Surface & Coatings Technology 409 (2021) 126896

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Surface & Coatings Technology

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

Corrosion of high-velocity-oxygen-fuel (HVOF) sprayed non-crystalline

alloy coating in marine environment
Hung-Bin Lee a, *, Tzu-Jing Lin a, Chun-Ying Lee b
a
Department of Optoelectronics and Materials Technology & Center of Excellence for Ocean Engineering, National Taiwan Ocean University, Keelung 202, Taiwan
b
Graduate Institute of Manufacturing Technology, National Taipei University of Technology, Taipei 106, Taiwan

A R T I C L E I N F O A B S T R A C T

Keywords: Amorphous alloys owing to their high hardness, strength, corrosion and wear resistance are regarded as one of
Amorphous Fe alloy coating the potential coating materials for applications in severely corrosive environment. A high-velocity‑oxygen-fuel
HVOF spraying process (HVOF) spraying process was employed in this study to prepare an amorphous Fe alloy coating on SUS316
Corrosion resistance
substrate. The prepared Fe40-Cr19-Mo18-C15-B8 alloys had high hardness but the micro-structural examination
showed micro-voids and micro-cracks permeated in the coating. Both x-ray diffraction (XRD) and transmission
electron microscopy (TEM) measurements confirmed the combined amorphous and nano-crystalline phases in
the coating. Thermal stress after cooling from the spray process caused the emergence of intensive cracking. The
potentio-dynamic polarization curves of the prepared coating were measured in four different solutions,
respectively: 0.5 M H2SO4, 1 M NaOH, 3.5 wt% NaCl, and seawater. Among them, the prepared coating had
better corrosion resistance in neutral solutions. The corrosion tests under different applied over-potentials in
seawater further revealed nearly ten-fold increase in corrosion current when the over-potential was raised from
− 100 mVSCE, +200 mVSCE, +600 mVSCE, to +800 mVSCE, respectively. Although the coating surface roughened
considerably at higher over-potentials, oxidation of Mo and Cr elements in this Fe alloy during corrosion test,
confirmed from the measured six-valenced ions of Mo6+ and Cr6+ in the x-ray photoelectron spectroscopy (XPS)
analysis, was beneficial in lowering the corrosion current.

1. Introduction
Among the six categories in atmospheric corrosion defined by ISO
12944-9, corrosion in maritime environment is listed as the first grade
[1]. Due to the fine particles of sodium chloride contained in the sea
spray, the coastal area within 200 m from the shore line still is under the
influence of maritime corrosion. The construction foundation and in­
dustrial facilities located in the maritime environment, therefore, suffer
serious consequences from corrosion in service durability [2,3]. With
the purpose of protecting the structure used in maritime environment,
several coating processes have been proposed. Among them, thermal
spraying which melts and sprays the molten alloy in high speed onto the
surface of the structure to protect the substrate from chemical and
electrochemical attack of corrosive environment has received well
recognition. The preparation of amorphous metal coating has evolved as
the third generation process. The amorphous metal coating is uniform in
composition without the inclusion of structural defects such as
dislocation and grain boundary usually seen in its crystalline counter­
part. Moreover, amorphous metal coating possesses ultra-high strength,
toughness, wear and corrosion resistance. These unique and superior
properties drive the quick research and development of the amorphous
metal coatings both in academia and industry [4]. Amorphous ferrous
alloy coating is a typical material showing excellent wear and corrosion
resistance and is widely used in the applications of maritime, petroleum,
coal-powered facilities [5].
Regarding the development of amorphous ferrous coating in material
and process, Miura et al. [6] first applied flame spraying technique in the
preparation of amorphous Fe-Ni-P-B coating. They confirmed the
amorphous nature of the prepared coating using X-ray diffractometry
(XRD) and differential scanning calorimetry (DSC). Subsequently, high
velocity oxygen fuel (HVOF) spraying becomes one of the primary
processes in preparing amorphous ferrous alloy coating. In 2003, De­
fense Advanced Research Projects Agency (DARPA) of the United States
proposed a project of using amorphous coating as the anti-corrosion

