Metals and Materials International (2021) 27:3269–3281

https://doi.org/10.1007/s12540-020-00697-7

Wear and Corrosion Properties of Stellite‑6 Coating Fabricated

by HVOF on Nickel–Aluminium Bronze Substrate
Seyed Elias Mousavi1 · Nastaran Naghshehkesh1 · Mohabbat Amirnejad2 · Hossein Shammakhi1 · Ali Sonboli3

Received: 12 November 2019 / Accepted: 13 March 2020 / Published online: 7 April 2020
© The Korean Institute of Metals and Materials 2020

Abstract
Ni–Al bronze (NAB) was coated with Stellite-6 through gas-fueled high-velocity oxyfuel spraying. Scanning electron micros-
copy observations revealed the accumulation of Tungsten-rich particles at the substrate-coating interface. These areas played
an important role in the enhancement of the mechanical properties of the coating. The coating hardness increased 5 times with
respect to the substrate one. The tribological analysis of the coating was done via pin on disk method. Results showed that
abrasive wear is the dominant mechanism for the substrate; on the contrary, delamination is the dominant wear mechanism
in the coating. The corrosion performance of bare and coated alloy was investigated by potentiodynamic polarization and
electrochemical impedance spectroscopy. The corrosion potential of coated sample increases in comparison with bare alloy,
corrosion current density decreases from 3.91 to 1.82 µA/cm2 and the capacitive resistance is much larger.

Keywords Ni–Al bronze · Stellite-6 · HVOF · Wear · Corrosion resistance

1 Introduction of these alloys, the service conditions in the seawater and

Ni–Al bronzes are copper-based alloys which have been
widely used in the shipbuilding industries due to their
good mechanical properties and corrosion resistance [1].
The presence of alloying elements such as Al, Ni, and Fe
is responsible for its good fatigue resistance, corrosion
resistance, low expansion coefficient, good toughness in
low and high temperatures and mechanical workability [2].
Easy casting and welding represent the main advantages
of these alloys. Accordingly, this class of alloys is largely
used to produce ship propellers, valve components, joints,
and pumps [3]. Moreover, the possibility of restrengthen-
ing after service accidents can lead to reduced production
and maintenance costs [4]. Despite the good properties
* Mohabbat Amirnejad
m.amirnejad@stu.nit.ac.ir
1
Department of Materials Engineering, Isfahan University
of Technology, Esfahān 84156‑83111, Iran
2
Department of Materials Engineering, Babol Noshirvani
University of Technology, Shariati Ave, Babol 47148‑71167,
Iran
3
Department of Materials Engineering and Metallurgy,
Faculty of Engineering, Arak University, Arāk 3815688349,
Iran
under alternating loads requires the control of their corrosion
behavior and the improvement of wear performances [5].
The destruction mechanisms of the components generally
start from the surface. Koul et al. [6] have been reported
that NAB alloys are susceptible to environmentally assisted
cracking (EAC) which allows defect size to increase over
time. Cavitation erosion is one of the most common failure
mechanisms of the NAB propellers in marine environment
which is largely dependent on the surface properties of the
material [7]. Furthermore, Cyclic loads applied to the pro-
peller blades under operating conditions in the seawater cor-
rosive environment will cause fatigue phenomena. It should
be noted that the fatigue crack initiation mainly starts at
surface defects of material [8]. As a result, it is necessary
to reinforce the surface of the marine alloys. Initial protec-
tion of surface could increase the life of components and
the overall system efficiency. Repair welding is one of the
most common treatments to improve surface damages [9].
However, it should be noted that heat input during welding
would lead to thermal stresses that can weaken the alloy
mechanical properties and change its microstructure. For
this reason, the heat treatment after welding is necessary
to stress relief which can cause grain growth in the micro-
structure and reduction of the mechanical properties [10].
Developing Cobalt-based coatings may be an appropriate

