Surfaces and Interfaces 22 (2021) 100885

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Surfaces and Interfaces

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Morphological and corrosion studies of ammonium phosphate and caesium

nitrate treated Al coating deposited by arc thermal spray process
Jitendra Kumar Singh a, Hyun-Min Yang a, *, Han-Seung Lee b, *, Sumit Kumar c, Fahid ASLAM d,
Rayed Alyousef d, Hisham Alabduljabbar d
a
Innovative Durable Building and Infrastructure Research Center, Hanyang University, 55 Hanyangdaehak-ro, Sangrok-gu, Ansan-si, Gyeonggi-do, 15588, Republic of
Korea
b
Department of Architectural Engineering, Hanyang University, 55 Hanyangdaehak-ro, Sangrok-gu, Ansan-si, Gyeonggi-do, 15588, Republic of Korea
c
Department of Chemistry, B.S.S College Supaul, B.N. Mandal University, Bihar, 852 131, India
d
Civil Engineering Department, College of Engineering, Prince Sattam Bin Abdul-Aziz University, Al-Kharaj, 11942, Saudi Arabia

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

Keywords: In the present studies, the Al coating deposited by arc thermal spraying process was treated with different
Al concentrations of ammonium phosphate mono basic ((NH4)H2PO4) and caesium nitrate (CsNO3) to improve the
Steel morphology and corrosion characteristics of the coating. As coated (AC) sample exhibits pores and defects onto
Coating
the surface but once the treatment was carried out, the coating shows reduction in porosity as observed by
Arc thermal spray
Corrosion
scanning electron microscopy (SEM). The treated coatings contain caesium aluminum oxide (CAO: Cs2Al2O3) and
Artificial ocean water ammonium aluminum hydrogen phosphate hydrate (AHP: (NH4)3Al5H6(PO4)8.18H2O) as composite oxides
identified by X-ray diffraction (XRD). Electrochemical impedance spectroscopy (EIS) results reveal that as the
exposure periods are increased, the resistance to coating/treatment (Rc/t) and charge transfer resistance (Rct) of
AC and 0.5 M NH4H2PO4 and 0.0025 M CsNO3 (CN2) are increased with exposure periods in artificial ocean
water solution. The improvement in total impedance values at 0.01 Hz of AC sample is attributed to formation of
corrosion products which fill the pores/defects of coating while CN2 sample owing to the treatment film i.e. AHP
and CAO and transformation of AHP into stable form. As the amount of NH4H2PO4 and CsNO3 is increased up to
1 M and 0.005 M i.e. CN3, the AHP film dissolved and enhances the corrosion reaction. Thus, cracking is
observed in corrosion products. The enhancement in corrosion resistance of CN2 sample is attributed to the
formation of α-Al(OH)3 (bayerite) and Al3(PO4)2(OH)3(H2O)5 (Aluminium hydroxide phosphate hydrate: AHPH)
in greater amount as corrosion products. These corrosion products of CN2 sample are stable, sparingly soluble
and protective.

1. Introduction
Plain carbon steel is prone to corrosion in aggressive environments
and causes catastrophic failure of structures. However, the corrosion of
steel structure depends on exposure conditions such as atmospheric,
splash/tidal, submerged and buried, therefore, coating is required to
mitigate the corrosion of steel structure. Coating is providing protection
to the steel from corrosion and erosion failure. But the types of coating to
be used on the steel substrate depend on exposure conditions. The steel
structure immersed in seawater or near to offshore need to be coated by
active metal i.e. Al, Zn and Mg which can provide cathodic protection
[1].
There are different coating processes to deposit the metallic coating i.
e. Al, Zn and Mg onto the steel substrate. However, the thermal spray
process is versatile process being used in different industrial sectors and
it can be applicable to protect the materials, metals and alloys from
corrosion in harsh environments [2–6]. The Al coating deposited by
thermal spray process are widely used to protect the offshore, risers,
pipes, and ship from corrosion [7,8] in immersed, tidal, splash zone and
marine atmosphere [9]. However, Al coating can provide barrier pro­
tection for long term exposure as well as cathodic protection to the steel
substrate [10–12]. The corrosion resistance properties of Al coating can
be achieved by alloying with active metals [13,14].
There are different thermal spray processes such as plasma, arc,

* Corresponding authors.
E-mail addresses: yhm04@hanyang.ac.kr (H.-M. Yang), ercleehs@hanyang.ac.kr (H.-S. Lee).

