable amounts of Mo, Al, and Fe, as well as Cr and Si for the
(JCPDS n 00-033-0945). One also notes the presence of the
P31 coating. In contrast, EDS analysis of Region 2 showed the
peaks of another phase of cubic structure, which is an
presence of Al as a significant element. In Region 3, the
intermetallic phase AlNi3 with a lattice parameter of
elements O and Al have been identified with the possibility of
3.5670A (JCPDS n 03-065-3245) and the appearance of
forming Al2O3-type oxides. Indeed, the presence of oxides in
residual oxide traces in the form of tetragonal Al2O3. The
the coating is to be expected since, on the one hand, the molten
formation of carbides of the Cr7C3-type (00-006-0687) was also
particles are projected under air pressure. On the other hand,
observed. After the heat treatment at 650 C, the FCC solid

Journal of Materials Engineering and Performance

solution Fe-Ni-Cr becomes dominant, 37wt.% (Fig. 7b), with Porosity can affect the same proportion of the indentation
the intermetallic phase AlNi3 (41 wt.%) decrease. The quan- modulus and hardness. To evaluate the post-treatment effect on
tification of the phases of the as-sprayed and heat-treated porosity, we can use the values of porosity rates from Table 3 to
materials shows that all these coatings are essentially consti- correlate them with the mechanical properties. In this way, as
tuted of a primary phase, which is the intermetallic AlNi3, a the ratio H/E is generally used to estimate the wear resistance of
solid solution of cubic-centered face structure (Fe-Ni-Cr) and a coatings (Ref 23), it can be plotted as a function of the porosity
weak proportion of Al2O3, approximately 3wt.% (Fig. 7b). For rate, as shown in Fig. 10. It is remarkable that the smaller the
the as-sprayed coating, the carbide formed is of a proportion of porosity, the higher the H/E ratio, independent on the coating
7 wt.% (Fig. 7b) and increases after the heat treatment, composition
especially at 450 C, with a content of 30 wt.%.
The crystallite sizes of as-sprayed (ST) and heat-treated 3.4 Electrochemical Behavior
coatings are depicted in Fig. 8. The average crystallite size or
3.4.1 Open-Circuit Potential (OCP). Figure 11 summa-
dimension is calculated by the X’Pert High Score software
rizes the evolution of OCP of the two coatings, P21 and P31,
from the half-value width of the more substantial diffraction
as-sprayed coatings (ST) and heat-treated at different temper-
peak using ScherrerÕs formula (Ref 21) for each coating. We
atures, 450, 550, and 650 C immersed for one hour in a 3.5
have considered two main phases for each coating, at least for
wt% NaCl solution.
applying this formula. From Fig. 8, the crystallite size of the as-
Observing Fig. 11, we can see that all the samples have
sprayed (ST) P21 and P31 coatings was found to be larger than
acquired a stable potential after about 2500 s except for the
that of the heat-treated coatings at 450, 550, and 650 C, in the
sample P31 treated at 450 C, which gives less stable OCP
order of 20.22 lm for the P21 coating and 9.46 lm for the P31
values over time. The two coatings, P21 and P31, treated at 550
coating. However, it is remarkable that this latter was refined
and 650 C, exhibit higher (more positive) OCP values than the
after the post-heat treatments for both coatings; the calculated
as-sprayed ones, which exhibit lower (more negative) OCP
values vary from 16.6 to 18.05 lm for P21 coatings and from
values. The high potential of both P21 and P31 coatings treated
7.53 to 8.84 lm for P31 coatings. The reduction in crystallite
at 550 and 650 C is associated with dense, homogeneous
size after heat treatment can be attributed to changes in the
microstructure with fewer pores and cracks (Fig. 2c, d and 3c,
crystalline structure of the phases and the lattice parameters of
d) after heat treatment, indicating the lowest sensitivity to
each structure formed.

