Surface & Coatings Technology 318 (2017) 365–373

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Surface & Coatings Technology

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

Microstructural characteristics and corrosion behavior of HVAF- and

HVOF-sprayed Fe-based coatings
E. Sadeghimeresht ⁎, N. Markocsan, P. Nylén
Department of Engineering Science, University West, 461 53 Trollhättan, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: Fe-based coatings have been shown to be viable alternatives to the more expensive and less environmentally
Received 20 July 2016 friendly Co- and Ni-based coatings. In the present work, the microstructural characteristics and corrosion behav-
Revised 22 November 2016 ior of Fe-based coatings deposited by high-velocity air fuel (HVAF) and high-velocity oxy fuel (HVOF) processes
Accepted in revised form 23 November 2016
were comparatively investigated. Different sets of powder composition and particle size were used to decrease
Available online 24 November 2016
the porosity and increase the corrosion resistance of the coatings. The corrosion behavior of the coatings was
Keywords:
studied using electrochemical techniques, including open-circuit potential (OCP) and polarization tests in
HVAF 3.5 wt% NaCl at 25 °C. Techniques such as scanning electron microscopy (SEM), energy dispersive spectrometry
HVOF (EDS), and X-ray diffractometry (XRD) were used to characterize the as-sprayed and corroded coatings. The re-
Thermal spray coating sults revealed that the HVAF coatings had lower porosity and oxide content than the HVOF coatings. The polar-
Corrosion protection ization tests confirmed that the HVAF coatings sprayed with finer particle size (− 36 + 20 μm) have higher
Polarization polarization resistance (Rp) than the coatings produced by powders (−53 + 20 μm). Based on SEM analysis, it
was observed that corrosion initiated and grew through the surface defects of the coating and propagated
through inter-lamellar boundaries.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Several components in marine engines, such as hydraulic piston
rods, two-stroke engine piston rods, and exhaust valve stems undergo
severe corrosion degradation [1–3]. Among several proposed solutions
to protect such components, Co- and Ni-based coatings have been
shown to be useful against corrosion [4]. However, the high cost and en-
vironmental restrictions of Co and Ni are barriers that limit a large in-
dustrial utilization of these materials [5–8]. It is reported that handling
of these powders in thermal spray shops leads to some hazards [9].
Ni-based alloys are allergenic and are labelled as suspect carcinogenic
materials [10]. Co-based alloys have also carcinogenic effect on humans
if it inhaled [11,12]. Therefore, new materials and coating alternatives
need to be developed to overcome these shortcomings. High-alloyed
Fe-based coatings could be a cheap, less hazardous and more environ-
mentally friendly alternative to conventional Co- and Ni-based coatings
[8,13–16].
High velocity thermal spraying technologies are more and more
used to protect various components in corrosive environments, as the
coatings produced are very dense and highly adherent. In this respect,
the recently developed high-velocity air fuel (HVAF) guns have received
considerable attention as potential replacers of high-velocity oxy fuel
⁎ Corresponding author.
E-mail address: Esmaeil.sadeghimeresht@hv.se (E. Sadeghimeresht).
(HVOF) ones used today in industry [13,17–19]. The HVAF process
brings significant advantages in terms of cost and coating properties
[18,20–22]. The higher velocity of the in-flight particles in HVAF (M2
™, Uniquecoat) (N700 m/s) compared to the HVOF (JP-5000™, Dia-
mond Jet) process (≈ 600 m/s) makes it possible to generate denser
coatings with less porosity and also a higher level of compressive resid-
ual stress [23]. Moreover, employing a lower in-flight particle tempera-
ture (b1900 °C) with higher particle velocity in the HVAF flame
compared to HVOF (N 2200 °C), leads to minimal feedstock phase trans-
formation and almost inexistent elemental depletion/decomposition of
in-flight particles [23]. Furthermore, replacing pure oxygen in HVOF
with air in the HVAF process reduces the in-situ oxidation significantly
during spraying, while retaining its ability to produce high-performance
coatings [21,24].
Previous works showed that the Fe-based coatings deposited by
HVAF process [2,18,22,26–28] have excellent properties, especially
good corrosion behavior in various environments such as acid, alkaline,
and chloride solutions. The main reported reasons for high corrosion
resistance are the amorphous structure that may give special properties
to coatings [2,22,26,29], the low oxide content, high retention of pow-
der chemistry, high density, and sufficient reservoir of Cr for the passive
film formation [1]. Several studies have focused on amorphous Fe-based
coatings [30], while others have considered alloying the Fe-based coat-
ings by Cr [31]. Cr dissolves in austenitic (γ) matrix and increases the
ability of the alloy to form a thin and protective surface passive film in