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approach to protect sensitive alloys from wear and corrosion
attacks [11]. Co-based alloys’ important role in the improve-
ment of corrosion and wear behavior was demonstrated by
many researchers [12, 13]. The resistance of these coatings
against severe wear conditions and the stability of mechani-
cal strength at high temperatures have been investigated
by Houdkava et al., [14]. Moreover, Ma et al. have shown
that these coatings are resistive to oxidation and corrosion
at elevated temperatures, thermal fatigue and creep [15].
One of the most important Co-based super-alloys is Stel-
lite 6 which contains chromium, tungsten, carbon, nickel,
and silicon as alloying elements [16, 17]. In addition to
the mentioned properties, this class of coatings has good
mechanical properties which are caused by the existence
of different intermetallic compounds and carbides in their
microstructure [18]. The effect of Stellite-6 coatings on the
wear properties of different substrates such as stainless steel
[11, 19], carbon steels [16], Ni-based superalloys [20] has
been studied previously. Nevertheless, there are few reports
on the effect of this coating on the Bronze substrates.
Various techniques like laser cladding [21], microlaser
welding [22], and cold spray [23] have been used to produce
stellite-6 coating on different substrates. In the last two dec-
ades, increased attention was given to the thermal spraying
techniques, due to their ability to strengthening wide ranges
of material and development of relatively homogeneous and
fine-grained layers [24]. High-velocity oxyfuel (HVOF) is
one of the best methods in thermal spraying techniques due
to the low temperature of its flame successfully used for sur-
face protection. On the other hand, the high gas velocity dur-
ing HVOF in comparison with conventional thermal spray
techniques will lead to increase in particles velocity, with
subsequent increase in coating density and adhesion [25].
In the present work, the Stellite-6 super-alloy was sprayed
on the Ni–Al Bronze using the HVOF method. The phase
composition and microstructure of Stellite-6 coating has
been investigated. Besides, the effect of stellite-6 coating
on surface hardness and wear properties of NAB coated
samples have been studied in comparsion with bare NAB
substrate. The electrochemical behavior of NAB substrate
and the effect of Stellite-6 coating on its corrosion properties
have been examined.
2 Experimental procedure
2.1 Materials
The material used as a substrate was C95500 alloy (ASTM
B 763). The chemical composition of the alloy was 10.2 Al,
4.3 Ni, 3.9 Fe, 2.8 Mn in mass percent and rest of copper.
Ni–Al Bronze disks with 30 mm in diameter and 5 mm in
thickness were cut from as-cast ingots. The surfaces were
sandblasted before the coating process.
The used stellite-6 powder was supplied by Delore Stellite
Company (Germany, code name Jet-Kote 576). The chemi-
cal composition of the used powder is given in Table 1.
2.2 Coating process
The coatings were made using an HVOF machine Metal-
lization Met-Jet ΙΙΙ (Birmingham, United Kingdom). The
coating parameters are listed in Table 2.
2.3 Characterization
XRD analysis was conducted on both powder and coatings
using a Philips, X’PERT MPD diffractometer at a constant
power of 30 kV and a current of 30 mA using monochro-
matic CuKα with a wavelength of 1.541 Å. The measure-
ment was performed at 10°–100° 2θ angular range with a
step time of 1 s and a step size of 0.03 degree and analysis
of obtained diffractograms was done using HighScore Plus
software equipped with JCPDS-ICDD database for phase
identification.
The morphological features of coating, microstructure,
and elemental composition were investigated by opti-
cal microscopy (OM) and scanning electron microscopy
(SEM) equipped with energy dispersive X-ray spectrom-
eter (EDS). In addition, Clemex Vision image analyzer was
Table 2  Spray parameters employed during HVOF
Parameter Magnitude
Oxygen pressure (psi/MPa) 3.19/2.2
Carrier gas rate (SLPM) 4
Spray distance (mm) 250
Fuel feed rate (SLPM) 0.280
Oxygen feed rate (SLPM) 830

Table 1  Chemical composition Element Co Cr W Ni Fe C Si Mn Mo

of the used stellite 6 powder
(weight percent) Weight percent Base 28.6 4.9 2.2 1.9 1.3 1.1 0.3 0.1<