https://doi.org/10.1016/j.surfin.2020.100885
Received 24 September 2020; Received in revised form 9 December 2020; Accepted 13 December 2020
Available online 17 December 2020
2468-0230/© 2020 Elsevier B.V. All rights reserved.
J.K. Singh et al.
detonation, high velocity oxy-fuel, high velocity air fuel, cold spraying
etc. to deposit the Al coating. But among them, the arc thermal spray
process is convenient, easy to application compared to other thermal
spray processes and the spray gun can be brought to onsite and deposit
the coating. The arc thermal spray process is based on melting of twin
wires at tip with an electric arc and the melted droplets are propelled by
a compressed air towards the substrate to be coated [15–17]. The arc
thermal spray process is economical and easy to application than hot dip
galvanized, flame spray, high-velocity oxy fuel etc. [15]. However, this
process possesses some inherent properties such as porosity and cracks
formation on surface attributed to the continuous deposition of coating
and sudden cooling of molten metal particles. Although, the porosity in
the deposited coating is inevitable. Moreover, it can be controlled by
selecting appropriate feedstock material and spraying parameters.
There are different sealants which fill out the porosity of thermal
sprayed coating and enhances the corrosion resistance properties of Al
coating [18]. The post-treatment or sealing of coating depends on the
coating materials and its service life conditions. Wang and Zhou (2019)
have used glass powder to seal the pores of Al coating deposited by arc
thermal spray process and found that sealed coating exhibited higher
corrosion resistance compared to as deposited one in 3.5 wt.% NaCl
solution [19]. The most of the often used sealants are epoxide, phenolic,
furans, polymethacrylates, silicones, polyester, polyurethanes and
polyvinyl ester. Waxes can be used as pore sealing agent but it depends
on service temperature. It can be used in cold condition whereas
phenolic resin resists up to 150-260 ◦ C and methacrylate up to 150 ◦ C
[20]. The organic paint can be used to fill out the pores of Al coating but
it causes active corrosion and blistering owing to the acidification un­
derneath of paint where water and Cl− ions can diffuse easily [21,22].
Thus, it is suggested to avoid the use of organic paint to seal the pores of
coating.
The inorganic sealants i.e. aluminum phosphate, sodium and ethyl
silicates, different sol-gel type solution and chromic acid have been used
as sealing agent to fill the porosity of the thermally sprayed coatings.
However, through the annealing of coating at melting point, the porosity
can be filled, but it may change the microstructure which causes
relaxation in residual stress [23]. Therefore, it is utmost required to fill
the porosity of coating deposited by arc thermal spray process using
Fig. 1. SEM images of (a) AC, (b) CN1, (c) CN2 and (d) CN3 at 1,000X.
2
Surfaces and Interfaces 22 (2021) 100885
proper chemicals. The use of solution based inorganic salt i.e. phosphate
as pore sealing agent dissolve in water and applied onto the Al coating
by brush. After the application of pore sealing agent, the Al react and
form composite oxide which fill the pores of coating and enhance the
corrosion resistance properties [24–27]. The phosphate based pore
sealing agent has promising properties on morphological and corrosion
resistance in aggressive environment. The different concentrations of
ammonium phosphate have been used as pore sealing agent and it was
found that 0.1 M exhibited excellent corrosion resistance properties but
once the concentration is increased, it shows deterioration attributed to
the formation of acidic film [24].
In the present study, the Al coating was deposited by arc thermal
spray process which possesses porosity. The porosity of the deposited
coating was filled by post-treatment with different concentrations of
ammonium phosphate mono basic (NH4H2PO4) and caesium nitrate
(CsNO3) to improve the properties of coating. The corrosion kinetics and
mechanism of as coated (AC) as well as treated coatings was assessed in
artificial ocean water solution [28] at prolonged exposure periods.
2. Methods and materials
2.1. Process of coating
A 8 cm x 6 cm x 0.1 cm dimensions of plain carbon steel plate con­
taining C=0.20, Mn=0.95, Si=0.26, P=0.02, S=0.01, Cu=0.02,
Cr=0.04, Ni=0.03, Fe=balance in wt.%.was coated with 1.6 mm
diameter of Al (99.95wt.%) twin wires by arc thermal spray process.
Prior to deposit the coating, steel plate was polished up to 1200 µm grit
paper followed by blasting with 0.7 to 0.8 mm steel balls to make the
surface rough for proper adhesion. The coating was deposited by
keeping the steel plate 20 cm away from the gun at 6 bars air pressure,
30 V voltage, and 200 mA current [29–31].
The coating thickness was measured by non-destructive Elc­
ometer456 (Japan, Tokyo) at three different locations and their average
value was considered as a result. The bond adhesion test of deposited
coating was measured according to KS F4716 standard [32] for four
different consecutive samples and their average was calculated for the
result. The bond adhesion measurement was performed by selecting 16
J.K. Singh et al.
cm2 area of the deposited coating.
2.2. Post-treatment of the coating
The post-treatment of the deposited Al coating was carried out with
nylon brush by dissolving 0.1 M NH4H2PO4+ 0.001 M CsNO3 (CN1), 0.5
M NH4H2PO4+ 0.0025 M CsNO3 (CN2) and 1 M NH4H2PO4+ 0.005 M
CsNO3 (CN3) in distilled water to reduce the porosity and enhance the
corrosion resistance properties in the aggressive environment. The pH of
respective treatment solutions i.e. CN1, CN2 and CN3 was found to be
4.36, 4.23 and 4.16 at 20 (±1)◦ C, respectively. The treatment of Al
coating was carried out for 24 hours at every 8 hours of interval (3 times
in 24 hours) subsequently kept in humidity chamber at 50 ◦ C and 95%
relative humidity for 7 days. The treated samples were kept in humidity
chamber to react the Al with treatment solutions and form composite
oxides to fill the defects/pores of the coating. The treated coating was
retrieved from humidity chamber after 7 days of keeping in humidity
chamber and then further characterization was performed.
2.3. Characterization of the coatings and corrosion products
The surface morphology of as coated (AC), treated coatings and
corrosion products was characterized by scanning electron microscopy
(SEM, MIRA3, TESCAN, Brno, Czech Republic) operated at 15 kV and
elemental analysis by energy-dispersive X-ray spectroscopy (EDS). The
porosity of AC and treated coatings was determined by ImageJ software
(version 1.52n).
The phases formed in the AC, treated coatings and corrosion prod­
ucts was accomplished by X-ray diffraction (XRD, Rigaku, Tokyo, Japan)
using Cu Kα radiation (λ = 1.54059 Å) generated at 40 kV and 100 mA.
The volume fraction (%) of each phases was determined by JADE2016
software.
2.4. Corrosion studies
The corrosion characteristics of AC and treated coating was per­
formed in artificial ocean water solution i.e. ASTM D1141 [28]. This
solution contains many aggressive ions such as Cl− , CO2− 2−
3 , SO4 and F
− CsNO3 which was not completely fill the pores/defects of coating thus,
which influence the corrosion reaction of coatings. The pH of artificial
ocean water solution was maintained up to 8.2 at 20 (±1)◦ C by adding
0.1 M NaOH solution. The electrochemical experiments of the samples
were performed by three electrode system where the treated/coated
samples act as the working electrode (WE), platinum wire as the counter
electrode (CE) and silver-silver chloride (Ag/AgCl) as the reference
electrode (RE). The electrochemical impedance spectroscopy (EIS) was
performed at open circuit potential (OCP) by VersaSTAT potentiostat
(Princeton Applied Research, Oak Ridge, TN, USA) from 100 kHz to 0.01
Hz with a 10 mV sinusoidal voltage. The potentiodynamic polarization
was performed by changing the impressed current from -0.4 V to +0.8 V
Vs Ag/AgCl at a 1 mV/sec scan rate. The analysis of the obtained data
was performed by Metrohm Autolab Nova 1.10 software.
3. Results and discussion
3.1. Characterization of coating
3.1.1. Coating thickness and adhesion measurement
The average thickness of the deposited coating is found to be 100