3.3 Indentation Modulus and Hardness Table 2 Indentation modulus (GPa) and Vickers
Figure 9 depicts the load–displacement curves from the hardness of tested coatings
instrumented indentation tests obtained under a 2N load. Low
Coating Indentation modulus, GPa Hardness HV0.2
indentation depths are recorded for the 550 C treated coatings,
while the as-sprayed ones experienced high values. P21-ST 168 ± 7 190 ± 14
Table 2 presents the average values for indentation modulus P21-450 C 174 ± 5 214 ± 21
and Vickers hardness. P21-550 C 191 ± 6 334 ± 31
The hardness of P31 coatings is always higher than those of P21-650 C 178 ± 8 331 ± 24
P21, compared to the same condition. The primary reason for P31-ST 181 ± 7 295 ± 12
that is the presence of Cr7C3 carbide in P31 coatings (Ref 22). P31-450 C 176 ± 8 343 ± 16
Post-treatments increased hardness in all conditions compared P31-550 C 210 ± 5 427 ± 25
to the as-sprayed ones. The same is impossible to affirm for the P31-650 C 180 ± 9 398 ± 11
indentation modulus values, in which the treatments only
increased slightly.

Fig. 9 Load–displacement curves obtained by the instrumented hardness of Ni-based coatings: (a) P21 and (b) P31

Journal of Materials Engineering and Performance

Table 3 Corrosion parameters of P21 and P31 coatings from potentiodynamic polarization curves
Condition Ecorr, mV icorr, lA/cm2 ba, mV bc, mV Pi, % Rp, kX/cm2 P, %

P21-ST  668.6 ± 1.2 3.182 ± 0.06 55.7  96.8 12.89 3.73 67.58
P21-450 C  455.6 ± 0.7 0.911 ± 0.02 82.9  80.5 75.06 15.55 59.6
P21-550 C  372.8 ± 0.4 0.305 ± 0.03 98.9  74.7 91.6 39.31 24.6
P21-650 C  276.1 ± 0.3 0.279 ± 0.09  76.1 59.62 92.3 59.62 23.05
P31-ST  684.7 ± 1.8 2.079 ± 0.02 117.5  69.9 15.71 7.05 60.10
P31-450 C  412.8 ± 2.7 2.632 ± 0.1 83.6  79.8 27.37 3.89 54.22
P31-550 C  390.03 ± 2.2 0.635 ± 0.07 89.7  67.9 85.35 21.17 19.21
P31-650 C  383.5 ± 0.5 0.915 ± 0.06 102.6  79 74.95 10.24 22.79

alloys formed an Al2O3 oxide film, increasing passivity at the

surface. The current density (icorr) of the two coatings, P21 and
P31, treated at 550 and 650 C, presented lower values
(Table 3). The polarization resistance (Rp) agrees with the
corrosion current density trend. From these results, it can be
concluded that the two coatings, P21 and P31, treated at 550
and 650 C, have excellent corrosion resistance; this corrosion
improvement is the result of the reduction of open pores,
preventing the penetration path of the corrosive solution after
heat treatment (Ref 20).
The efficient protection Pi (%) of the P21 and P31 coatings
is another parameter that can be determined from the polariza-
tion tests using Eq 2:
 