The powder particle size was in the range of 10–30 µm

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used to measure the coating’s thickness and porosity. The
porosity measurement was done on the coating cross-section
prepared with the usual metallographic technique and the
average of three measurements was reported as the average
porosity value.
Micro-hardness investigation was performed on a pol-
ished cross-section of the coated sample at an interval of
1 mm using a Koopa micro-harness model MH3 machine.
Five measurements were performed at each distance and
the average value with associated standard deviation was
determined. During all the hardness measurements, the force
was 50 gr with 10 s dwell time.
The pin on disk standard method (according to ASTM
G99-17) was employed to measure the abrasive wear resist-
ance of bare NAB alloy and stellite-6 coating under the dry
sliding wear condition. Wear pin of size 3 mm in diameter
from UNS52100 steel with 64 HRC hardness was used.
The contact surface was ground against 600-grit SiC paper
and cleaned with acetone. The tests were conducted with
a normal load of 40 N at a constant sliding speed equal to
0.14 mm/s for a distance of up to 1000 m. The samples were
weighed using an electronic balance with ± 0.1 mg accuracy
before and after the sliding. Wear surfaces were investigated
using an Olympus optical microscope and a Plihips XL30
scanning electron microscope.
The effect of stellite-6 coating on corrosion behavior
of NAB alloy has been evaluated by the potentiodynamic
polarization test. The electrochemical test was performed
in 3.5% NaCl solution at room temperature. A conventional
three-electrode cell with a saturated calomel electrode
(SCE, 0.244 V vs. SHE at 25 °C) as a reference electrode,
Fig. 1  X-ray diffraction patterns of the Stellite 6 powder and Stellite 6 coating
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the platinum sheet as an auxiliary electrode, and a work-
ing electrode (sample) were used. The exposed area of the
working electrode is equal to 1 cm2 for all experiments. The
potentiodynamic polarization curves were obtained using
AMETEK PARSTAT 2273 potentiostat–galvanostat device
with power suit software. The scan rate used was 1 mV/s.
All the polarization experiments were performed after stabi-
lization of the free corrosion potential for 60 min. The Tafel
extrapolation method was used to measure the corrosion cur-
rent density of samples from obtained polarization curves.
The electrochemical impedance spectroscopy (EIS) meas-
urements were accomplished at open circuit potential with
a voltage amplitude of 10 mV. The frequency range used
for the electrochemical impedance spectroscopy tests was
between 0.1 Hz and 100 kHz. The EIS spectra have been
reported via Nyquist and Bode diagrams. EIS parameters
were calculated using ZView software.
3 Results and discussion
3.1 X‑ray diffraction
Figure 1 depicts the diffraction patterns related to the Stel-
lite-6 coated NAB alloy by HVOF and stellite-6 feedstock
powders. The comparison between the two patterns shows
the peaks corresponding to different phases for stellite-6
coating is identical to the peaks of feedstock stellite-6 pow-
der. Both of the diffracted patterns showed the FCC struc-
ture of Co and Cr solid solutions as the main characteristic
phase. This confirms that there is no significant change in
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the structure of stellite-6 powder during the HVOF process.
The lower temperature of powder particles during HVOF as
compared with other thermal spray processes will decrease
the particle melting or oxidation. The same results have been
reported by many researchers [26–28]. However, there is
a peak broadening and peak shift in stellite-6 coating pat-
terns as compared with stellite-6 feedstock powder. The peak
broadening can be attributed to the structural refinement of
stellite-6 powder during HVOF spray where the high cool-
ing rate upon the HVOF spray leads to the formation of
refined structure of the coating compared to that of feedstock
powder [29]. Furthermore, low temperature and high impact
velocity of powder particles during HVOF spray deform the
particles. During deformation, local lattice rotation and cur-
vature will occur due to dislocation motion on slip planes
and displacement region nearby the dislocation will change
the interatomic spacing. These two effects result in broaden-
ing and shift in XRD peaks, respectively [30]. On the other
hand, the recrystallization of a deformed portion of particles
may happen because of the transformation of particles high
kinetical energy to thermal energy. The mentioned mecha-
nism will form fine equiaxed recrystallized grains as well
as the broadened peaks of X-ray diffraction pattern [30, 31].
The characteristic peaks shift can be ascribed to the lattice
parameter changes due to residual stresses that formed in the
coating during the HVOF process.
The carbide characteristic peak is located at diffraction
