Process Safety and Environmental Protection 141 (2020) 366–379

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Process Safety and Environmental Protection

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

Corrosion behaviour of Zn-Ni alloy and Zn-Ni-nano-TiO2 composite

coatings electrodeposited from ammonium citrate baths
Shams Anwar, Faisal Khan ∗ , Yahui Zhang
Centre for Risk, Integrity, and Safety Engineering (C-RISE), Faculty of Engineering & Applied Science, Memorial University, St. John’s, Newfoundland and
Labrador, A1B 3X5, Canada

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

Article history: Electrochemical and corrosion behaviour analysis of Zn-Ni alloy and Zn-Ni-nanoTiO2 composite coatings
Received 13 April 2020 electrodeposited on steel from ammonium citrate containing bath was performed. The complexation
Received in revised form 28 May 2020 of zinc and nickel ions in citrate stabilized the electroplating bath. The electrochemical behaviour of
Accepted 29 May 2020
samples showed that Zn-Ni alloy with the incorporation of 0.003 mol/l of titania (TiO2 ) nanoparticles
Available online 5 June 2020
exhibited noble corrosion potential (Ecorr ) and decreasing corrosion current (Icorr ). This leads to increase
impedance modulus with a more compact and durable uniform coating of 25.84 nm grain size. The
Keywords:
surface characterization and crystalline phase texture of the coatings were investigated by scanning
Electrodeposition
Zn-Ni-nanoTiO2
electron microscopy (SEM) integrated with energy dispersive spectroscopy (EDS) and X-ray diffraction
Corrosion prevention (XRD). The topographical structure of the coating was analyzed by atomic force microscopy (AFM). The
Process safety chemical composition result showed that the Zn-Ni+0.003TiO2 coating electrodeposited from a citrate
Loss prevention bath in various immersion tests reduced dezincification in the coating. The presence of higher intensity of
Impedance spectroscopy the ␥-phases (␥-NiZn3 ) (815) and ␥-Ni2 Zn11 (330) (631) plane orientation and ␤-Ti phase provide better
corrosion resistance performance of the coating. The most significant corrosion products for Zn-Ni alloy
electroplating are simonkolleite, hydrozincite, zincite, and wulfingite.
© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction Co-deposition of TiO2 (Myagmarjav et al., 2004; Fustes et al.,

Zinc coatings are broadly used to protect steel structures and
process equipment from corrosion. Significant efforts have been
achieved to increase the corrosion resistant properties of steel in
a harsh environment (Roev et al., 2001; Blejan et al., 2011). Zinc
coatings usually form alloys with metals i.e., iron (Fe), cobalt (Co),
and nickel (Ni) to use in the anti-corrosion purposes. According
to the research (Fratesi et al., 1997; Karahan and Güder, 2009),
Zn-Co, Zn-Ni, and Zn-Fe can improve the corrosion resistant prop-
erties in comparison to pure zinc coating. Currently, Zn-Ni alloy
coatings have become an important and eco-friendly alternative
to toxic cadmium coatings (Sriraman et al., 2013). A further alter-
native approach to increase corrosion resistance and mechanical
properties of the coatings is to introduce Zn-Ni composite coatings.
The inclusion of reinforcing particles can improve various proper-
ties of the alloy coatings such as dispersal toughening, oxidation
resistance at elevated temperatures, self-lubricity, wear resistance,
and anti-corrosion performance (Praveen and Venkatesha, 2011).
∗ Corresponding author.
E-mail address: fikhan@mun.ca (F. Khan).
2008; Momeni et al., 2016), Al2 O3 (Shourgeshty et al., 2019), ZrO2
(Vathsala and Venkatesha, 2011), SiO2 (Lotfi et al., 2018; Hammami
et al., 2012), Fe2 O3 (Kumar et al., 2012; Jin et al., 2016; Winand
et al., 2011) and SiC (Chen, 2002) explored on a Zn-Ni alloy was per-
formed to further enhance the corrosion resistance and mechanical
properties of the coating (Praveen and Venkatesha, 2011; Zhao
et al., 2014a; Blejan et al., 2011; Zhao et al., 2005; Makise et al.,
2018). Lotfi et al. (Lotfi et al., 2018) reviewed the studies con-
ducted on Zn-Ni alloy and Zn-Ni composite coating to observe the
effect of different parameters on electrodeposition. The Zn-Ni coat-
ing with SiO2 particles increased microhardness form 140 HV for
pure Zn-Ni comparison to 360 HV for the samples prepared by
SiO2 particles. It can also help to observed better polarization resis-
tance than pure alloy. When SiC is added to the Zn-Ni bath, then
no change is observed in the chemical composition of the phase,
only difference is that the orientation of crystal plates is changed.
Using ultrasonic power, the amount of the Al2 O3 co-deposition is
increased from 4.5–9.0 wt.% leading to an increase in the coatings’
corrosion-resistant and mechanical properties. The addition of par-
ticulates on the Zn-Ni surface refine the crystal size and shape,
which increase the corrosion resistance, microhardness, and wear
resistance properties (Momeni et al., 2016; Zhao et al., 2014b).