* Corresponding author at: Department of Optoelectronics and Materials Technology& Center of Excellence for Ocean Engineering, National Taiwan Ocean
University, Keelung 202, Taiwan, ROC.
E-mail address: lhb6018@mail.ntou.edu.tw (H.-B. Lee).

https://doi.org/10.1016/j.surfcoat.2021.126896
Received 12 November 2020; Received in revised form 5 January 2021; Accepted 6 January 2021
Available online 26 January 2021
0257-8972/© 2021 Elsevier B.V. All rights reserved.
H.-B. Lee et al. Surface & Coatings Technology 409 (2021) 126896

Fig. 1. FESEM microscopy: (a) metallic powder of the ferrous alloy, (b) surface of the sprayed coating, (c) cross section of the sprayed coating, the number 1–4
labeled in (a) and (c) are locations for the composition measurements reported in Table 1, (d) an enlarged view at arrow-pointed portion in (c).

coating for naval vessels. Amorphous ferrous alloys SAM2X5 and sand particles. The wear rate in erosion usually depends on the fluid
SAM1651 were employed in the development of high performance speed, particle size and content. Amorphous ferrous alloy coating
corrosion-resistant coatings [7]. The microstructure of the thermal revealed better local corrosion resistance than overall uniform one while
sprayed coating usually is influenced by the compositions and thickness. SUS304 showed the opposite performance [22].
The alloying Mo is better in obtaining an amorphous phase than its Cr In this study, a thermal spray process was employed in the prepa­
counterpart while amorphous content increases with coating’s thickness ration of an amorphous ferrous alloy coating consisting of Cr, Mo, C and
[8]. In addition, the number of via holes decreases with increasing B elements. The element contents of the prepared coating, its crystal­
thickness of amorphous coating. Via hole may disappear totally as the linity and microstructure were investigated. Through the corrosion tests
amorphous coating reaches certain thickness [9]. The porosity in the in different solutions and detailed analyses on the corroded surface, the
thermal sprayed coating also diminishes and the deposition rate speeds possible interaction between the coating and solution, and the dissolu­
up when the fuel in spraying process is raised [10]. Nonetheless, the tion behavior of the prepared coating was further discussed.
content of amorphous phase lowers accordingly. Moreover, nearly all
the reported amorphous ferrous coatings reveal the passivation with 2. Experimental
extreme low current density and outstanding corrosion resistance.
Similar excellent performance of ferrous coatings by plasma sprayed 2.1. Preparation of amorphous ferrous alloy coating
process [11–13] and arc spraying process [14] were also reported. With
increasing current in plasma intensity, the content of amorphous phase The substrate used in this study was a cylindrical tube made of
increases accompanied by lower porosity. But as the thickness of coating SUS316 with outside diameter of 20 mm and axial length of 16 mm. The
increases, the content of amorphous phase decreases. The coating re­ surface of the specimen was first degreased and cleaned using thinner
veals a desired combination of high hardness and superior resistance and alcohol. Sand blasting using SAE G16 steel grit was performed 1 h
against corrosion and erosion. The reduction in porosity was also ach­ before spraying to enhance the adhesion of the sprayed coating. On the
ieved by annealing treatment [14]. other hand, the metallic powders of Fe-Cr-Mo-C-B alloy with particle
In the anti-corrosion respect, amorphous ferrous coating, like its sizes between 20 and 50 μm were baked in an oven at 100 ◦ C for 1 h to
amorphous counterparts of other alloys, has superior performance based remove the water content. Before the spraying process, the substrate was
on its homogeneous chemical composition and microstructure. The ex­ preheated with the torch gun to have its surface temperature elevated to
istence of local electrochemical cells from different crystalline phases
[15] or the gas voids [16] in the amorphous matrix could render the
increase in corrosion current. On the other hands, the incorporation of Table 1
more Cr [17–19], Mo [17,19,20], W and Mn [20] in the composition of Elemental compositions of the coating at the labeled positions shown in Fig. 1.
the amorphous ferrous coatings was beneficial in raising the coating’s Elements Fe (at. Cr (at. Mo (at. C (at. B (at. Total
corrosion resistance. The formation of stable and compact oxides in the location %) %) %) %) %)
passivation film usually contribute to the corrosion protection of the
1 40.01 18.76 17.4 15.17 8.66 100.00
substrate metals. In the erosion environments, Zheng and coworkers 2 39.67 19.38 17.57 14.98 8.40 100.00
[21] demonstrated that the amorphous ferrous coating had far less wear 3 39.89 19.34 17.46 15.01 8.30 100.00
rate than SUS304 in the attack of 3.5% NaCl solution mixed with 2% 4 40.29 18.87 17.66 14.75 8.43 100.00