http://dx.doi.org/10.1016/j.surfcoat.2016.11.088
0257-8972/© 2016 Elsevier B.V. All rights reserved.
366 E. Sadeghimeresht et al. / Surface & Coatings Technology 318 (2017) 365–373

corrosive environments. Thus, a high Cr level in the coating is generally
believed to increase the corrosion resistance [32].
This study aims to compare the microstructure and corrosion behav-
ior of Fe-based coatings produced by HVAF and HVOF. Three powder
compositions – Fe30Cr11Ni, Fe28Cr17Ni4Mo1.8C, and Fe10Cr5Mo2C –
with two particle sizes – −36 + 20 and −53 + 20 μm – were investi-
gated in order to increase the density and corrosion resistance of the
coatings. Corrosion properties were studied with two electrochemical
techniques i.e. open-circuit potential (OCP), and polarization measure-
ment. The role of corrosive species was analyzed using techniques
such as scanning electron microscopy (SEM), energy dispersive spec-
trometry (EDS), and X-ray diffractometry (XRD).
platinum foil as the counter-electrode. The surface area exposed to the
electrolyte was 0.2 cm2. All of the potentials were recorded against the
SCE. The OCP was monitored for 3 h to measure the corrosion potential
of each coating over time, whereas the polarization tests were per-
formed in order to evaluate the corrosion mechanisms and the ability
of the coatings for the passivation. Prior to each polarization measure-
ment, the as-sprayed samples were immersed in the electrolyte at the
OCP for 1 h in order to gain a stable state. The polarization curves
were plotted at the scanning rate of 0.2 mV·s−1 by scanning the poten-
tial range, which varied from −250 to +2000 mV (vs. OCP). The polar-
ization resistance (Rp) values were calculated based on the Stern-Geary
equation; see Eq. (1) [18]:

2. Experimental procedures dE 1 βa βc
Rp ¼ ¼ ð1Þ
di icorr 2:303ðβa þ βc Þ
2.1. Materials
where icorr (A·cm− 2) is the corrosion current density, and βa and βc
Coupons (25.5 mm in diameter and thickness of6 mm) of a low- (V·dec−1) are anodic and cathodic Tafel slopes, respectively. Three
alloyed carbon steel (0.10C-0.03Si-1.5Mn-0.02P-0.01S-0.2V- sets of measurements were made on each sample to ensure the repro-
0.15Ti wt%) were used as the substrate material. Three agglomerated ducibility of the polarization test results.
and sintered Fe-based powders were used with the nominal chemical
composition given in Table 1. Two powder particle size distribution of 2.5. Microstructure analysis of coatings
−36 + 20 μm and −53 + 20 μm, were used for each powder.
Cross-sections of the coatings were metallographically prepared for
2.2. Solution preparation microstructure characterization. The samples were polished using dia-
mond disks and diamond spray solutions, sequentially. The morphology
The corrosion tests were performed in a 3.5 wt% NaCl solution, pre- of the specimens was evaluated with a Hitachi SEM (TM3000, Tokyo,
pared from analytical grade reagents using distilled water. The corro- Japan) equipped with an EDS. The constitutional phases of the top and
sion experiments were conducted under thermostatic conditions bond coats, before and after the corrosion tests, were characterized by
(24 ± 0.1 °C). XRD using an X'Pert PRO diffractometer (Kristalloflex D500, Siemens,
Germany) with Cu Kα (λ = 0.154 nm) radiation and a range of diffrac-
2.3. Thermal spray experiments tion angles (2θ) between 25° and 80°.