(±5) µm by measuring at three different locations using nondestructive
Elcometer456. The average bond adhesion of 100 (±5) µm thick Al
coating deposited by arc thermal spray process is obtained to be 4.86
(±0.08) MPa. The bond adhesion value of Al coating deposited by arc
thermal spray process in present study is greater than as recommended
in ISO 2063-1 [33]. In ISO 2063, the bond adhesion of Al coating
deposited by thermal spray process is reported to be 4.5 MPa which is
lower than present study value. However, the bond adhesion value of
3
Surfaces and Interfaces 22 (2021) 100885
thermal sprayed Al coating can be increased more than 4.5 MPa, if the
coating thickness is increased greater than 100 µm [34].
3.1.2. SEM analysis
Corrosion is the surface phenomenon, thus, it is necessary to study
the morphology of coatings by SEM. The top surface morphology of
coatings is shown at 1,000X and 10,0000X in Figs. 1 and 2, respectively.
Fig. 2 is the respective image marked by square red color in Fig. 1 at
higher magnification. The cross sectional SEM images of the coatings are
shown in supporting Fig. 1 (Fig. S1). From cross sectional images, it can
be seen that AC samples (Fig. S1 a) exhibited around 100 (+3) µm
thickness which is in good agreement with Elsometer456 measurement.
However, as the post-treatment is performed, the coating thickness is
slightly higher (Fig. S1 b-d) attributed to the formation of composite
oxide films. From Figs. 1a and 2a it can be seen that AC sample exhibits
severe defects, porosity, inflight and splats particles onto the surface
attributed to the sudden cooling of melted metal particles whereas once
the post-treatment of deposited Al coating was accomplished with
different concentrations of NH4H2PO4 and CsNO3, they show improve­
ment in the morphology. In Figs. 1a and 2a, the white deposition is
inflight particles around 1-10 µm whereas chunk morphology exhibited
the splats particles around 50 µm and defects as well as pores are found
all over the surface. The pores and defects are in deep which are very
perilous for corrosion. Through the pores, the aggressive ions and so­
lution pierce and causes the severe corrosion of the coating as well as
substrate too. If the coating thickness is high then the penetration of
solution can be reduced but in low thickness coating, it may corrode
early and the service life of the structure would be decreased. CN1
sample shows compact and dense morphology (Fig. 1b) attributed to the
reaction of treatment solution and Al metal which fill out the porosity of
coating by forming composite oxides result in slight increment in
thickness. The particles size of the coating reduced compared to AC and
found to be around 10-20 µm attributed to the formation of composite
oxides. These oxides are looks as needle, elongated and attached to each
other. Thus, the diameter of needle particles is found around 1-2 µm but
the length is around 5-10µm. However, at the periphery it shows few
pores (Fig. 1b and 2b) owing to less concentration of NH4H2PO4 and
there would be some possibility to cause the corrosion in aggressive
environment. But, once the concentration of NH4H2PO4 and CsNO3 is
increased i.e. CN2 (Fig. 1c) and CN3 (Fig. 1d), they show agglomeration
and dense morphology which cover the coating surface and reduce the
porosity of deposited coating. After the post-treatment of the Al coating,
the composite oxide particles are petal like having around 5-10 µm size
which uniformly covered all over the surface and make the coating
surface defects free (Fig. 2c). Once the amount of NH4H2PO4 and CsNO3
is increased up to 1 M and 0.005 M, respectively i.e. CN3 exhibits
smaller and thin composite oxide particles (Figs. 1d and 2d) which
causes space between two particles therefore, there will be a possibility
to ingress the aggressive ions result in enhancement in deterioration of
coating. The particles of composite oxides are elongated and needle like.
The dimension of composite oxides is around 1 µm in diameter and 5 µm
in length. However, crack is observed in CN2 (Fig. 1c) and CN3 (Fig. 1d)
at the periphery of coating surface attributed to the formation of brittle
composite oxide film [24] which allow to penetrate the solution.
The porosity of the coating was determined by ImageJ software at
lower magnification SEM images and found to be 47, 27, 16 and 12% for
AC, CN1, CN2 and CN3, respectively. As the amount of treatment so­
lution is increased, the porosity is decreased. The highest porosity is
found by AC attributed to the process of coating. However, it is signif­
icantly reduced by 42.55, 65.96 and 74.47% for CN1, CN2 and CN3
compared to AC, respectively.
The chemical analysis of the coating is determined by EDS and the
results are shown in Table 1. From this table it can be seen that AC
sample contain only 2.85% oxygen (O) and rest of Al. The O content is
very less and it might be coming from atmosphere. This result suggests
J.K. Singh et al.
Fig. 2. SEM images of (a) AC, (b) CN1, (c) CN2 and (d) CN3 at 10,000X.
that the coating deposited by arc thermal spray process does not show
oxidation of the coating. As the concertation of NH4H2PO4 and CsNO3 is
increased, O, P, N and Cs amount increased. This result suggests that
these elements came from the treatment solution and some composite
oxide has been formed on the coating surface. Thus, it is required to
analyze the phases formed onto the coating surface by XRD. In subse­
quent paragraphs XRD results are discussed.
3.1.3. XRD analysis
The phases formed onto the AC and treated Al coating surface is
determined by XRD and results are shown in Fig. 3. The XRD results
shown in Fig. 3a reveal the presence of Al, caesium aluminum oxide
(Cs2Al2O3: CAO) and ammonium aluminum hydrogen phosphate hy­
drate ((NH4)3Al5H6(PO4)8.18H2O: AHP) in treated coating [24] while
AC sample exhibits only Al. The formation of CAO and AHP is described
in Eq. (1).
7Al + 8NH4 H2 PO4 +2CsNO3 +22H2 O + 3e− →(NH4 )3 Al5 H6 (PO4 )8 .18H2 O + Cs2 Al2 O3 +7NH4 OH + 3H+
AHP CAO
Al react with treatment solution i.e. NH4H2PO4 and CsNO3 and form
AHP as well as CAO as composite oxide film which fill the porosity of the
Al coating deposited by arc thermal spray process. Moreover, due to the
intense peak of Al, the low intensity peaks of AHP and CAO are sup­
pressed at lower scan range. Thus, the XRD results are re-plotted in
Fig. 3b from 2θ=10-30◦ . The XRD result of AC sample suggests that there
is no phase transformation after deposition of Al coating by arc thermal
spray. Generally, most of the thermal spray coating processes attributed
4
Surfaces and Interfaces 22 (2021) 100885
oxidation of coating which decrease the properties of coating. But, there
is no oxidation of Al coating occurred after deposition by arc thermal
spray process. This result corroborates the EDS analysis where only
2.85% O present which is not able to form Al2O3 film and detected by
XRD. There is possibility that film is very thin and beyond the limitation
of XRD to detect the oxide phase. It can be seen from Fig. 3a that the Al
peak is very intense and well define in AC sample but once the post-
treatment is performed, this peak becomes broad as well as intensity is
decreased. It is attributed to the participation of AHP and CAO phases as
observed in Fig. 3a and b.
The volume fraction (%) of composite oxides are determined by
JADE software built in XRD instrument and the results are shown in
Table 2. It can be seen from this table that AC sample contain 100% Al
which suggests that there is no phase transformation of Al during
coating process. However, as the concentration of NH4H2PO4 and CsNO3
are increased, the volume fraction of AHP is increased while Al is
decreased. AHP is highly acidic and brittle in nature, thus, CN3 sample
shows cracking in coating as observed in SEM images (Figs. 1d and 2d).
(1)
However, CN2 contain higher volume fraction of CAO compared to
other treated coatings. The CAO is sparingly soluble and thermody­
namically stable. Due to high amount of NH4H2PO4 compared to CsNO3
in CN3, greater AHP has formed.
3.2. Corrosion studies
3.2.1. EIS with exposure periods in artificial ocean water
The corrosion characteristics of coatings are performed in artificial
ocean water with exposure periods and the EIS results are shown in
J.K. Singh et al. Surfaces and Interfaces 22 (2021) 100885