2
H.-B. Lee et al.
Fig. 2. Measured results of the sprayed coating: (a) XRD spectrum, (b) DSC curves.
200 ◦ C. The process parameters of the HVOF were set at propane flow
rate of 48 F.M.R., oxygen flow rate 29 F.M.R., powder feed rate 35 g/
min, travelling speed of torch gun 800 mm/s, nozzle distance 330–360
mm.
2.2. Corrosion test
A rotating corrosion tester was employed in this study [23]. The
specimen was attached to the rotating spindle which ran in a speed of
200 rpm and tested duration was set at 2400 s. A tri-electrode config­
uration for the electrochemical measurement of potentio-dynamic curve
was adopted using a Zennium E electrochemical workstation (Zahner-
Elektrik GMBH & Co., Germany). The rotating spindle with attached
specimen, a saturated calomel electrode and a platinum plate were used
as working electrode, reference electrode and counter electrode,
respectively. Four different solutions were used in the corrosion tests:
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Surface & Coatings Technology 409 (2021) 126896
0.5 M H2SO4, 1 M NaOH, 3.5% NaCl and seawater from Keel-Long
harbor in Taiwan. Characteristics analyses of the Keel-Long’s seawater
revealed the following properties: temperature 25.5–26.0 ◦ C, oxygen
content 4.5–8.4 mg/L, concentration of chlorine ion 14,000–24,300
ppm, pH 7.25–8.64, electrical conductivity 38.0–52.5 mΩ/cm. Corro­
sion potential (Ecorr) and corrosion current density (Icorr) were obtained
from the potentio-dynamic curve measured from − 1500 mVSCE to
+1500 mVSCE with a scanning rate of 1 mV/s, where the potential was
measured by using a saturated calomel electrode (SCE). The corrosion
test was also conducted at five different applied over-potentials: open-
circuit potential (OCP), − 100 mVSCE, +200 mVSCE, +600 mVSCE and +
800mVSCE. The terminology “overpotential” used in this study is only to
denote the potential is higher than the OCP of the coating. Therefore, the
coating under corrosion testing is in anodic polarization. It is not
intended to represent the potential measured with respect to the OCP
basis.
H.-B. Lee et al. Surface & Coatings Technology 409 (2021) 126896

Fig. 3. (a)Potentio-dynamic polarization curves of the coating measured in different solutions, (b) Potentio-dynamic polarization curves of the coating and two
stainless steels measured in seawater.

2.3. Property measurement and microstructure examination

Table 2
The hardness of the coating was measured directly on its surface Corrosion potentials and corrosion current densities of the coating measured in
using micro-Vickers hardness tester (Shimadzu HMV-2, Japan) under different solutions.
100 g loading magnitude and 10 s loading duration. For the thermal Corrosion parameters 0.5 M H2SO4 3.5 wt% NaCl 1 M NaOH Seawater
stability of the prepared amorphous ferrous coating, both thermogra­
Ecorr (mV) − 418.7 − 799.4 − 1173.1 − 536.7
vimetric analysis and differential calorimetric scanning was performed Icorr (μA/cm2) 300 145 236 27.2
using a simultaneous thermal analyzer (SDT Q600, TA, U.S.A.). A pH 0.6 6.3 12.9 7.3
sample of amorphous ferrous coating of 3–5 g in mass was pressed in an
aluminum pan and heated in a nitrogen environment from 300 K to
1700 K with heating rate of 10 ◦ C/min. For the microstructure and
texture examination of the coating, both an x-ray diffractometer (Shi­ Table 3
madzu XRD-6000, Japan) and a transmission electron microscope (JEOL Corrosion potentials and corrosion current densities for the coating and two
JEM-2100F, Japan) were employed for the overall and the cross- stainless steels measured in seawater.
sectional characterization, respectively. As for the surface morphology
Ecorr Icorr
of the coating, a field-emission scanning electron microscope (JEOL
304 SS − 853.4 mV 101 μA/cm2
JSM-7401F, Japan) was used. The composition of the coating was
316 SS − 753.2 mV 13.6 μA/cm2
measured using its associated energy-dispersive x-ray spectroscopy FeCrMoCB − 536.7 mV 27.2 μA/cm2
(EDS) module. The x-ray photoelectron spectroscopy (ULVAC-PHI, PHI
5000 Versa Probe, XPS) was employed in the determination of the
elemental compositions and chemical valences of the specimen before
and after the corrosion test. Moreover, the elemental distribution
through-the-thickness was obtained by step-by-step Ar+ ion ablation
from the coating’s surface.