The specimens were sprayed with a DJ2600 Hybrid HVOF gun
(Sulzer-Metco, Westbury, NY, USA) and a HVAF system equipped with
a M3 gun (Uniquecoat M3™, Oilville, VA, USA). Several spray parameter
sets were employed to produce dense and defect-free coating systems.
Table 2 presents the details for 12 sets of coatings sprayed using the
HVAF and HVOF processes, along with their process parameters.
Prior to spraying, all the substrates were grit-blasted in order to be
cleaned and roughened using the same HVAF spray gun (M3) with a
standard configuration (long nozzle of 4L2, large combustion chamber,
and stand-off distance of 315 mm) and DURALUM White F220 alumi-
num oxide powder (mesh 220) as grit-blasting media, and propane as
combustion gas.
2.4. Corrosion tests
2.5.1. Porosity, microhardness, and surface roughness measurements
The coatings porosity was evaluated by an image analysis (IA) tech-
nique using ImageJ software [33]. More details about the IA procedure
are given elsewhere [34].
The surface roughness of the coatings was measured using a stylus-
based profilometer (Surftest 301, Mitutoyo, Japan). Ten measurements
on three different directions were performed and the measurement
values were averaged.
Hardness measurements were performed on the polished cross-sec-
tions of the coatings according to the ASTM E384 standard with a micro
Vickers indenter (Shimadzu, HMV-2, Tokyo, Japan) with a load of 300 g
and a dwell time of 15 s [35]. The hardness of each coating was deter-
mined as the average of 20 measurements made on three different
samples.

The corrosion behavior of the as-sprayed coatings was examined 3. Results and discussion
through electrochemical corrosion tests. Prior to the corrosion tests,
the coated samples were ultrasonically degreased and rinsed in distilled 3.1. Characterization of coatings
water, followed by ethanol-/air-drying.
Fig. 1 presents the cross-sectional SEM micrographs of the as-
2.4.1. Open-circuit potential (OCP) and potentiodynamic polarization sprayed Fe-based coatings produced by HVAF (a) and HVOF (b) pro-
measurements cesses. Morphology of all the coatings showed some degree of laminar
The setup for electrochemical measurements comprised a three- microstructures with the elongated axis of the impacted splats aligned
electrode cell with the as-sprayed sample as the working electrode, firmly with the substrate surface. The lamellar structure was more visi-
the saturated calomel electrode (SCE) as the reference electrode, and ble in series 3 (A3, B3 and C3), which verified that the small powder par-
ticle size (− 36 + 20 μm) used in the HVAF process provides higher
cohesion strength. It can be seen that the size of pores was greater in se-
Table 1
Chemical composition of powders (wt%). ries 4 (sprayed by HVOF) than in the other series in which the samples
were coated by the HVAF process. In series 4 (A4, B4 and C4), a higher
Powders C Si Cr Ni Mo Mg B Cu V Fe
amount of pores can be observed at the coating/substrate interface
A 0.6 – 30 11.0 – – 3.4 – – Bal. that usually leads to a lower adhesion of the coatings. For instance, in
B 1.8 1.3 28 17.0 4.5 0.8 – 0.1 – Bal. C4, a distinct debonding could be observed at the interface, whereas in
C 2.0 2.0 10 4.0 5.5 0.3 3.7 1.5 1.5 Bal.
the HVAF coatings, no sign of debondings or cracks at the interface
 E. Sadeghimeresht et al. / Surface & Coatings Technology 318 (2017) 365–373 367

Table 2
Different sets of coatings produced by HVAF and HVOF processes.

Powder Coatings Powder Spray Nozzle Powder Pass Pass Air Fuel 1 pressure Fuel 2 pressure Powder carrier SoD
chemistry particle size process feed rate velocity spacing pressure (propane) (propane) gas (N2) (mm)
(μm) (g/min) (m/min) (mm/rev.) (MPa) (MPa) (MPa) flow (l/min)

A A1 −53 ± 20 HVAF Short (3L2G) 100 100 5 0.8 0.69 0.69 60 365
A2 −36 ± 20 HVAF Long (4L2) 100 100 5 0.8 0.69 0.69 60 400
A3 −36 ± 20 HVAF Short (3L2G) 100 100 5 0.8 0.69 0.69 60 400
A4 −53 ± 20 HVOF – 100 90 2 0.69 O2 pressure (MPa) 1.17 12.5 360
H2 pressure (MPa) 0.97
B B1 −53 ± 20 HVAF Short (3L2G) 100 100 5 0.8 0.69 0.69 60 365
B2 −36 ± 20 HVAF Long (4L2) 100 100 5 0.8 0.69 0.69 60 400
B3 −36 ± 20 HVAF Short (3L2G) 100 100 5 0.8 0.69 0.69 60 400
B4 −53 ± 20 HVOF – 100 90 2 0.69 O2 pressure (MPa) 1.17 12.5 360
H2 pressure (MPa) 0.97
C C1 −53 ± 20 HVAF Short (3L2G) 100 100 5 0.8 0.69 0.69 60 365
C2 −36 ± 20 HVAF Long (4L2) 100 100 5 0.8 0.69 0.69 60 400
C3 −36 ± 20 HVAF Short (3L2G) 100 100 5 0.8 0.69 0.69 60 400
C4 −53 ± 20 HVOF – 100 90 2 0.69 O2 pressure (MPa) 1.17 12.5 360
H2 pressure (MPa) 0.97

Fig. 1. Cross-sectional backscattered SEM micrographs of as-sprayed coatings.