angles of 38º and 45º in the XRD pattern of stellite-6 powder
and coating diffractograms. It should be noted that during
solidification of stellite-6, a (Co/Cr/W)7C3 carbide phase
with a composition of (0.85Cr-0.14CO-0.01 W)7C3 will be
formed. This carbide phase which also forms during cooling
after HVOF coating is called ­M7C3 [27].
3.2 Morphological studies
Figure 2 shows the cross-section stellite-6 coating on the
NAB substrate. As illustrated, a homogeneous coating with
approximately uniform thickness is formed via the HVOF
process. Quantitative image analysis has revealed that the
average thickness of the coating is 90 µm with a standard
deviation of 10.3 µm.
Fig. 2  Cross-section view of the
stellite 6 coating and the NAB
substrate
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Figure 3 shows the detailed features of the coating-sub-
strate interface in which the black points at the interface are
coating’s porosities. According to image analysis data, the
porosity of the coating was less than 1.5%. the formation of
dense coatings with low porosity by the HVOF process can
be attributed to the high-velocity impact of particles to the
substrate surface which can deform unmelted particles that
results in dense coating development. On the other hand,
particles reheating due to the conversion of kinetical energy
to thermal energy upon high-velocity particle impacts can
also be another important factor in the formation of coatings
with low porosity during HVOF [32, 33]. Dobbins et al. [34]
have stated that solid-state sintering during HVOF process
that results from the conversion of kinetical energy to ther-
mal energy could be another reason for the formation of
high-density coatings with increased particle cohesion.
The light contrast regions at the substrate-coating inter-
face (see Fig. 3) were identified by point EDS analysis and
its corresponding chemical composition have been plotted
in Fig. 4. It can be seen from Fig. 4 that these regions are
mainly composed of W with smaller quantities of Co, Cr,
and Fe. These were identified as η carbides. The presence of
this carbides is probably due to the local depletion of Cr and
Co ions and increased concentration of W in these regions.
As a result of higher concentration of W, the η carbides for-
mation will be favored energetically [35]. The effect of such
W-rich regions on microhardness and wear properties of the
Fig. 3  The SEM micrograph of a selected area from Stellite-6 coating
Metals and Materials International (2021) 27:3269–3281
Fig. 4  Point analysis of the white areas of the coating-substrate inter-
face
stellite-6 coating is discussed in further detail later in this
study.
The microstructure of the substrate-coating interface is
depicted in much more detail in Fig. 5 by optical micros-
copy and SEM observation at higher magnifications. As
seen, local melting zones, where the microstructure at
some regions immediately outside the substrate is different
from the microstructure of coating and substrate itself, and
voids as a dark contrast region in the SEM micrograph were
revealed at the interface.
Figure 5 shows that in some regions, the stellite-6 parti-
cles penetrated into the NAB substrate due to the high-veloc-
ity impact of stellite-6 particles which increases the coat-
ing’s thickness. Indeed, the penetration of coating particles
into the substrate probably occurs as a result of the localized
melting of the NAB substrate. It should be noted that the
NAB substrate melting point (i.e. ~ 1065 °C) is lower than
that of the stellite-6 Co-based alloy (i.e. ~ 1330 °C). There-
fore the high temperature sprayed stellite-6 can lead to the
local melting of the NAB substrate. On the other hand, the
oxygen flow rates during HVOF can be another significant
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Fig. 5  The microstructure of the coating-substrate interface, a optical
microscopy (OM), b SEM micrograph
parameter in substrate melting. At great oxygen flow rates,
fuel was ignited at the high melting condition of powder par-
ticles. The heat transfer from gas to inflight particles resulted
in high particle temperature and subsequent overheating of
the substrate [33].
A relatively high cooling rate upon HVOF spray will
result in the formation of voids. Basically, during solidifi-
cation of melted coating and substrate, they will shrink and
voids formation and growth in the vicinity of the interface
will be facilitated as a result of induced thermal stress con-
centration originated from coefficient of thermal expansion
mismatch between stellite-6 coating (11.34 µm/ °C) and
NAB substrate (15.5 µm/°C) [17]. The effect of voids on
mechanical properties and corrosion resistance of the stel-
lite-6 coating is discussed in further detail later in this study.
3.3 Microhardness
Figure 6 depicts the microhardness profile of stellite-6 coat-
ing on the NAB substrate. As can be seen, the stellite-6 coat-
ing presents greater microhardness compared to the NAB
substrate so that the substrate microhardness is about 120