Table 1 impedance is observed compared to CN2 and CN3.

EDS analysis (wt.%) of coatings. As the exposure periods are increased up to 6 d, the magnitude of
Sample ID Elements (wt.%) complex-plane impedance of all samples increased attributed to the
O P N Cs Al owing to self-healing process of coating by deposition of corrosion
AC 2.85 0.00 0.00 0.00 Balance products in pores/defects [12]. The trend in magnitude of impedance
CN1 12.48 7.63 5.24 0.10 Balance plots for the all samples are identical as obtained after 1 h of exposure.
CN2 37.51 19.96 6.15 0.12 Balance There is small tail at lower studied frequency and big semi-circle from
CN3 39.47 26.01 7.36 0.13 Balance high to middle frequency ranges observed which reveal that corrosion
process is occurred by dissolution of coating and deposition of corrosion
Figs. 4–6. The complex-plane impedance plots of coatings after 1 h of products simultaneously. Therefore, it is necessary to know the corro­
exposure in artificial ocean water solution are shown in Fig. 4a. It can be sion characteristics of coatings at extended exposure periods. It is found
seen from this Fig. that AC sample exhibited lowest in magnitude of by SEM images (Figs. 1 and 2) that CN1 has some porosity while CN2
complex-plane impedance compared to treated coatings owing to the and CN3 exhibit cracking owing to the formation of greater amount of
presence of heavy defects/pores and inflight particles onto the surface AHP film. Thus, there is possibility to dissolve the AHP film at prolonged
which enhances the deterioration of coating and allow to ingress the exposure periods and decrease the corrosion resistance properties of the
solution. The defects/pores work as active site (anode) and profoundly coatings.
activate the corrosion reaction, thus, lower in magnitude is found. Fig. 4c shows the complex-plane impedance plots of coating after 37
However, once the post-treatment was applied onto the Al coating, the days of exposure in artificial ocean water solution. It can be seen from
porosity is decreased. Thus, higher in magnitude of complex-plane this Fig. that there is no improvement in magnitude of complex-plane
impedance is observed. CN2 exhibited higher in magnitude owing to impedance of CN1 and CN3 samples while AC and CN2 increased
the formation of greater amount of CAO (Table 2) onto the surface which dramatically. This result suggests that CN1 and CN3 neither improve nor
inhibit the ingress of solution and protect the coating from corrosion. decrease the corrosion resistance properties of coating but remain
CN3 exhibited lower in magnitude compared to CN2 attributed to the consistent. CN1 sample has not completely fill the porosity of coating
higher amount of acidic film i.e. AHP and cracks onto the coating surface while CN3 exhibit cracks and high amount of AHP which dissolved and
which influences the corrosion reaction while in case of CN1, some transformed into another phases. But, simultaneously the corrosion
defects/pores are still present after post-treatment which influences the products are deposited onto the surface. Moreover, there is possibility
deterioration of coating, thus, lower in magnitude of complex-plane that these corrosion products are not stable and uniform. On the other
hand, AC sample initially enhances the corrosion reaction owing to the
many active sites (defects/pores) result in dissolution of coating and
formation of heavy corrosion products which fill out the pores/defects
significantly but it requires some time i.e. 37 days to uniformly deposit
the corrosion products onto the surface. This exposure period is signif­
icant to dissolute the coating and simultaneously deposit the stable
corrosion products onto the surface and pores/defects of coating. These
corrosion products fill the porosity of coating and uniformly distributed
onto the surface which stifle the ingress of solution. Thus, the higher in
magnitude of complex-plane impedance (Fig. 4c) is observed compared
to CN1 and CN3. However, CN2 sample exhibited highest in magnitude
of complex-plane impedance attributed to the presence of greater
amount of CAO as complex oxide after post-treatment of Al coating
whereas AHP film start to dissolve and transformed into stable phases.
Thus, the highest in complex-plane impedance is observed. In this case,
synergistic effect is caused by AHP film which transformed into another
phase while CAO itself is protecting the coating from corrosion.
As the exposure periods are extended up to 65 days, the magnitude of
complex-plane impedance is increased for all samples attributed to the
formation of corrosion products as shown in Fig. 4d. There is an inter­
esting observation found that the magnitude of complex-plane imped­
ance of CN1 is higher compared to CN3 compared to earlier exposure
periods owing to the filling of porosity by corrosion products. CN3
contain highest amount of AHP which dissolve and maintain the resis­
tance for corrosion. This finding suggests that CN3 neither improve nor
deteriorate but maintain the properties while AC and CN1 samples
deteriorate but subsequently fill out the porosity by corrosion products
result higher in magnitude. On the other hand, CN2 has formed highest
amount of CAO which initially provide protection whereas AHP