368 E. Sadeghimeresht et al. / Surface & Coatings Technology 318 (2017) 365–373

were observed which may illustrate a good adhesion at coating/sub-
strate interface [5]. The better contact in the HVAF coatings could also
be attributed to the cleaner interface owing to higher spray velocity,
which led a greater plastic deformation and thus a better conformation
to the substrates asperities as well as to shot peening effect [36]. The
lower temperature and higher impact velocity in HVAF compared to
HVOF presented a significant peening effect on the previously deposited
particles promoting further compaction on the deposited layers [36].
The presence of unmelted particles in series 1 (A1, B1 and C1) con-
firmed that the coarse particles used in the HVAF process were not
able to adsorb enough heat, whereas the HVOF coatings using the
same particles size did not show any sign of unmelted particles; this is
most probably attributed to the higher flame temperature in the latter
process. The thermal energy of the flame in HVOF is produced by burn-
ing mixtures of fuel gas (hydrogen) in pure oxygen, while HVAF uses a
mixture of air and a fuel (propane), hence the heat produced in the for-
mer technique is greater [37]. In addition, some micro-cracks were
found among the splats of the HVOF coatings, which could be due to ex-
cessive shrinkage rates of the large number of fully molten particles
being sprayed at a rapid cooling rate [21]. The HVAF coatings sprayed
with the long nozzle (series 2) presented a more uniform microstruc-
ture than those sprayed with the short nozzle (series 1 and 3). Using
the long nozzle leads to a higher acceleration of the in-flight particles,
decreased dwell time of the particles spent in the jet stream, which
means that the particles did not have enough time to adsorb more
heat and to be oxidized before reaching the substrate. The coarse parti-
cle size (−53 + 20 μm) used in the HVAF-sprayed coatings of series 1
resulted in some non-uniformities and defects compared to the HVAF
coatings of series 3 sprayed with the fine particle size (−36 + 20 μm).
Table 3 shows the surface roughness, thickness, and microhardness
of the coatings. The surface roughness is important for corrosion protec-
tion, as the lower surface roughness leads to a lower surface area ex-
posed to corrosive environment, which can result in less susceptibility
to both general and localized corrosion [38]. The higher value of rough-
ness in the HVOF coatings (A4, B4, and C4) followed by the HVAF coat-
ings series 1 (A1, B1, and C1) showed higher susceptibility to uniform
and localized corrosion compared to the HVAF coatings of series 2 and
3, which had the smoother surface. The samples produced in this
study were not machined after spraying, in order to gain their functional
performances in the as-sprayed state (a technical solution that is much
feasible for industrial applications).
The porosity is another important factor that can affect the corrosion
behavior of the thermal spray coatings [39]. The porosity level was
lower for the HVAF coatings, reaching maximums of 3.9, 3.7, 3.2 vol.%
for the A1, B1, and C1 coatings respectively, than for the HVOF coatings
which had 4.8, 6.5, and 4.0 vol.% of A4, B4, and C4, respectively. The
densest coating was produced by the HVAF-sprayed Fe-based coatings
using a finer powder particle size (−36 + 20 μm).
The microhardness of the A4, B4, and C4 coatings sprayed by the
HVOF process was around 815, 674, and 599 HV0.3, respectively. The
coatings sprayed using powder A reached the greatest hardness, while
the coatings sprayed using powder C obtained the lowest values. A sim-
ilar trend was observed for other coatings produced by the HVAF pro-
cess, confirming that the powder A could be used in wear resistance
applications. The high hardness of the coatings could be attributed to
the formation of carbides and borides during the spraying process due
to the presence of C and B in the powder chemistry. The high hardness
can be attributed to the formation of Cr3C2 and probably the fine micro-
structure of individual lamellae. Moreover, high scattering (standard
deviation) in the microhardness values of the HVOF coatings and
HVAF coatings series 1 could be due to the presence of heterogeneities
in the composition and microstructure of the coatings. Non-uniform
distribution of carbides or pores, and oxide inclusions along lamellae
boundaries could increase the microhardness scattering. The non-ho-
mogeneities enhance the coatings' sensitivity to certain types of corro-
sion, particularly microgalvanic corrosion [16]. The location of non-
uniformities can be preferential sites for corrosion processes, as galvanic
microcells are probably established between them and the metal ma-
trix, resulting in galvanic corrosion of the matrix due to its higher ten-
dency for corrosion [40–43].
Thickening the coating has also been reported as an approach that
can reduce the penetration rate of corrosive ion through the coating de-
fects [18]. Thinner coating allows the electrolyte to quickly meet the
substrate through the coating defects (e.g. pores, cracks). However, it
has also been reported that the chemical composition of the coating
(for instance, the presence of alloying elements such as Cr) could com-
promise the detrimental effect of the defects [44]. The thickness of all
as-sprayed coatings deposited by the HVAF and HVOF processes were
in the range of 300–400 μm in order to avoid the contribution of thick-
ness into the corrosion behavior.
XRD patterns (Fig. 2) illustrate the presence of austenitic (γ) matrix
with a small amount of martensite in all Fe-based coatings. Moreover, a
small presence of Cr2O3 was observed in some coatings due to the in-
crease of the peak intensity at 38°. Further, some low intensity peaks
were attributed to the complex carbide of (Cr,Fe)23C6 and the complex
boride of (Cr,Fe)2B. The former appeared to be the most abundant of
the secondary phases, while the latter appeared in very low amounts.
The XRD could not identify the presence of more oxides in the HVOF
coatings, probably due to the higher coating roughness [4].
Based on the XRD patterns, the coating series A underwent at
spraying larger microstructural changes compared to series B and C.
Wider peak broadening at 2θ of approximately 44° and the formation
of a broad band in the range of 2θ between 35° and 50° were observed.
Peak broadening is attributed to the formation of a finely-structured su-
persaturated austenitic solid solution, whereas the underlying broad
band is associated with amorphous phase formation [25]. Apart from
the effect of heating and melting, it is worth mentioning that the peak
broadening might be also attributed to high plastic deformation of the
particles at impact [45]. A combined effect of melting, rapid quenching,
and plastic deformation of particles in series 4 most likely resulted in the