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H.-B. Lee et al.
Fig. 4. FESEM microscopy of sprayed coating tested in seawater and at different over-potentials: (a) pristine coating, (b) OCP, (c) -100 mVSCE, (d) +200 mVSCE, (e)
+600 mVSCE, (f) +800 mVSCE. Red dash line denotes the datum line.
3. Experimental results
3.1. Microstructural examination
Fig. 1 shows the FESEM microscopy of the ferrous alloy powder and
the thermal sprayed coating. In Fig. 1(a), it shows that the particle sizes
are around 20 μm − 50 μm which have an average hardness of 1020 Hv
from hardness testing. For comparison, this hardness is much larger than
those of 304SS and 316SS, which have measured hardness of 195 Hv and
183 Hv, respectively. The surface of the sprayed coating, presented in
Fig. 1(b), reveals a rough morphology with voids and scattered un-
melted particles. The cross-sectional views in Fig. 1(c) and (d) reveal
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Surface & Coatings Technology 409 (2021) 126896
the existence of 5 μm − 20 μm sized micro-voids and 20 μm–70 μm long
micro-cracks in the coating of about 270 μm thick. Possible cause for
these defects is the low heating power used in the spraying process
which was not sufficient to melt the powders and generate smooth
surface. In the meantime, the insufficient bonding between droplets
formed by the poorly melted powders paves the way for developing
cracks while the temperature drop induced thermal contraction [24].
Although it is not further pursued in this study, with the raise in heating
power during spraying, the emergence of micro-voids and micro-cracks
should diminish because the accelerated melting provides more thermal
energy to reduce the surface tension of droplets [22,25]. The EPMA
measurements on the ferrous powders and the sprayed coating,
H.-B. Lee et al.
Fig. 5. The variations of measured current densities of the sprayed coating in seawater under different applied over-potentials.
Table 4
The average of current densities of the sprayed coating in seawater under
different applied over-potentials as seen in Fig. 5.
Applied over- OCP − 100 +200 +600 +800
potential mVSCE mVSCE mVSCE mVSCE
Current density 0.0035 0.0055 0.0365 0.2246 2.2814
(mA/cm2)
presented in Table 1, demonstrate no significant difference in compo­
sitions occurred.
In the XRD diffraction spectrum shown in Fig. 2(a), it is clearly seen
the existence of a wide peak near 2θ = 43o. Thus, the barely existence of
obvious Bragg’s diffraction peak denotes the nearly amorphous nature
of the sprayed coating. The measured DSC curves for both ferrous
powder and the sprayed coating, presented in Fig. 2(b), demonstrate
high similarity. Crystallization temperature and melting point for the
powder and coating are 960 K, 1405 K and 961 K, 1410 K, respectively.
These close temperatures in crystallization and melting for powder and
coating show they had similar amorphous nature and non-crystallinity.
High coating’s hardness of 1024 Hv, an average from ten measured
points, was also observed.
3.2. Corrosion measurement and morphology examination
As mentioned previously, the potentio-dynamic polarization curves
of the prepared coating were measured in four different solutions,
respectively: 0.5 M H2SO4, 1 M NaOH, 3.5 wt% NaCl, and seawater. All
the polarization curves shown in Fig. 3(a) demonstrate the sequential
activation, passivation and over-passivation transition as the applied
potential increased. The corresponding corrosion potential (Ecorr) and
corrosion current density (Icorr) from each measurement are listed in
Table 2. The lowest Icorr occurred in seawater at 27.2 μA/cm2 while the
others in 0.5 M H2SO4, 1 M NaOH, and 3.5 wt% NaCl were 300 μA/cm2,
236 μA/cm2 and 145 μA/cm2 in descending order. These results denote
the relatively inferior corrosion resistance for this sprayed coating in
either acidic or basic solution due to its high measured corrosion cur­
rent. Nevertheless, the developed passivation film in all four solutions
provides the protective and stable corrosion resistance for the coating.
For comparison, Fig. 3(b) also presents the potentio-dynamic
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Surface & Coatings Technology 409 (2021) 126896
polarization curves of the prepared coating and both 304SS and 316SS
plates measured in seawater. Their associated Ecorr and Icorr are listed in
Table 3. The Icorr of the prepared coating is 27.2 μA/cm2, which is larger
than 316SS (13.6 μA/cm2) but much smaller than 304SS (101 μA/cm2).
These results demonstrate this amorphous coating has comparable anti-
corrosion performance as the 316SS while superior performance over its
304SS counterpart. Better corrosion resistance of similar amorphous Fe-
alloy coatings, such as Fe48Cr15Mo14C15B6Y2 alloy [11], FeCrNi-based
alloy [26] and Fe42.87Cr15.98Mo16.33C15.94B8.8 alloy [27], in neutral
3.5 wt% NaCl solution than acidic and basic solutions was also reported.
Fig. 4 presents the FESEM micrographs of the coating after tested in
seawater at different over-potentials. At low over-potentials such as OCP
and − 100 mVSCE, both the surface and cross-sectional views did not
show much variation from the pristine coating. At +200 mVSCE, both the
number and size of voids on coating’s surface increased. The cross-
sectional view also revealed the emergence of 20 μm sized void. With
the over-potential raised to +600mVSCE, the void in the cross-sectional
view grew in number and enlarged in size to 45 μm. At +800 mVSCE,
further growth in void size was observed. Accompanying the raise in
over-potential, it is realized that the corrosion started from the emer­
gence of voids, propagated into the coating through micro-cracks,
weakened the coating’s structure, until the partial coating peeled off
and generated big voids.
4. Discussion
4.1. Micro-structural analysis of the coating after corrosion test
Fig. 5 presents the variations of measured current densities of the
sprayed coating in seawater under different applied over-potentials.
During this 20-min corrosion test, the average of each current density
curve under different applied over-potentials was calculated and listed
in Table 4. For the corrosion tests at low over-potentials, i.e. OCP and
-100mVSCE, similar current density magnitudes around 0.0035 mA/cm2,
were measured. No serious deterioration on coating’s surface and
thickness was noted from the FESEM examination. However, near ten
folds increase in corrosion current density appeared each time when the
over-potential was raised to +200mVSCE, +600mVSCE and +800mVSCE,
respectively. Because of the large increase in current density for test at
+800mVSCE, its result was only displayed in the inset of Fig. 5. The
H.-B. Lee et al. Surface & Coatings Technology 409 (2021) 126896