Table 2
Volume fraction (%) of phases formed on the coatings.
Sample ID Volume fraction (%)
AHP CAO Al

AC 0.00 0.00 100

CN1 2.30 4.04 93.66
CN2 30.18 9.13 60.69
CN3 40.71 7.02 52.27
Fig. 3. XRD of coating from (a) 2θ=10-90◦ and (b) 2θ=10-30◦ .

5
J.K. Singh et al.
deteriorates and transformed into another phase result in two phe­
nomena for protection. At longer duration of exposure, AHP completely
transformed into stable corrosion products which significantly cover the
surface as well as CAO and improve the corrosion resistant properties of
coating at longer duration of exposure.
The total impedance of coating with exposure periods are shown in
Fig. 5. AC samples exhibited lowest in impedance attributed to the
presence of many active sites (pores/defects) which influences the
corrosion while CN2 shows highest in impedance values at 0.01 Hz
(Fig. 5a). The post-treated coatings show greater in impedance values
owing to the filling of pores/defects by composite oxides i.e. AHP and
CAO. However, once the exposure periods of coatings are increased in
artificial ocean water up to 6 days, the total impedance values of all
samples are gradually increased as shown in Fig. 5b owing to the
deposition of corrosion products onto the surface. In case of AC sample,
initially coating enhances the corrosion reaction owing to the presence
of active sites but once the exposure periods are extended, the corrosion
products simultaneously deposited into the defects/pores which reduce
the active sites resultant increase in impedance values. Moreover, the
treated coating exhibited AHP as well as CAO film where AHP is acidic in
nature and started to dissolve and transformed into another phases
therefore, there is possibility to deteriorate the coating at faster rate but
at the same time CAO film at the coating surface reduces the deterio­
ration. Due to the presence of CAO film, the coating exhibited protection
and the corrosion products of AHP film deposit onto the coating surface,
thus, impedance is increased up to 6 days of exposure. As the exposure
periods are increased up to 37 days, the total impedance values are
increased (Fig. 5c). There is not ample increment in total impedance
values of CN1 and CN3 compared to 6 days of exposure while AC and
Fig. 4. Complex-plane impedance plots of coating after (a) 1 h, (b) 6 d, (c) 37 d and (d) 65 d of exposure in artificial ocean water solution.
6
Surfaces and Interfaces 22 (2021) 100885
CN2 increased significantly. In case of AC sample, the impedance is
increased owing to the greater filling ability of pores/defects by corro­
sion products. Initially AC samples corroded very fast but as the expo­
sure periods are increased, the dissolution of coating decreased
attributed to the deposition of corrosion products onto the surface.
Nevertheless, the active surface area is decreased resultant increase in
total impedance values. CN1 is found to be lowest in total impedance
values among all samples after 37 days of exposure attributed to the
presence of defects/pores on surface (Fig. 1b) as well as presence of AHP
film which make the surface brittle and acidic while CN3 contain highest
amount of AHP which make the solution acidic result in deterioration of
coating. But, subsequently, CAO protect the surface from corrosion and
AHP transformed into another phase. CN2 exhibited highest in imped­
ance attributed to the formation of uniform, regular and composite ox­
ides film. AHP dissolved and transformed into another form but CaO
provides the protection. The transformed corrosion products and CAO
both are present onto the coating surface. Thus, barrier type of protec­
tion is exerted by the corrosion layer. But, as the exposure periods are
extended up to 65 days from 37 days, the total impedance values of CN1
and CN3 at 0.01 Hz are remained constant but AC sample increased
might be owing to uniform deposition of stable and uniform corrosion
products (Fig. 5d). The highest impedance values are observed by CN2
attributed to the deposition of uniform, stable and thick corrosion
products which stifle the ingress of solution. CN3 samples exhibit the
lowest impedance values owing to the dissolution of AHP film result in
studied solution become acidic. On the other hand, CN1 sample shows
higher in impedance compared to CN3 might be owing to the less
amount of AHP film onto the surface which easily dissolved and trans­
formed into another phases. Due to lowest amount of AHP in CN1, it is
J.K. Singh et al.
not able to make the solution acidic while during corrosion process, the
corrosion products deposited onto the surface result in higher imped­
ance values compared to CN3 after 65 days of exposure.
The phase-frequency Bode plots of coting samples immersed in
artificial ocean water with exposure periods are shown in Fig. 6. It can
be seen from Fig. 6a that all treated samples shifted the phase angle
maxima at higher angle from high to middle frequency ranges while AC
shifts at low angle. It is attributed to the formation of composite oxide
film after treatment [25] whereas AC sample contain defects which
possesses capacitive properties. At the highest studied frequency i.e. 100
kHz, the phase angle of CN2 sample is found to be highest among all
samples which infers that barrier type of protection exerted by CAO film
[35-38]. As the exposure periods are increased up to 6 days, the phase
angle at highest and lowest studied frequencies of all samples found to
be about to identical as shown in Fig. 6b owing to the corrosion phe­
nomena is controlled by corrosion products. In treated coating, the
treatment film started to dissolved and transformed into the other form
as corrosion products while due to the greater in active sites of AC
samples, initially formed corrosion products deposit into the por­
es/defects of the coating. AC sample shows asymmetric peak on 40 Hz at
-45◦ reveal the deterioration of coating whereas CN2 samples cover
broader ranges of studied frequency followed by CN3 and CN1 owing to
the formation of protective film. As the exposure periods is extended up
to 37 days (Fig. 6c), AC samples slightly shifted phase angle towards
higher side in middle frequency and the asymmetric peak become broad
which infer that corrosion products cover the active sites of coating and
reduce the surface area of coating resultant increased in impedance
value (Fig. 5c). However, CN2 samples show the broadening in phase
angle from 2000 Hz to 0.25 Hz in between -38◦ to -51◦ which reveal that
Fig. 5. Modulus-frequency Bode plots of coating after (a) 1 h, (b) 6 d, (c) 37 d and (d) 65 d of exposure in artificial ocean water solution.
7
Surfaces and Interfaces 22 (2021) 100885
surface being strengthened by the corrosion products and cover the
surface uniformly. CN1 sample shows the asymmetric peak at -55◦ on 92
Hz which divulge the deterioration of coating. CN3 sample exhibits the
lower in phase angle compared to CN1 but the broadening in peak from
8912 Hz to 0.73 Hz which confirm that the corrosion products are
providing the protection and uniformly cover the surface and stifle the
ingress of aggressive ions towards coating surface. At highest (100 kHz)
and lowest (0.01 Hz) studied frequencies, CN2 and AC samples exhibited
higher in phase angle maxima shift owing to the corrosion products and
coating itself compared to CN1 and CN3, respectively. At lowest studied
frequency, CN2 is found the phase angle shift at -19◦ which is highest
followed by AC, CN3 and CN1. This result corroborates with total
impedance value at 0.01 Hz where CN1 samples show lowest in its value
(Fig. 5c). As the exposure periods reached at 65 days, the broadening in
maxima shift of CN2 sample from 1039 Hz to 0.42 Hz around -50◦
(Fig. 6d) confirm that coating is being protected by corrosion products
and cover all over the surface uniformly and strengthen the film. Thus,
the highest in impedance is observed after 65 days of exposure (Fig. 5d).
AC sample is also showing identical characteristics as observed by CN2
but the phase angle maxima shift is lower i.e. around -48◦ which infer
that corrosion products are providing the protection against deteriora­
tion rather than coating. This finding can be corroborated with the phase
angle maxima shift on 100 kHz where it is found at -19◦ attributed to the
corrosion products which provide barrier for corrosion reaction. CN3
sample shows the lowest in phase angle maxima shift at middle as well
as lowest studied frequency which reveal that surface is deteriorating
owing to the acidic in nature of AHP film which enhances the corrosion
at longer duration of exposure. CN1 sample shows identical phase angle
at middle frequency as observed after 37 days of exposure but at lowest
J.K. Singh et al. Surfaces and Interfaces 22 (2021) 100885