icorr
Pið%Þ ¼ 1  0  100 ðEq 2Þ
Fig. 10 Hardness-to-indentation modulus ratio as a function of the icorr
porosity rate of tested coatings. The post-treated at 550 or 650 C
marked as notable results
where icorr and i0corr indicate the corrosion current density of the
coating and substrate, respectively.
Based on the results obtained in Table 3, the two coatings,
corrosion reactions. Coatings without heat treatment showed a
P21 and P31, treated at 550 and 650 C, present efficient
more negative potential due to the porosity and cracks. For P31
protection, higher than that of the as-sprayed coatings.
coatings treated at 450 C, the potential is less stable, moving
The corrosion resistance was related to the microstructural
toward negative values
changes of the coating. The corroded surfaces of the coatings
On the other hand, the potential of the P21 coating treated at
were examined using SEM (Fig. 13 and 14). The EDS analyses
450 C decreased significantly during the initial immersion and
were performed in magnified areas, indicated in each figure.
reached a stable and higher value than that of the P21 as-
Figure 13 shows different aspects depending on the coating
sprayed coating after about 2500 s. The initial decrease in
condition. The as-sprayed and the coating treated at 450 C are
potential can be attributed to the change in surface activity
covered with oxide scales. The presence of iron in the EDS
caused by the penetration of the electrolyte into the coating
spectrum is worthwhile. There are many cracks along with the
pores. Based on these results, it can be concluded that the 550
oxidized areas, indicating the brittle behavior of oxides.
and 650 C coatings offer better corrosion protection than the
However, the presence of aluminum oxide improves the
untreated coatings (ST). Therefore, there is a good correlation
corrosion resistance after the heat treatment. The pattern
between heat treatments and corrosion protection (Ref 24).
changed significantly for other conditions. The much more
3.4.2 Potentiodynamic Measurements. Figure 12 de-
homogeneous microstructure assured the best corrosion resis-
picts the potentiodynamic polarization curves of the substrate
tance. The formed film contains a much lower content of
and both P21 and P31 coatings before and after heat treatment
oxygen in Fig. 13c, and after treatment at 650 C, the surface is
in a 3.5 wt.% NaCl solution. The relevant parameters are
not covered with oxides as observed in Fig. 13(a) and (b).
identified through the results in Fig. 12 by the Tafel extrap-
Corroded surfaces of coating P31 are different from those
olation method and are given in Table 3.
observed in Figure 13. The oxidation process is governed by
The results in Fig. 12 show that the two coatings, P21 and
the presence of iron in the microstructure, but there is an
P31 as-sprayed (ST), exhibit more negative corrosion potentials
exciting effect after treatment conducted at 450 C. Corroded
(  668.6 and  684.7 mV, respectively). However, the cor-
areas were preferentially the zones among splats. The formation
rosion potentials of the two heat-treated coatings (P21 and P31)
of chromium carbide can cause that, forming galvanic areas
moved toward more positive potentials. The coatings heat-
with matrix, turning the corrosion resistance equivalent to the
treated at 550 and 650 C presented higher potential values
as-sprayed condition. For treatments performed at 550 and
(  372.8,  276.1,  390.3, and  383.5 mV), indicating
650 C, the fraction of chromium carbides was reduced, and the
that these coatings were more challenging to corrode. This
presence of aluminum in the matrix increased the formation of
characteristic can be attributed to the reduction of pores after
a more stable oxide scale (Fig. 14).
heat treatment. Thus, the aluminum element in P21 and P31

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Fig. 11 Open-circuit potential Ecorr of P21 and P31 coatings without heat treatment and post-treated at different temperatures immersed for one
hour in 3.5 wt.% NaCl solution
Fig. 12 Potentiodynamic polarization curves of P21 and P31 coatings emerged in a 3.5% NaCl solution
3.4.3 Electrochemical Impedance Spectroscopy (EIS).
EIS measurements were performed to study the electrochemical
behavior of the coatings in 3.5 wt. % NaCl solution after one
hour of immersion. The impedance diagrams for all samples
evaluated are shown in Fig. 15. Both P21 and P31 alloys
present similar capacitive properties with a semicircular arc; the
resistance of the coatings to electrolyte penetration, which is
related to the defects in the coatings, is designated by the arc in
the high-frequency region, while the low-frequency arc repre-
sents the impedance at the electrodeÕs and solutionÕs interface.
The Bode impedance patterns in Fig. 15(b) and (d) reveal that
both the P21 and P31 coatings heat-treated at 550 and 650 C
have higher impedance values in the low-frequency ranges.
Significantly elevated impedance values in the low-frequency
domain also indicate more excellent corrosion resistance for
both P21 and P31 treated at 550 and 650 C, which is also in
agreement with the results of the polarization curves (Fig. 12).
Based on the bode results of the phase angles shown in
Fig. 15(b) and (d), we can further note that the highest phase
angles of both P21 and P31samples heat-treated at 550 and
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650 C were 50 and 65 of the average frequency of 101 to
101 Hz, respectively. The most significant phase angle region
occurred around the maximum angle; the frequencies stayed
broader, which means that the surface of the coating is steady.
Therefore, the larger phase angle and the broader spectrum of
the P21 and P31 coatings heat-treated at 550 and 650 C
exhibit better corrosion protection than other coatings after
immersion in the 3.5 wt.% NaCl solution for 1 hour, the most
appropriate equivalent circuit used to improve the EIS results of
the P21 and P31 coatings was [Rs ((Rpore (Qdl.Rc)) Qct)], where
Rs, Rpore, Rc, and Qct symbolize the solution resistance, the
resistance of the solution within the pores, the charge transfer
resistance, and the constant phase element related to the
capacitance of the coatings, respectively, Additionally, Qdl is a
constant phase element that denotes the electrode/electrolyte
interfaceÕs non-ideal capacitive behavior.
From the results obtained in Table 4, the charge transfer
resistance values are higher for the P21 and P31 coatings
treated at 550 and 650 C, respectively. It is inversely
proportional to the current density results icorr (Table 3).
Generally, materials with high charge transfer resistance and
Fig. 13 SEM images and EDS analysis of corroded surfaces of coatings P21: (a) as-sprayed; (b) treated at 450 C; (c) treated at 550 C; and
(d) treated at 650 C. The main elements are indicated in % at.