Fig. 6. Schematic diagrams of the coatings after corrosion tests at different over-potentials: (a) OCP, (b) -100 mVSCE, (c) +200 mVSCE, (d) +600 mVSCE, (e)
+800 mVSCE.

corrosion pits not only increased in number but also in size and grew crystalline grains along the cracking path, such as those observed at A,
deeper into the coating. The stable passivation film formed at low over- C and E, should be induced by the high strain energy during crack
potentials ensured the protective function for the coating. At high over- propagation. The associated compositional analyses from EDS mea­
potentials, the passivation film was not stable and sufficient to protect surements revealed the drop in Fe content while a raise in O content. It is
the coating’s surface from corrosion. The enlargement and intercon­ inferred that the coating may contain Cr2O3, CrO3, MoO2 and MoO3
nection of voids generated cracking and flakes peeled away from the from the passivation film. A further analysis using XPS is required for
coating. Fig. 6 presents the schematic diagrams for the corrosion char­ studying the micro-structure and chemical composition of the passiv­
acteristics of the coatings under aforementioned corrosion tests at ation film in the corroded coating.
different over-potentials.
The micro-structure of the coating was further examined by TEM
4.2. Corrosion mechanism of the ferrous coating
microscopy. Fig. 7 shows the results from TEM-SAED-EDS analyses of
the coating after corrosion tests at different over-potentials. In Fig. 7(a)
The interaction between the alloy elements and corrosion behavior
and (b), the pristine coating prepared from thermal spray process con­
can influence the formation of the passivation film through their
tained a mixture of crystalline and amorphous phases. There were cracks
elemental states and chemical compositions. For obtaining the infor­
inside the coating and nano-crystalline grains of 20 nm to 50 nm in size
mation, the XPS spectra of the coating after corrosion tests at different
scattered along the side of cracks. The inset of selected area electron
over-potentials in seawater were measured. Fig. 8 presents these
diffraction (SAED) result at A revealed its nano-crystalline nature. The
measured full spectrum results of the passivation films. Some critical
associated TEM-EDS analysis indicated the main elemental ingredients
binding energy peaks were labeled in the spectra. Although the spectra
of Fe, Cr, Mo, C, probably the result from Cr7C3 or Fe–Cr structure
showed overall similarity, differences in peak intensity existed. Different
[22,28]. The SAED diagram at B demonstrated the diffused halo pattern
chemical state and composition of the alloy elements caused the varia­
which indicated this HVOF sprayed coating was amorphous in nature.
tion in the measured intensity of the binding energy. For analyzing the
This amorphous structure was consistent with the measured XRD spec­
compositions of the passivation films formed at different over-
trum reported in Fig. 2.
potentials, the binding energy peaks corresponding to those main
The TEM microscopy on the specimens tested at high over-potentials
alloying elements such as Fe, Cr and Mo had to be further decomposed.
of +200 mVSCE and +600 mVSCE were presented in Fig. 7(c) and (d),
In the detailed analysis of the measured XPS spectrum, a software
respectively. From the insets of SAED patterns measured at D and F
package XPS Peak Version 4.0 was employed in this study. The spectrum
confirmed again its amorphous nature. The occurrence of nano-
was first processed with Shirley background subtraction method and the