HV, whereas the coating hardness is approximately equal
to 700 HV. The substrate hardness in the areas close to the
coating-substrate interface is slightly higher than that of
the other points along the substrate. The work hardening
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Fig. 6  Micro-hardness variation from the substrate to the coating
caused by sandblasting before the coating procedure could
be responsible for these hardened areas [28]. In addition,
the great peening effect of high-velocity particles’ impact
on the substrate will result in compressive residual stresses
and subsequent work hardening. Similar results have been
reported by Pukasiewicz et al. [36].
Stellite-6 is commonly composed of elements such as
W, Cr and a certain amount of C. Cr as the major alloying
element and W could react with C and as a result, the hard
and stable carbide phase will be formed. The microhardness
of stellite-6 coating will be increased due to the presence
of such stable carbides, which do not decompose even at
elevated temperatures [37].
Fig. 7  Weight loss as a function
of the sliding distance for the
wear test performed at 40 N
load
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3.4 Wear behavior
Figure 7 shows the weight loss diagram of the NAB alloy
and the Stellite-6 coating during the wear tests. As was
expected, the weight loss of the Stellite-6 coated sample
is much lower than the NAB alloy, indicating the increase
of wear resistance due to the coating process. The wear
characteristics of the NAB substrate and the Stellite-6
coating are related to the mechanical properties, surface
activity and the behavior of the transitional layer [38]. The
wear properties improvement in Stellite-6 coating in com-
parison to the substrate is probably due to the changes in
Metals and Materials International (2021) 27:3269–3281
microstructure and improvement of mechanical properties
especially the hardness of this coating.
According to the Archard equation (see Eq 1), the
weight loss of the coating during the wear tests is inversely
proportional to the coating hardness [31]:
W
Q=K (1)
H
where Q is the wear volume in the unit of slip length, W is
the amount of applied load, H is for hardness and K is wear
coefficient.
The higher wear resistance of stellite-6 coating may be
attributed to the increased hardness. The high hardness
values of the stellite-6 coated sample surface effectively
hindered the friction material from squeezing into the sur-
face, and hence better wear resistance will be achieved
[39]. Cr is the major alloying element in stellite-6 chemi-
cal composition. As stated in Sect. 3.3, Cr provides oxi-
dation and corrosion resistance as well as hardness by the
formation of M­ 7C3 and M­ 23C6 carbides. W contributes to
the hardness via precipitation hardening by forming MC
and ­M6C carbides [15]. Dwivedi et al. [40] reported that
the shape and size of the carbide particles are vital in wear
resistance behavior of Co-based alloy coatings such as
stellite-6.
Additionally, in a sliding system, the material in the
contact surface undergoes compressive stresses and maybe
plastically deformed. The deformed area usually has lower
wear resistance and leads to roughening in the surfaces
during wear test. The mentioned mechanism leads to the
disruption of the protective layers on the surface. So, it is
believed that, in addition to hardness, coating toughness
is an effective parameter for the coatings wear resistance
[41]. In the case of HVOF coatings, the surface resist-
ance against wear is related to additional factors such as
Fig. 8  Wear route in NAB alloy
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porosity and adhesion of the splats to each other. These
factors can be dominant in the overall wear behavior of
these coatings.
The mean friction coefficient for the NAB alloy is 0.20
and for the Stellite-6 coating, this value is 0.11. The first
factor, which caused higher resistance of coating against
the wear, is probably the hardness of the coating. However,
the existence of the wear debris or oxides may affect the
friction coefficient. Moreover, this hard coating is respon-
sible for resistance against cracking and failure. On the
contrary, the high friction coefficient in the NAB alloy
may be due to the cracking and weakening of the surface
atomic layers [42]. Dosta et al. [43] have been reported
that the martensitic transformation can play an important
role in the wear behavior of stellite coatings. This transfor-
mation can be triggered by mechanical forces and strains.
The FCC to HCP transformation in Co-based alloys occurs
even at room temperature. The friction coefficient of the
FCC phase is higher than that of the HCP phase. The HCP
crystals promote work hardening of coating and have a
greater wear resistance [42]. The greater difference in
the weight loss of NAB substrate and stellite-6 coating at
higher sliding distance arises from the greater work hard-
enability of the coated sample.