Fig. 14 SEM images and EDS analysis of corroded surfaces of coatings P31: (a) as-sprayed; (b) treated at 450 C; (c) treated at 550 C; and
(d) treated at 650 C. The main elements are indicated in % at.

low Icorr have high chemical stability, which gives them better
corrosion resistance. Both P21 and P31 coatings treated at 550
and 650 C show superior corrosion resistance and lower
current density than the other coatings. Other studies on the
corrosion behavior of materials show similar corrosion mech-
anisms. Cheng et al. (Ref 25) studied the corrosion behavior of
Ni-Al bronze manufactured by an electric arc and as-cast in a
NaCl solution. They showed that after 30 days of immersion,
the film formed on additively manufactured NAB contained
more Al2O3 and Ni, and the mass loss of WAAM-produced
NAB alloys decreased by 35.21% compared to as-cast samples
(Ref 25).

Journal of Materials Engineering and Performance

Fig. 15 Electrochemical impedance spectroscopy of P21 and P31 coatings in 3.5 wt% NaCl solutions: (a) Nyquist plots P21, (b) Bode phase
plots P21, (c) Nyquist plots P31, (d) Bode phase plots P31

Table 4 Equivalent circuit parameters of EIS results for P21 and P31 coatings in 3.5 wt.% NaCl solution
Samples Rs, X cm2 CPE1 31025 (X-1 sn cm2) n1 Rpore, X cm2 CPE1 3 10-5, X 21
sn cm2 n2 Rct 3 104, X.cm2

P21-ST 189.3 ± 2.3 0.002964 0.8753 0.2797 3.584 0.6876 0.1905

P21-450 C 200.3 ± 1.8 2.13 0.9537 4321 11.09 0.8343 1.121
P21-550 C 203.4 ± 1.6 2.067 0.9038 0.9599 5.71 0.8343 4.978
P21-650 C 176.5 ± 1.2 10.97 0.8449 18.82 25.66 0.7844 5.982
P31-ST 205.2 ± 0.8 18.49 0.7732 3.696 9 104 13.07 0.6144 0.75295
P31-450 C 162.4 ± 1.3 18.03 0.7634 6.287 9 10-10 8.534 0.8626 2.025
P31-550 C 168.6 ± 2.2 4.92 0.8458 1849 6.817 0.7844 6.472
P31-650 C 177.3 ± 1.6 7.896 0.7273 54.53 0.5143 0.7487 6.068

3.5 Tribological Behavior cracks, and oxides—leading to a significant variation of the

adhesion component. As the load increases, the deformation
Figure 16 summarizes the variation of the friction coefficient
becomes more critical, but the increasing hardness can reduce
of studied coatings as a function of the load for the as-sprayed
the plastic deformation, and consequently, harder coatings
(ST) and post-treated at different temperatures. All curves
present lower friction coefficients at high loads. This reasoning
described in Fig. 16 have the same pattern: the smaller the
can clarify the behavior regarding the wear rates, presented in
applied load, the higher the friction coefficient. Regarding
Table 5.
frictionÕs adhesion and deformation components, we can infer
Generally, for all conditions, the coating P31 presented more
that the adhesion component is most relevant for tests with low
minor wear than P21 compared to a similar condition. An
loads. The initial surface roughness of disks is relatively high to
exception is observed for 450 C tested under 5 N, but we will
block the movement of polished pins. Additionally, the
consider another discussion in this load level. The coating P31
superficial defects are exposed to the initial contact—pores,

Journal of Materials Engineering and Performance

Fig. 16 Friction coefficient of as-sprayed and heat-treated coatings as a function of load: P21 and (b) P31

Table 5 Average wear rates (mg/N.m) 3 1023 determined in pin-on-disk experiments for different applied loads (5, 15,
and 25 N) of tested coatings
Load, N P21-ST P21-450, °C P21-550, °C P21-650, °C P31-ST P31-450, °C P31-550, °C P31-650, °C