Fig. 6. Phase-frequency Bode plots of coating after (a) 1 h, (b) 6 d, (c) 37 d and (d) 65 d of exposure in artificial ocean water solution.

studied frequency, it is shifted towards higher angle i.e. -14◦ (Fig. 6d). and constant phase element for charge transfer, respectively. The first
The shifting of phase angle maxima at higher angle on 0.01 Hz reveal time constant from high to middle frequency is associated to corrosion
that coating is providing protection. Initially, the protection to the products which exerted barrier types of protection whereas the second
coating is provided by treatment film i.e. AHP and CAO while at longer time constant is associated for coating/treatment (top) layer from
duration of exposure by corrosion products and coating simultaneously. middle to low frequency. Initially, coating/treatment layer come in
In the case of AC sample at longer duration of exposure, the protection is contact to solution, thus, corrosion has started at
provided by corrosion products while CN2 sample by corrosion products coating/treatment-solution interface while in the meantime, corrosion
as well as coating surface simultaneously, thus, highest in impedance is products deposit onto the coating surface and provided the protection.
observed from initial periods of exposure to 65 days. After best fitting of EIS in suitable EEC, CPE coefficient (Qeff) could be
The suitable electrical equivalent circuit (EEC) to fit the EIS data is derived on the basis of imaginary impedance (Zj) when CPE exponent (n)
shown in Fig. 7. It can be seen from this Fig. that all EIS data is fitted in = 1, by Eq. (2) [43]:
∕
one EEC with two times constant at high to middle and middle to lower (nπ) − 1
studied frequencies [39–42]. In this EEC, Rs, Rc/t, CPEc/t, Rct and CPEct Qeff = sin (2)
2 Zj (f )(2πf )n
corresponds to solution resistance, resistance of coating/treatment,
constant phase element of coating/treatment, charge transfer resistance
where f is frequency. But, once n become 1 then Qeff becomes a capac­
itance (Ceff), therefore, Eq. (2) can be written as:
− 1
Qeff = Ceff (3)
Zj (f )(2πf )

However, it is not possible to n become 1 due to the heterogeneity on

the surface of coating/treatment surface where corrosion would start
once exposed to solution. Therefore, the blocking characteristics of the
coatings/treatments surface by corrosion products between the inter­
facial capacitance and CPE coefficient (Q) can be calculated by Brug’s
equation [44] and others [45,46]:

Ceff = Q1/n RS (1− n)/n

(4)

The electrochemical parameter after fitting of EIS plots in suitable

Fig. 7. EEC of coatings exposed in artificial ocean water solution at different EEC is shown in Table 3 and Fig. 8. The Rs values of coatings at different
exposure periods.