Scanning electron microscopy used to investigate the
wear surfaces for the identification of the dominant wear
mechanism. Figure 8 shows the worn route in the NAB
alloy.
The wear surfaces after sliding wear tests were covered
with grooves parallel to sliding direction indicating the
contribution of the abrasive wear mechanism. Moreover,
the micrograph shows deep carvings on the surface which
may be caused by detachment of the particles. This obser-
vation reveals that the dominant wear mechanism for bare
NAB alloy is abrasive wear. However, adhesive (lamellar)
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wear particles were also observed and in some areas, there
were small cavities and cracks on the surface that are char-
acteristics of adhesive wear [38].
Figure 9 shows the electron micrographs of the worn route
in the Stellite-6 coated sample. As depicted in Fig. 9 there
are some ledge areas and delamination, which are signs of
plastic deformation. The mentioned observations suggested
that the primary wear mechanism for stellite-6 coating was
the adhesive wear. However, there were some detachments in
the sample, which show the possible occurrence of abrasive
wear during the wear test. It should be noted that the wear
lamellas are mainly produced by the accumulation of dislo-
cations under the wear surface. During sliding contact, the
dislocations start to accumulate near the surface. The forma-
tion of voids and cavities in such areas with a high density
of dislocations decreases the energy; accordingly, in these
areas, small cavities will be formed [38]. Upon subsequent
growth of voids through applied loads, their length reaches
Fig. 9  Wear route in the Stel-
lite-6 coating
Fig. 10  Open circuit potential
vs time for bare NAB alloy and
stellite-6 coating
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to a critical length for transformation into cracks. By coa-
lescence of these cracks, the wear particles detach from the
surface in the shape of a thin sheet. From the SEM analysis,
the main wear mechanism of stellite-6 coating is adhesive
wear. Indeed, the formation of high-density coatings has led
to a drastic increase in obtained hardness values which is an
important factor in the wear behavior of it.
3.5 Corrosion behavior
Plots of open circuit potential versus time for NAB substrate
and stellite-6 coated specimen in 3.5% NaCl solution are
shown in Fig. 10. The OCP of the NAB substrate started at
− 0.241 V and then dropped to − 0.391 V after 600 s. After
that, the OCP value increased to values that are more posi-
tive and then became approximately constant at − 0.251 V.
The change from more positive potential to negative one is
due to the dissolution of surface films produced by the wet
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polishing procedure. Compared with the NAB substrate, the
OCP of stellite-6 coated sample was stabilized in the nobler
potential demonstrating higher thermodynamic stability
because of the inert stellite-6 coating. As can be seen from
Fig. 10, during the immersion for 60 min the OCP of coated
sample increased from − 0.151 to − 0.134 V. the increase in
the OCP of stellite-6 coating can be ascribed to the forma-
tion of passive film upon immersion.
Figure 11 represents the potentiodynamic polarization
curve for bare substrate and stellite-6 coated specimen.
Electrochemical measurements revealed that stellite-6
coating could protect NAB alloy from corrosion in NaCl
3.5% solution. The corrosion current densities of samples
were calculated by the Tafel extrapolation method from the
potentiodynamic polarization curves. These results are sum-
marized in Table 3.
According to Fig. 11 and Table 3, the corrosion potential
of NAB substrate and stellite-6 coated samples are − 0.28 V
and − 0.24 V versus SCE, respectively. The corrosion poten-
tial of coated sample shifts to the more positive values in
comparison with the NAB bare sample showing the higher
tendency of corrosion resistance. Furthermore, stellite-6
coating led to an increase in polarization resistance from
6.3 KΩ/cm−2 for the NAB substrate to 21.2 KΩ/cm−2 for
coated sample. As can be seen, the uncoated NAB substrate
possesses lower corrosion resistance likewise higher cor-
rosion current density equal to 3.91 μA/cm2. After apply-
ing the stellite-6 coating, the corrosion current density got
decreased to 1.82 μA/cm2. It seems that the stellite-6 coating
Fig. 11  Potentiodynamic polari-
zation curves for bare NAB
alloy and stellite-6 coating
Table 3  The electrochemical Sample βa (V/dec)
corrosion data calculated from
polarization curves NAB substrate 0.07
Stellite-6 coating 1.00
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acts as a physical barrier layer against the corrosion, which
would reduce the corrosion current density.
As depicted, after a while the anodic branch of the NAB
substrate polarization curve shifts to the lower current den-
sities, which may be caused by the formation of the oxide
layers on the surface of the alloy. In other words, the NAB