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H.-B. Lee et al.
Fig. 7. The results from TEM-SAED-EDS analyses of the coating after corrosion tests at different over-potentials: (a) (b) pristine coating, (c) +200 mVSCE, (d) +600
mVSCE, (e) composition analyses at the labeled positions.
binding energy peaks of Fe, Cr and Mo were then decomposed into
components. Fig. 9 presents the de-convolution curve fitting results on
the binding energy peaks of Fe, Cr and Mo elements in the measured XPS
spectra of the coating after corrosion tests at different over-potentials in
seawater. The reference binding energies for Fe, Cr and Mo elements,
respectively, were denoted in Table 5, which were employed to discern
the corresponding binding energies in Fig. 9.
The 2p3/2 spectrum of Fe was composed of elemental Fe and oxidized
Fe2+ and Fe3+. After corrosion test at OCP or − 100 mVSCE, there were
peaks at B.E. = 707.3 eV and B.E. = 709.6 eV, which corresponded to Fe0
and Fe2+ peaks of Fe and FeO. At higher over-potentials of +200 mVSCE
or +600 mVSCE, Fe3+ peak of Fe2O3 with B.E. = 710.9.0 eV
[21,19–21,33] appeared in addition to the aforementioned Fe0 and Fe2+
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Surface & Coatings Technology 409 (2021) 126896
peaks at low over-potentials. Stockbridge proposed the Fe3O4 peak in
the Fe 2p3/2 spectrum could manifest as the existence of FeO and Fe2O3
[29]. Therefore, the measured XPS spectrum near the Fe 2p3/2 peak of
the corrosion tested coating demonstrated the existence of Fe0, FeO and
Fe2O3 while probable appearance of Fe3O4 [36].
The decomposition of the XPS spectrum near the Cr 2p3/2 peak
revealed, at low overpotential of OCP or − 100 mVSCE, the existence of Cr
and Cr2O3 associated with the Cr0 and Cr3+ peaks which had B.E. =
574.2 eV and B.E. = 575.9 eV, respectively. With the over-potential
raised to +200 mVSCE, the Cr3+ peak was noted more obviously. Addi­
tional Cr6+ peak of CrO3 with B.E. = 577.7 eV [19,20,21,24,33,36]
emerged in addition to the mentioned Cr0 and Cr3+ peaks. This XPS
analysis confirmed the existence of Cr0, Cr2O3 and CrO3 in the corroded
H.-B. Lee et al.
Fig. 8. The measured XPS spectra of the coating after corrosion tests at different over-potentials in seawater.
coating.
In the decomposition of XPS spectrum near Mo 3d peak, because of
the nearly overlapped peaks of two oxidized states the analysis became
more complicated. Thus, a fixed intensity of 3.1 eV was assigned to both
Mo 3d5/2 and Mo 3d3/2 peaks [34]. For the coating tested under over-
potential of OCP or -100mVSCE, the appearance of Mo0 and Mo4+
peaks at B.E. = 228.0 eV and B.E. = 231.1 eV denoted the existence of
Mo and MoO2. Additional peak at B.E. =232.1 eV, which was associated
to Mo6+ peak of MoO3 [19,21,33–36], emerged when the over-potential
was raised to +200 mVSCE or +600mVSCE. This Mo6+ peak showed
significant increase in intensity with respect to +200 mVSCE. The result
from this XPS analysis near Mo 3d3/2 spectrum validated the composi­
tions of Mo0, MoO2 and MoO3.
From the above overall analysis in the XPS spectra, the corrosion
mechanism of the prepared ferrous coating in seawater can be clarified.
At low over-potential of OCP or -100 mVSCE, the corrosion products
mainly consisted of oxides such as Cr2O3 and MoO2 which were bene­
ficial in impeding the corrosion progression [35]. At higher over-
potentials of +200 mVSCE and +600 mVSCE, additional oxides of CrO3
and MoO3 emerged in the corrosion product. The presence of six-
valenced Mo6+ and Cr6+ further raised the coating’s anti-corrosion
performance [21,36]. The combined effect from these oxides
improved the stability of the passivation film at different over-
potentials.
Fig. 10 shows the through-the-thickness composition variations of
the coating after corrosion tests at different over-potentials in seawater.