Table 3
Surface roughness, thicknesses, microhardness, and porosity of as-sprayed coatings.

Series Coatings Roughness, Thickness Hardness Porosity

Ra (μm) (μm) (HV0.3) (vol.%)

A A1 8.0 ± 0.4 302 ± 15 830 ± 84 3.9 ± 0.5

A2 7.9 ± 0.3 359 ± 9 846 ± 75 2.3 ± 0.2
A3 7.9 ± 0.4 381 ± 13 951 ± 78 2.6 ± 0.2
A4 8.2 ± 0.9 397 ± 12 815 ± 99 4.8 ± 0.5
B B1 7.4 ± 0.5 305 ± 23 719 ± 86 3.7 ± 0.3
B2 6.9 ± 0.4 368 ± 12 733 ± 59 3.0 ± 0.5
B3 7.0 ± 0.6 379 ± 16 691 ± 52 3.3 ± 0.5
B4 7.9 ± 0.3 398 ± 22 674 ± 92 6.5 ± 0.6
C C1 7.8 ± 0.5 316 ± 24 551 ± 68 3.2 ± 0.4
C2 7.5 ± 0.4 378 ± 17 587 ± 53 2.7 ± 0.3
C3 7.4 ± 0.4 384 ± 18 493 ± 46 3.0 ± 0.2
C4 9.1 ± 0.8 395 ± 18 599 ± 77 4.0 ± 0.3
Fig. 2. XRD patterns of as-sprayed HVAF and HVOF coatings.
 E. Sadeghimeresht et al. / Surface & Coatings Technology 318 (2017) 365–373
dissolution of carbides and borides into the super-saturated austenitic
matrix.
3.2. Open circuit potential (OCP)
The penetration of the corrosive species of the electrolyte along the
coating thickness towards the substrate over time was evaluated by
OCP measurements up to 3 h of immersion (Fig. 3). The higher OCP
values (more noble) were detected for the HVAF-sprayed coatings (se-
ries 1, 2, and 3), while the lower values (more active) were recorded for
HVOF-sprayed coatings (series 4). This behavior showed that HVAF
coatings presented a better barrier effect than HVOF coatings. The
HVAF coatings, particularly series 3, illustrated a better barrier effect,
which was mainly associated with the lack of interconnected pores [34].
At the beginning of the OCP test, the HVOF coatings (Fig. 3d) showed
an initial low potential, which slowly increased and then gradually de-
creased over time. This drop was detected for the other coatings when
the test started. The initial potential decrease can be due to two factors:
(1) the variation in the surface activity primarily due to the electrolyte
penetration along the coating, and (2) the dissolution of the initial
oxide layer, which was naturally formed after immersion into the elec-
trolyte [44]. The decrease of potential over time confirmed the penetra-
tion of the corrosive ions through open porosity or localized defect.
However, its potential became steady after such a drop, probably due
to clogging of open-pores rather than the passivation of the coating
[43]. Some fluctuations in OCP values illustrated the susceptibility of
the coatings to localized corrosion such as pitting [46].
3.3. Potentiodynamic polarization measurements
Fig. 4 shows the potentiodynamic polarization plots of various coat-
ings immersed in 3.5 wt% NaCl at 25 °C, in order to determine the overall
kinetic and thermodynamic of corrosion processes. Table 4 provides all
of the electrochemical parameters, including the corrosion potential
(Ecorr), corrosion current density (icorr), anodic (βa) and cathodic (βc)
Tafel slopes and polarization resistance (Rp) derived and calculated
from the potentiodynamic polarization plots and Stern-Geary equation
depicted in Fig. 4.
Slight passivation could have resulted from Cr content in the
coatings. As described in the literature [47], the “passive-like” stage
Fig. 3. OCP plots of various coatings over 3 h in 3.5 wt% NaCl, at 25 °C, (a) series 1, (b) series 2, (c) series 3, and (d) series 4.
369
where the current density is independent of the applied potential,
is due to a partially protective oxide layer formed on the coating
surface. The series A and C1 coatings showed one “passive-like”
stage, whereas the passivation was not clearly detected in the
other coatings. This means that Cr favored the coating acting as a cor-
rosion barrier in corrosive environment; however, further corrosion
protection is neglected with Cr N10 wt%. Therefore, 10 wt% Cr could
be considered as a critical level in the Fe-based coatings studied in
the present work.
It is generally believed that Fe-based coatings free of defects
could probably not be achieved due to the inherent characteristics
of the thermal spraying process. For instance, Cr content of the
alloy might oxidize during spraying (due to a great susceptibility of
Cr for oxidation). Formation of Cr2O3 within the spraying consumes
Cr, which could be used later in corrosion protection by formation
of the surface passive layer. Therefore, Cr-depletion zones are
formed due to the lack of Cr reservoir, which ultimately leads to cor-
rosion [48]. Therefore, increasing the level of accessible Cr in the
coating could improve the corrosion behavior. In the present study,
however, it was observed that the uniform coating microstructure
outweighed the Cr addition.
It could be hypothesized that “passive-like” stages were produced
due to the formation of a thin passive oxide film; however, defects
such as pores, oxide inclusions, and interlamellar boundaries led to a
disruption in passivity. The initial breakaway of the “passive-like”
stage might be connected to the galvanic microcells or selective corro-
sion along lamellae boundaries, based on the mechanism identical to
pitting. The galvanic microcells produce quite low damage, which can
be attributed to lower anodic current density. However, the corrosion
along lamellae boundaries inflicts more damage, resulting in higher an-
odic current density.
The corrosion potential of the HVOF coatings (series 4) varied from
−0.56 to −0.53 V/SCE, showing negligible differences thermodynami-
cally among three powder chemistries sprayed by this process. As
discussed, the coatings series B showed the highest passive current den-
sity, while the coatings series C had the lowest density. The coatings
series A exhibited a passivation stage at medium current density with
some tiny fluctuations. The coatings series B underwent active dissolu-
tion at the low potential without clear passivation stage. This behavior
could be attributed to the structural defects of coatings like pores. This
370 E. Sadeghimeresht et al. / Surface & Coatings Technology 318 (2017) 365–373

Fig. 4. Potentiodynamic polarization plots of the samples. All specimens were immersed in 3.5 wt% NaCl, at 25 °C (at a scan rate of 0.2 mV·s−1), (a) series 1, (b) series 2, (c) series 3, and
(d) series 4.