8
J.K. Singh et al. Surfaces and Interfaces 22 (2021) 100885

Table 3 but once the exposure periods are increased, this value gradually
Electrochemical parameters of coatings exposed in artificial ocean water solu­ decreased as well as nc value increased (Table 3). The nc value of AC
tion at different exposure periods. samples after 65 days of exposure is found to be 0.59 which suggests that
Sample Time Electrochemical parameters coating is still heterogeneous whereas Qt value of CN2 samples is found
ID Rs (Ω. CPEc/t Rct CPEct to be lowest from 1 h to 65 days of exposure (Table 3). The Rct and nct
cm2) Qc/t (1 × nc/t (kΩ. Qct (1 × nct values of all samples with exposure periods are increased and Qct is
10− 5) cm2) 10− 5)
decreased. The nct value of CN2 samples after 65 days of exposure is
(Ω− 1. (Ω− 1.
cm− 2.s− n) cm− 2.s− n) found to be 0.75 which infer that corrosion products are homogeneous
and cover all over the surface. In this case, treatment film as well as
AC 1h 23.45 17.60 0.52 0.67 31.10 0.55
CN1 9.03 14.50 0.54 0.74 27.70 0.56 corrosion products both participating in corrosion reaction. Thus, best
CN2 14.59 2.74 0.62 0.83 17.86 0.60 corrosion resistance performance is shown by CN2 sample.
CN3 19.26 3.70 0.60 0.80 23.30 0.58
AC 6d 24.77 15.80 0.53 1.09 26.40 0.59 3.2.2. Potentiodynamic polarization after 65 days of exposure in artificial
CN1 19.07 15.10 0.53 1.35 24.30 0.62
ocean water
CN2 18.60 1.30 0.64 1.55 14.30 0.68
CN3 21.22 10.10 0.56 1.44 22.90 0.60 The potentiodynamic polarization of coatings exposed in artificial
AC 37 d 21.39 9.20 0.56 2.15 20.30 0.66 ocean water solution after 65 days are shown in Fig. 9. It can be seen
CN1 16.63 18.96 0.52 1.45 23.80 0. from Fig. 9 that CN1 and CN3 samples exhibited higher cathodic current
62
density whereas AC and CN2 are found to be least. An interesting
CN2 26.22 0.86 0.67 3.25 9.91 0.72
CN3 23.40 14.40 0.53 2.04 21.30 0.66 observation can be seen after corrosion potential (Ecorr) of the coating
AC 65 d 26.44 4.30 0.59 4.00 8.20 0. where anodic current density of CN1 and CN3 samples are abruptly
73 increased suggesting that these coatings possesses pitting corrosion
CN1 14.53 16.28 0.52 3.16 10.20 0.70 whereas AC and CN2 samples exhibited passive region. The anodic
CN2 15.00 0.61 0.69 4.20 5.36 0.75
current density of AC and CN2 samples increased gradually after Ecorr
CN3 27.86 16.51 0.51 2.70 18.13 0.69
attributed to the formation of stable, protective and uniform corrosion
products. The AC sample exhibited limiting current at 6.41 mA.cm− 2
exposure periods in artificial ocean water is found to be in between 9 to from -0.720 to -0.224 V vs Ag/AgCl while treated coatings do not show
28 Ω.cm2 (Table 3). This value is very less and does not participate such behavior. The limiting current tendency in AC sample is attributed
significantly in overall impedance. It can be seen from Fig. 8 that the Rc/t to the deposition of thick corrosion products onto the coating surface
values of AC and CN2 samples are gradually increased with exposure which causes resistance for penetration of solution [47].
periods while CN3 is almost constant. CN1 sample initially up to 37 days It can be seen from Fig. 9 that all coatings exhibited Ecorr value
of exposure is decreased but once the duration is increased, Rt is greater than -0.870 V vs Ag/AgCl which infer that coatings are providing
increased. The Ceff of AC sample after 1 h of exposure is found to be the sacrificial protection to the steel [48]. AC sample shows -1.177 V vs
highest attributed to the highly defective coating but once the exposure Ag/AgCl which suggests that this coating is deteriorating until 65 days
periods are increased, it is decreased. CN2 samples show lowest in Ceff of exposure in artificial ocean water solution even though corrosion
value with exposure periods attributed to the deposition of uniform products are deposited. There is possibility that thick corrosion products
treatment film as well as once the exposure periods are increased, the have formed but these are porous where chances for penetration of so­
corrosion products are less defective, thus, the highest impedance is lution is significant. The corrosion phenomena are controlled by thick
observed in all exposure periods. corrosion product which can be confirmed by morphology of corrosion
The Qc of the AC sample is found to be highest after 1 h of exposure products. In subsequent paragraph, the SEM of corrosion products are

Fig. 8. Rc/t and Ceff plots of coatings exposed in artificial ocean water solution at different exposure periods.

9
J.K. Singh et al. Surfaces and Interfaces 22 (2021) 100885

Fig. 9. Potentiodynamic polarization plots of coatings after 65 day of exposure in artificial ocean water solution.

Fig. 10. SEM images of (a) AC, (b) CN1, (c) CN2 and (d) CN3 after potentiodynamic polarization studies exposed in artificial ocean water solution.

10
J.K. Singh et al. Surfaces and Interfaces 22 (2021) 100885

Table 5
Volume fraction (%) phases of corrosion products formed after 65 days of
exposure in artificial ocean water solution.
Sample ID Volume fraction (%)
AHPH α-Al(OH)3 NaCl Al