These results were distilled from the analyses of the measured XPS
spectra of the coating after ablations. The ablations were performed
using Ar+ etching at 2 kV over a scanning area of 2 mm × 2 mm. The
corresponding etching rate of 18.44 nm/min was calibrated on SiO2
sample with the same ablation parameters. From Fig. 10(a), an average
content of 35 at.% of Fe was observed. At -100mVSCE, Fig. 10(b), Fe
content decreased slightly because the Fe element oxidized preferably to
Cr and Mo, and the formed loose oxide detached easily from the surface.
Moreover, the Cr2O3 formed from oxidation of Cr was more protective
than FeO, and Mo element was less reactive than Fe due to its higher
corrosion potential. Thus, relatively more weight loss was from Fe
element and the decrease in Fe content was measured. At +200 mVSCE
and +600 mVSCE, O contents became dominant and other element
contents except C dropped drastically in Fig. 10(c) and (d). The results
denoted the more serious attack by the seawater at high over-potentials,
which were consistent with the FESEM microscopic observations and the
corrosion current measurements, presented in Figs. 4 and 5,
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Surface & Coatings Technology 409 (2021) 126896
respectively. The return of Fe, Cr, and Mo contents back to nominal level
revealed the thickness of corrosion film was around 100 nm. Consid­
ering the relatively small thickness affected by the corrosion test, this
thermal sprayed amorphous Fe alloy coating demonstrated high corro­
sion resistance in seawater. Although the annealing of the sprayed
coating can alter its crystalline property, the increase in the content of
crystalline phase usually degrades the anti-corrosion performance of the
prepared coating [36]. Therefore, the relationship between the amor­
phous structure of coating and corrosion resistance is not pursued in this
study.
5. Conclusion
A HVOF thermal spray process with following parameters was
employed in this study to prepare amorphous Fe alloy coating on
SUS316 substrate: propane and oxygen feeds in 48 F.M.R. and 29 F.M.R.,
respectively; powder size of 20–50 μm and feed rate of 35 g/min; nozzle
spacing of 330–360 mm and travelling speed of 800 mm/s. The prepared
coating was then tested with a rotating corrosion tester in four different
solutions: 0.5 M H2SO4, 1 M NaOH, 3.5 wt% NaCl solutions and
seawater, respectively. The corrosion study then focused on the per­
formance and plausible mechanism of the coating in seawater and under
different applied over-potentials. The important findings were summa­
rized in the following:
1. The spraying process under the specified process parameters pre­
pared the coating having rough surface with voids and incompletely
melted powders. There were micro-voids and linear micro-cracks
found in the cross-sectional SEM examination. These micro-cracks,
originated from the stress concentration sites near the micro-void
defects, should be induced by the release of high thermal stress
during cooling and the brittle nature of the amorphous phase. As for
the micro-structure, nano-crystalline grains distributed along the
crack in the overall amorphous phase denoted the strain energy in
the crack tip during crack propagation could initiate recrystallization
reaction.
2. With the raise of applied over-potential in corrosion test from − 100
mVSCE, +200 mVSCE, +600 mVSCE, to +800 mVSCE, the measured
current density increased in nearly ten folds each time. At low over-
potential, the passivation film developed had good protective per­
formance against corrosion in seawater. However, at high over-
potentials, surface roughening by the formation of larger voids,
cracking, and peeling off appeared. Nevertheless, the corrosion
H.-B. Lee et al. Surface & Coatings Technology 409 (2021) 126896