also implied a poor ability for the surface passive films to be stable.
However, broad passive regions were identified for coatings series C
by high transpassive potential, 1.0 V/SCE, which confirmed the protec-
tion ability of these coatings from localized corrosion. On the contrary,
the very limited passive region of coating series A illustrated a low abil-
ity to hinder localized corrosion. This low passive region might be asso-
ciated with the lamellar characteristics of these coatings. The presence
of the lamella boundaries hinders the outward migration of Cr to
reach the top surface of the coating, which eventually leads to weak pas-
sivation. The fluctuation of the passive region implied a continuous pro-
cess of active solution and passivation. The corrosion potential of
coatings series 4 (sprayed by HVOF) was lower than that of HVAF coat-
ings, which confirmed that the former were more active and susceptible
to corrosion in galvanic couples than the latter.
The lowest corrosion current density was observed for coatings C2
and C3 (0.15 and 0.10 μA·cm−2, respectively) due to the formation of
stable and protective passive films. The low icorr value of the coating se-
ries C confirmed better corrosion protection resulting from the powder
composition of C, whereas the powder compositions of B and A followed
it. The coatings series 2 sprayed by HVAF process using the long nozzle
showed lower icorr and higher Ecorr values than the other coatings
sprayed by short nozzle, which verified the better corrosion perfor-
mance of the coatings sprayed with the long nozzle. The icorr and Ecorr
values of the coatings series 1 were worse than those values in series
3 and 4. It can be concluded that the HVAF coating sprayed with the im-
proper particle size (−53 + 20 μm) could show worse results than the
HVAF coating sprayed with the right particle size (−36 + 20 μm), and
also worse results than the HVOF coating sprayed with the right particle
size (−53 + 20 μm). Therefore, the HVAF coatings having enough res-
ervoir of passive-forming elements such as Cr and fine feedstock parti-
cle size could be efficient as a protective barrier and could keep the
excellent corrosion properties to control localized corrosion. The results
confirmed the effects of the elemental composition and microstructure
on corrosion behavior of the coatings.
High resistance to localized corrosion (such as pitting) of the Fe-
based coatings was considered to be determined by the presence of
Cr-rich passive surface films formed on the coatings, which could pro-
tect the coatings from further attack by the corrosive solution. More-
over, the Mo content of the coating series B and C could also reduce
the possibility of pitting, and improve the corrosion resistance and pas-
sivating ability, as it could control the consumption of Cr during passiv-
ation [49]. The coatings series C, which contained the critical level of Cr
(10 wt%) with a high amount of Mo (5.5 wt%), was observed to have
very low corrosion current densities and, therefore, high resistance to
corrosion. Hence, it is indicated that the corrosion resistance was sensi-
tive to the chemical composition of the Fe-based coatings.

Table 4
Electrochemical values of the coatings, immersed in 3.5 wt% NaCl at 25 °C.

Series Coatings Ecorr (V/SCE) icorr (μA·cm−2) βa (V·dec−1) βc (V·dec−1) Rp (kΩ·cm2)