AC 0.00 8.83 19.44 71.53

CN1 6.96 2.36 14.97 75.70
CN2 9.74 8.61 14.65 67.00
CN3 8.69 7.50 35.08 48.73

Fig. 11. XRD of corrosion products from (a) 2θ=10-90◦ and (b) 2θ=10-30◦
formed after 65 days of exposure in artificial ocean water solution.
discussed. CN1 and CN3 are at boundary line where their Ecorr are found
to be -0.901 and -0.872 V vs Ag/AgCl, respectively. It means these
treatments could not provide sacrificial protection to the steel substrate
if the exposure periods are extended beyond 65 days. It is attributed to
the severe dissolution of treated film where solution can penetrate and
causes steel corrosion.
3.3. Characterization of corrosion products
The morphology of corrosion products by SEM are shown in Fig. 10.
The AC samples show thick and agglomerated net like morphology
(Fig. 10a) which contain micro and nano pores as well as some space
between two corrosion particles. Due to the deposition of thick and
agglomerated corrosion products, AC samples exhibit higher corrosion
resistance compared to CN1 and CN3. On the other hands, the CN1
sample shows horizontal cracks as well as porous corrosion products
morphology (Fig. 10b) which are not able to resist the penetration of
aggressive ions, solution and moisture towards coating surface. Thus,
greater corrosion is observed compared to AC. CN2 sample deposits the
fine and globular corrosion products onto the coating surface without
any defects as shown in Fig. 10c, thus, protection is provided. However,
CN3 shows heavy cracks and porous morphology in corrosion products
(Fig. 10d) through which solution can penetrate and start the corrosion
of steel substrate. From this figure it can be seen that AC, CN1 and CN3
show heavy corrosion products deposition while CN2 exhibits less
amount of corrosion products. This finding suggests that the corrosion
process of AC, CN1 and CN3 samples are controlled by corrosion prod­
ucts while CN2 by treated film as well as corrosion products.
The EDS analysis of corrosion products are shown in Table 4. There
are many elements present in corrosion products owing to the solution
composition, corrosion products and treatment film. This result suggests
that corrosion products contain composite oxides. C, Na, Mg, Cl, K, Ca in
all samples are coming from solution composition (ASTM D1141) where
each element respective salt was dissolved in distilled water. The
amount of N, P and Cs in corrosion products of treated coating is
decreased owing to the dissolution of coating compared to after treat­
ment (Table 1). Cs is very less amount in corrosion products of treated
coating.
The nature of corrosion products formed onto the coating surface
was determined by XRD after 65 days of exposure in artificial ocean
water solution. The XRD pattern of corrosion products formed onto the
coating surface are shown in Fig. 11. From Fig. 11a it can be seen that all
samples exhibited Al and NaCl phases. Al comes from the coating
whereas NaCl from the ASTM D1141 solution where 24.53 g/l NaCl was
added in distilled water. NaCl was deposited onto the coating surface,
therefore, it was observed in corrosion products. However, at lower scan
angle i.e. 2θ=10-30◦ exhibited some small peaks which is suppressed by
highly intense peaks of Al and NaCl. Thus, it is replotted from 2θ=10-30◦
and results are shown in Fig. 11b. It can be seen from this Fig. that α-Al
(OH)3 (bayerite) is formed on all coatings while on treated coating
contain bayerite along with Al3(PO4)2(OH)3(H2O)5 (Aluminium hy­
droxide phosphate hydrate: AHPH) due to the transformation of AHP
during corrosion process [24]. The bayerite and AHPH are thermody­
namically stable and sparingly soluble.
The volume fraction (%) of each phases i.e. Al, NaCl, bayerite and
AHPH are calculated by JADE software and the results are shown in
Table 5. It can be seen from this table that the corrosion products formed
onto CN2 sample contain highest amount of AHPH as well as second
highest bayerite among all sample and accountable for reduction in
corrosion. It can be seen that the corrosion products formed onto the
CN3 sample mostly contain NaCl attributed to the affinity of AHP film
with NaCl thus, severe corrosion is shown by this coating (Fig. 10d). AC
sample contain 8.83% bayerite which is highest among all sample thus,

Table 4
EDS analysis of corrosion products formed after 65 days of exposure in artificial ocean water solution.
Sample ID Elements (wt.%)
C N O Na Mg P Cl K Ca Cs Al

AC 5.23 0.00 48.57 2.23 1.57 0.00 3.62 0.40 1.22 0.00 37.16
CN1 8.60 1.62 29.01 1.75 0.80 4.53 4.81 0.47 1.28 0.04 47.09
CN2 7.48 2.02 40.05 0.89 0.50 8.14 6.63 0.35 0.97 0.06 32.91
CN3 6.43 2.66 44.08 0.51 0.15 13.68 8.44 0.29 0.46 0.09 23.21

11
J.K. Singh et al.
higher corrosion resistance is observed by this sample compared to CN1
and CN3.
4. Conclusions
From above results and discussion, it can be concluded that post-
treatment of Al coating deposited by arc thermal spray process with
NH4H2PO4 and CsNO3 has positive influence on morphology and
corrosion resistance. AC sample exhibited defects and pores whereas
once the coating was treated with NH4H2PO4 and CsNO3, the pores and
defects are filled uniformly and porosity is reduced dramatically from
47% (AC) to 12% (CN3). It was observed by XRD that treated coating
contain AHP and CAO as composite oxides. CN2 samples exhibited
highest Rt and Rct with exposure periods in artificial ocean water solu­
tion attributed to the treatment film and transformation of AHP into
stable and uniform corrosion products. The formation of Aluminum
Hydrogen Phosphate Hydrate (AHPH) and α-Al(OH)3 (bayerite) as
corrosion products onto the treated coating stifle the ingress of solution
therefore, enhancement in corrosion resistance is observed. The
morphology of corrosion products formed onto the CN2 samples after 65
days of exposure show compact and less porous while CN3 shows heavy
crack and porous morphology.
Authors’ contribution
Jitendra Kumar Singh: methodology, data curation, investigation,
formal analysis, writing-original draft and writing-review and editing.
Hyun-Min Yang: methodology, formal analysis, writing-original draft
and writing-review and editing. Han-Seung Lee: Conceptualization,
supervision, funding, writing-original draft and writing-review and
editing. Sumit Kumar: formal analysis, writing-original draft and
writing-review and editing. Fahid ASLAM: formal analysis, writing-
original draft and writing-review and editing. Rayed Lyousef: formal
analysis, writing-original draft and writing-review and editing. Hisham
Albduljabbar: formal analysis, writing-original draft and writing-
review and editing.
Declaration of Competing Interest
All authors declare that there is no conflict of interest.
Acknowledgements
This research was supported by basic science research program
through the National Research Foundation (NRF) of Korea funded by the
Ministry of Science, ICT and Future Planning (no. 2015R1A5A1037548)
and the Deanship of Scientific Research at Prince Sattam Bin Abdulaziz
University under the research project no. 2020/01/16810.
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.surfin.2020.100885.
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