Fig. 9. The de-convolution curve fitting analyses on the binding energy peaks of (a)Fe, (b)Cr and (c) Mo elements in the measured XPS spectra of the coating after
corrosion tests at different over-potentials in seawater.

10
H.-B. Lee et al. Surface & Coatings Technology 409 (2021) 126896

Table 5
Measured and Reference binding energies for the XPS analysis taken from NIST USA.
Element Spectral line Formula Binding energy (eV)

NISTa Reference Experimental on the surface

Fe 2p3/2 Fe 707.3 707.4[27–29] 707.3

Fe 2p3/2 FeO 709.6 709.3[28,30] 709.6
Fe 2p3/2 Fe2O3 710.9 710.9[28,30] 710.9
Fe 2p1/2 FeO(Fe3O4) 708.2 708.2[27,31,36]
Fe 2p3/2 Fe2O3 (Fe3O4) 710.4 710.3[27,31,36]
Cr 2p3/2 Cr 574.1 574.1[28,32] 574.2
Cr 2p3/2 Cr2O3 576.0 575.9[28,30] 575.9
Cr 2p3/2 CrO3 578.3 577.7[32,36] 577.7
Mo 3d5/2 Mo 228.0 227.8[32,34,36] 228.0
Mo 3d5/2 MoO2 231.1 232.3[32,34,36] 231.1
Mo 3d5/2 MoO3 232.2 234.5[32,34,36] 232.1
a
Reference data are taken from XPS data base of NIST USA: http://srdata.nist.gov/xps/.

Fig. 10. The through-the-thickness composition variations of the coating after corrosion tests at different over-potentials in seawater: (a)OCP, (b)-100 mVSCE, (c) +
200 mVSCE, (d) + 600mVSCE, distilled from the analyses of the measured XPS spectra of the coating after ablations.

11
H.-B. Lee et al.
affected 185 nm in depth from the coating’s surface still revealed the
excellent corrosion resistance of the prepared ferrous coating.
3. The XPS analysis conducted in this study helped to understand the
interaction among the Mo, Cr, and Fe elements corrosion in
seawater. The emergence of Cr2O3, MoO2, CrO3 and MoO3 during
corrosion, confirmed from the measured six-valenced ions of Mo6+
and Cr6+, was beneficial in reducing the corrosion current.
Declaration of competing interest
None.
Acknowledgement
The financial support from Ministry of Science and Technology,
Taiwan under Grant No. MOST 109-2221-E-019-041 and University
System of Taipei Joint Research Program, USTP-NTUT-NTOU-109-04
are gratefully acknowledged.
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