A A1 −0.44 ± 0.02 1.26 ± 0.06 0.07 ± 0.003 0.04 ± 0.002 8.8 ± 0.5
A2 −0.25 ± 0.01 0.47 ± 0.02 0.04 ± 0.002 0.03 ± 0.001 15.9 ± 0.8
A3 −0.43 ± 0.02 0.72 ± 0.03 0.07 ± 0.003 0.04 ± 0.002 15.5 ± 0.78
A4 −0.56 ± 0.03 2.88 ± 0.14 0.10 ± 0.005 0.16 ± 0.007 9.3 ± 0.47
B B1 −0.44 ± 0.02 8.88 ± 0.44 0.08 ± 0.004 0.03 ± 0.002 1.1 ± 0.06
B2 −0.47 ± 0.02 0.20 ± 0.01 0.09 ± 0.004 0.09 ± 0.005 97.7 ± 5.1
B3 −0.52 ± 0.03 0.31 ± 0.01 0.09 ± 0.004 0.08 ± 0.005 59.3 ± 3.7
B4 −0.53 ± 0.03 9.45 ± 0.50 0.10 ± 0.005 0.09 ± 0.005 2.2 ± 0.2
C C1 −0.51 ± 0.02 8.62 ± 0.43 0.05 ± 0.002 0.02 ± 0.001 0.7 ± 0.03
C2 −0.47 ± 0.02 0.15 ± 0.007 0.18 ± 0.009 0.07 ± 0.004 145.9 ± 7.8
C3 −0.46 ± 0.02 0.10 ± 0.005 0.09 ± 0.005 0.05 ± 0.003 139.6 ± 7.4
C4 −0.53 ± 0.02 2.88 ± 0.15 0.05 ± 0.002 0.02 ± 0.001 2.2 ± 0.1
 E. Sadeghimeresht et al. / Surface & Coatings Technology 318 (2017) 365–373
Fig. 5. Cross-sectional backscattered SEM micrographs of corroded coatings after 3-hour OCP test in 3.5 wt% NaCl solution, at 25 °C.
The polarization resistance calculated in Table 4 showed that the
largest Rp was measured for coating C2 (145.9 kΩ·cm2), which was ba-
sically due to its low current density. The large Rp confirmed the high re-
sistance between the corrosive solution and the coatings, which led to
the best protection in the corrosive environment.
3.4. Characterization of corroded samples
Fig. 5 shows the cross-sectional SEM micrographs of the corroded
coatings after 3-hour immersion in OCP test. The coatings series C ex-
hibited the comparatively lower degree of damage, as observed from
the integrity of the top surface in the corroded samples, whereas the
coatings series B showed complete loss of original surface after 3 h of
exposure.
The corrosion mechanism that occurred in different coatings was
similar to crevice or pitting corrosion. The pores in the coatings acted
as blocked cells, which could have catalytic influences on the corrosion
reactions. Indeed, as reported in other literatures [16], the corrosion
products are mainly consisted of iron oxyhydroxide FeO(OH), which
could form in the coating pores. Accumulation of the corrosion products
371
in the pores provides physical obstacles to ionic diffusion and/or due to
their reduced electronic conductivity, and eventually hinders corrosion.
As the diffusion of O2 into these defects is much slower than that of
small Cl−, the electrolyte pH in the pores declines rapidly, and the
passivation is interrupted, as there is not enough O2– to react with, for
instance, Cr [7]. That is the most probable reason why a partial passiv-
ation was observed in the polarization curves of some coatings. The
Cl− that penetrated into the crevices favored the hydrolysis reactions,
which further decreased the electrolyte pH. The trans-passive potential
observed in a potential near to 1.0 V/SCE in the polarization plots is due
to the diffusion of Cl− and interruption in the passivation process. Over
time, the inner corrosion products of Fe2 + migrated to the coating