substrate exhibited a passive region with ­ipass = 4.2 mA/cm2.
By contrast, the coated sample underwent pseudo-passive
behavior between its corrosion potential of − 0.24 V vs SCE
and breakdown potential of − 0.003 V vs SCE. Repassiva-
tion of stellite-6 coated sample occurred at − 0.7 mA/cm2.
The corrosion resistance of the substrate is related to a
protective layer formed during the corrosion. This protective
layer is about 900–1000 nm thick, which consists of both
aluminum and copper oxides with ­Cu2O in outer regions
and ­Al2O3 in adjacent the base metal [2]. It has been made
clear that aluminum has a greater affinity for oxygen than
that of copper. During corrosion of NAB alloy in chloride-
containing media, A ­ l2O3 will be formed as a result of alu-
minum dissolution via the following reactions [3]:
Al + 4Cl− → AlCl4− + 3e− (2)
AlCl4− + 2H2 O → Al2 O3 + 3H + + 4Cl− (3)
The ­Al2O3 layer formed on the surface of NAB alloy con-
tinues to growth thus preventing the further diffusion of
aluminum ions.
The dissolution of copper and C­ u2O formation on the
NAB alloy surface as exposed to the 3.5% NaCl corrosive
βc (V/dec) Ecorr (V vs SCE) Rp (KΩ/cm−2) icorr (μA/cm2)
0.29 -0.28 6.3 3.91
0.10 -0.24 21.2 1.82
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medium will occur through the underneath processes [44].
At the first stage, the cuprous chloride species will be
formed from the metal via the following reaction:
Cu + 2Cl− → CuCl2− + e− (4)
Afterward, the ­Cu2O precipitation will occur with the fol-
lowing reaction.
2CuCl2− + 2OH − → CU2 O + H2 O + 4Cl− (5)
In the coated sample, all of the abovementioned reactions
occur at the coating-substrate interface with a reduced reac-
tion rate due to the physical barrier nature of satellite-6 coat-
ing. The presence of satellite-6 coating prevents the further
diffusion of corrosive species toward the coating-substrate
interface as well as electrons. In other words, the stellite-6
coating decreases the diffusion rate by increasing the diffu-
sion path length between corrosive medium and substrate-
coating interface. In addition, another important feature of
the stellite-6 coating is the existence of the elements such
as Co and Cr, which can trigger an additional protective
mechanism. The presence of electrochemically more active
elements (Co and Cr) which are in electrical contact with
NAB substrate, preserve sacrificial protection mechanism
[45]. A dense oxide layer that contains Co and Cr oxides
will be formed upon corrosion. This oxide layer could ham-
per the transportation of aggressive species toward the sub-
strate-coating interface thus providing improved corrosion
resistance. As stated by Bolelli et al. [11], pseudo-passive
behavior can be ascribed to the presence of stable layer of
protective species (such as chromium oxide in this study)
which acts as a barrier to attenuate the corrosion process.
Fig. 12  Nyquist diagrams from
EIS analysis for the coating and
the substrate
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Metals and Materials International (2021) 27:3269–3281
Electrochemical impedance spectroscopy was also used
to provide better intuition into the corrosion mechanism
of the bare substrate and coated alloy. Figure 12 shows the
Nyquist diagrams of the substrate and of the Stellite-6 coat-
ing in which the imaginary part of Impedance (Im Z) has
been plotted versus real part of Impedance (Re Z).
As can be seen from Fig. 12, the impedance of the coated
sample is in the order of 3500 Ω/cm−2 and it shows a larger
radius of curvature compared to the bare NAB substrate. It
should be noted that the presence of a high diameter of the
capacitive loop in the Nyquist diagram corroborates better
polarization resistance. The mentioned behavior shows the
corrosion resistance of the coating in 3.5% NaCl solution is
higher than that of substrate.
Bode phase angle diagram (Phase angle vs frequency)
and Bod magnitude diagram (Module |Z| vs frequency)
obtained for bare NAB alloy and stellite-6 coated samples
are illustrated in Figs. 13 and 14.
As can be seen, the total resistance of the coating, which
is identified at a very low frequencies range, (upper left side
of Fig. 14), is relatively higher than that of bare NAB alloy
revealing its higher resistance against corrosive ions.
In addition, the bare NAB substrate has a single time
constant where the mentioned semicircle is related to the
charge transfer reactions in the electrical double layer. How-
ever, the coated sample shows a two-time constant behavior,
which represents the presence of two distinct interfaces in
the corroding system. The first one is the coating-electrolyte
interface and the second one assigns to the substrate-coating
interface. The mentioned time constants appear at the high-
est and lowest frequency ranges, respectively. The first semi-
circle results from the interaction of the corrosive species
with the coating layer and its ingredients. On the contrary,
Metals and Materials International (2021) 27:3269–3281 3279