5 15.74 ± 0.5 2.63 ± 0.14 6.12 ± 0.5 20.98 ± 0.31 2.43 ± 0.4 5.58 ± 0.2 4 ± 1.4 9.13 ± 0.13
15 51.56 ± 0.2 41.95 ± 1.02 20.11 ± 0.3 35.83 ± 0.4 11.63 ± 0.21 16.75 ± 0.4 10.83 ± 5.2 26.21 ± 0.4
25 169.52 ± 0.4 47.19 ± 2.14 36.71 ± 0.4 42.82 ± 2.2 68.11 ± 1.42 31.07 ± 0.3 28 ± 1.2 26.34 ± 2.5

treated at 450 C resulted in the lowest values of COF

compared with others of the same composition. In this
condition, the presence of chromium carbide is noted, and the
corrosion resistance decreased significantly. The presence of
hard phases contributing to the tribological behavior and
denying the corrosion is reported in the literature for several
materials (Ref 26-28). Then, it is the reason to find a
suitable balance of microstructure when components are subject
simultaneously to wear and corrosion.
Trying to establish a correlation between the wear rate and
mechanical properties in tests conducted under 5 or 15 N, this
finding was not possible. Apart from the high level of friction,
probably caused by the initial roughness of the disk, which
caused adhesion, this level of loads did not promote enough
deformation to evidence the benefits of post-treatments.
Therefore, the wear was controlled by random events caused
primarily by superficial defects or the alumina oxides found in Fig. 17 Wear rates (mg/m N) resulted from tests with 25 N of
the P31 coating after heat treatments. applied load as a function of the hardness-to-indentation modulus
On the other hand, for tests performed under 25 N, the ratio
mechanical properties controlled the wear process. A reason-
able proof for this sentence is the correlation between the H/E
ratio and the wear rate, normalized by the load for better
visualization, as shown in Fig. 17. In this case, all conditions The SEM images show fragmented flakes interlaced with
are plotted together, and the relationship was kept reasonable, oxides. The debris is mainly composed of O, Al, Ni for the P21
independent on the coating composition or the applied heat coating (Fig. 18a) and O, Al, Fe, Cr for the P31 coating
treatment. (Fig. 18b). Therefore, a certain level of oxidation is present
Observing Fig. 17, the best wear resistances were achieved during the wear process, besides the presence of aluminum
by P31 coating after post-treatments conducted at 550 or oxide, revealed in the XRD analysis in a minor fraction.
650 C, i.e., the higher the H/E, the higher the wear resistance. Therefore, the relationship between wear and H/E ratio means
The wear behavior after tests with a 25 N load can be that the combination of properties is the bearing support for
checked by looking at the wear debris for each tested coating maintaining oxide scales at the contact, protecting the surface
treated at 550 C, as shown in Fig. 18. against more severe wear.

Journal of Materials Engineering and Performance

Fig. 18 SEM micrographs and EDS analysis of wear debris at 25 N, (a) P21 coating, and (b) P31 coating. Both were treated at 550 C
4. Conclusions
From the results presented in this investigation, the follow-
ing conclusions can be extracted on the effects of heat
treatments on the microstructural, tribological, and electro-
chemical behavior of NiAlFeMo (P21) and NiAlMoFeCr (P31)
coatings obtained by the flame spraying process.
• The post-treatment applied at 550 or 650 C reduced the
porosities, which were decisive in improving the mechani-
cal properties and the corrosion behavior of all coatings;
• An essential constituent to mechanical properties was
M7C3 carbide in coating P31, which was decisive in
increasing the mechanical properties compared to the P21
coating;
• Electrochemical tests on P21 and P31 coatings have
shown a good correlation between heat treatment and cor-
rosion protection. The coatings treated at 550 or 650 C
present better corrosion protection than the untreated ones,
and;
• Sliding wear tests conducted at low load levels did not de-
tect the beneficial effect of post-treatments on mechanical
properties. At the highest level applied—25 N—the best
wear resistance was achieved with the highest H/E ratio.
This ratio indicated the bearing protection for oxides once
the wear debris is composed by them.
Finally, we can explore the future resistance of the selected
coatings to high-temperature dry sliding wear since the
resulting microstructures after non-intermetallic phases formed
post-treatments and relevant applications of nickel alloys are
subject to these wear conditions.
Journal of Materials Engineering and Performance
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