surface, where the oxyhydroxide was generated [16].
The figures with higher magnification (×2000) show how the elec-
trolyte in the coatings series A found preferential paths along the pores
and lamellar boundaries towards the substrate. On the contrary, no
visible through-paths were observed for the coatings series C. Corrosive
attacks were only limited at the very superficial layers due to very few
loose particles. Several factors affect the corrosion behavior. Firstly, be-
cause defects like pores or weak interlamellar cohesion were present in
372 E. Sadeghimeresht et al. / Surface & Coatings Technology 318 (2017) 365–373
coating surface, they became preferential sites for corrosion nucleation.
Moreover, the lamellae boundaries became preferential sites for corro-
sion growth. In the coatings series A and B, the defects served as open
channels, which eventually led to a direct path between the electrolyte
and inner part of the coating. In the coatings series B, the formation of
the passive film (although imperfect) slowed down the penetration of
corrosive species to reach the substrate. Therefore, it presented better
corrosion resistance in contrast to the coatings series A.
In order to achieve corrosion protection of the components, the coat-
ing must have a dense and defect-free microstructure to control the cor-
rosive ions to penetrate through defects (in particular, interconnected
pores) and reach the substrate [50]. Otherwise, localized corrosion
such as pitting and crevice may occur [51].
4. Conclusions
The corrosion behavior of HVAF and HVOF thermally sprayed Fe-
based coatings was studied using electrochemical measurements. The
major conclusions can be summarized as follows:
1. The HVAF-sprayed Fe-based coatings using a long nozzle and fine
particle size protected the underlying substrate against corrosion
better than HVOF-sprayed and HVAF-sprayed coatings with a short
nozzle and coarse particle size.
2. Adding Cr did not increase the corrosion resistance of the Fe-based
coatings, whereas higher uniformity of the coating decreased the
corrosion. The uniform and pore-free microstructure of the
Fe-based coatings outweighed the effect of chemical composi-
tion, particularly the addition of Cr.
3. The preferred sites for corrosion nucleation and growth were surface
defects such as pores, cracks, and interlamellar boundaries.
4. The HVAF-sprayed Fe-based coatings with the fine powder particle
size (− 36 + 20 μm) and composition containing medium level of
Cr (10 wt%) and high level of Mo (5.5 wt%) are recommended as a
potential alternative to the HVOF-sprayed Fe-based coatings.
Acknowledgement
The authors would like to express their acknowledgement to Mr.
Jonas Olsson, Mr. Kenneth Andersson and Mr. Stefan Björklund for their
advice in processing, engineering, and developing of the HVAF and
HVOF thermal spray experimental work in this study.
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