Fig. 13  Bode phase angle dia-

gram of the NAB substrate and
stellite-6 coating

Fig. 14  Bode magnitude dia-

gram of the NAB substrate and
stellite-6 coating

the second semicircle is due to the charge transfer resistance

Fig. 15  Equivalent circuits related to a substrate and b Stellite-6 coat-
ing
in the coating-substrate interface. In addition, Fig. 15a, b
show the single time constant equivalent circuit and two-
time constant equivalent circuit for the bare NAB alloy and
coated sample, respectively, where, Rs is the uncompensated
solution resistance between the working electrode and ref-
erence electrode, Rct is charge transfer resistance, which
indicates the amount of resistance against the occurrence
of the corrosion reaction in the substrate-solution interface
and Rc is related the coating resistance. Moreover, there are
two constant phase elements or CPE’s: C ­ PEedl is the double-
layer capacitance, and C
­ PEc is the coating-capacitive nature.

13
3280
Table 4  Equivalent circuit Rs (Ω/cm−2) CPEc (F/cm2) n1
parameters simulation for bare
NAB and Stellite-6 coated NAB substrate 3.5
sample in 3.5% NaCl solution
Stellite-6 coating 15.57
The EIS plots were fitted accurately using ZView soft-
ware. The obtained fitted parameters are given in Table 4.
The ­n2 value for the NAB substrate was found to be 0.71
showing the deviation from ideal capacitance behavior. The
solution resistance values have been increased from 3.5
Ω/cm−2 for NAB Substrate to 15.57 Ω/cm−2 for stellite-6
coated sample. It can be attributed to increase in corrosion
resistance of sample due to the presence of stellite-6 coating,
which decreases ion dissolution from substrate to electro-
lyte. The charge transfer resistance (Rct) of coated sample
was increased three times as compared to bare NAB alloy
illustrating the higher corrosion resistance of coated sample.
This goes in accordance with the results from polarization
results (see Fig. 11 and Table 3). The mechanism of the
corrosion in NAB alloy is controlled by the formation of
the oxide layers on the surface during the corrosion process.
On the contrary, the stellite-6 coating can act as a physi-
cal barrier layer against the corrosive species. Furthermore,
the double-layer capacitance (CPEdl) of coated sample was
about 3.354E−04 F/cm2 with ­n2 = 0.84 which confirmed the
presence of a relatively compact barrier layer on the NAB
substrate. It should be noted that the CPEc in the coated
sample is revealing the diffusion of the species along with
the coating layer. There may be the diffusion of the chloride
ions from electrolyte to the coating, which controls the cor-
rosion behavior. As revealed by the EIS results, it is obvious
that the stellite-6 coating did not show a flawless nature.
Open pores and splat boundaries could be considered as easy
diffusion paths. Along these paths, the penetration of cor-
rosive spices like chloride into the substrate and the diffusion
of NAB substrate elements toward the surface will occur.
The formation of Co and Cr oxides upon corrosion in 3.5%
NaCl solution can block easy diffusion pathways and will
prevent further corrosion of coated samples [20].
4 Conclusions
In this research, the Co base Stellite-6 coating was applied
successfully on NAB using HVOF spray. The effect of stel-
lite-6 coating on microhardness, wear resistance and cor-
rosion performance were investigated. Based on results
obtained in this study, the following conclusions have been
drawn
Microhardness assessments showed 500% increase in the
coating hardness by applying the Stellite-6 coating which
includes different carbides in the coating. The stellite-6
13
Metals and Materials International (2021) 27:3269–3281
Rc (Ω/cm−2) CPEdl (F/cm2) n2 Rct (Ω/cm−2)
– – – 3.525E−04 0.71 3317
3.493E−04 0.72 60.2 3.354E−04 0.84 10,257
coating largely improved the tribological properties of the
NAB. Accordingly, the amount of weight loss and mean fric-
tion coefficient of the coating were relatively low. Moreover,
it was observed that the dominant wear mechanism for the
NAB is abrasive wear. On the contrary, the dominant mech-
anism for coating was adhesive wear. Polarization curves
showed lower corrosion current densities for the coating in
3.5% NaCl solution, which showed higher corrosion resist-
ance. Moreover, the electrochemical impedance spectros-
copy tests proved the polarization data and showed higher
corrosion resistance for coated samples.
Data availability The raw/processed data required to reproduce these
findings cannot be shared at this time as the data also forms part of an
ongoing study.
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