https://doi.org/10.1016/j.psep.2020.05.048
0957-5820/© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 S. Anwar et al. / Process Safety and Environmental Protection 141 (2020) 366–379
Among the nanomaterials considered titanium dioxide (TiO2 ) has
gained more attention in recent years. Successful results have been
reported on the co-deposition of TiO2 with Ni, Cu, Zn, and Ag metals
(Fustes et al., 2008).
Significant advancement has been made in various aspects of
the nanoscale materials because of the abundant availability of
nanoparticles, and they are mostly used in composite coatings
for achieving better corrosion resistant and mechanical proper-
ties. There are different types of titanium dioxide incorporated
in the Zn-Ni matrix that have been studied by several authors,
Vlasa et al. (Vlasa et al., 2010) reported two different types of TiO2 ,
Anatase and degussa incorporated with pure Zn. The anti-corrosion
behaviour of Zn-nanoTiO2 coating electropdeosited on steel surface
was analysed. It was specified that the pure zinc coating exhibited
lower corrosion resistant properties in comparison to the porous
nanocomposite coatings and this was significantly influenced by
the TiO2 texture and concentration. Kumar et al. (Punith Kumar
et al., 2012) prepared the composite coating with rutile (a mineral
composed primarily of TiO2 ) TiO2 nanoparticles (size ≤ 100 nm).
The impedance spectroscopy measurements found that the coat-
ings obtained from 6 g/l of rutile TiO2 nanoparticles (D2 ) showed a
higher impedance modulus relative to other coatings. It was con-
cluded that the Kumar et al. (Punith Kumar et al., 2012) successfully
deposited Zn-TiO2 composite coatings on mild steel from a bath
solution containing 2, 6, and 10 g/l of rutile TiO2 nanoparticles. The
percentage of TiO2 content in D2 provides a condensed and uni-
form surface to the D2 deposition. The decrease of the size was
expected to increase their catalytic activity and total surface area
(Myagmarjav et al., 2004). However, the authors found that the
study of titania TiO2 incorporated with the Zn-Ni alloy matrix has
not been explored.
The phase crystalline structure and morphology of the Zn-Ni-
TiO2 have been studied by Praveen et al. (Praveen and Venkatesha,
2011); they analyzed the effects and behaviour of TiO2 as com-
posites coating deposited on mild steel. The potential cathodic line
reduced the hydrogen reduction process and the corrosion rate. It
was deduced that Zn-Ni-TiO2 composite coating has a superior cor-
rosion inhibition property than the pure Zn-Ni alloy, while the steel
surface always possesses cracks, gaps, crevices, and micro holes.
Therefore, those gaps were filled by TiO2 and composite coating
dispersed on the metal.
Anwar et al. Anwar et al. (2018, 2019a) studied the constancy
of pure Zn and Zn-Ni alloy electroplating bath and found that the
addition of potassium citrate and EDTA in the plating bath extends
the precipitation of metal oxide (MO) to an elevated pH (from 2
to 5) and suppresses the formation of hydrogen evolution reaction
(HER). Zhang and Ivey Zhang and Ivey (2004) prepared the Co-Fe-
Ni plating bath by the addition of potassium citrate to stabilize the
plating bath and deposit uniform coating, inhibiting the precipita-
tion of metal hydroxide M(OH)2 at high pH. Based on those studies
on the citrate bath, it was found that citrate significantly increases
the stability of the bath and that denser plating’s are deposited, due
to higher bath pH. This was examined from the preceding this liter-
ature. There is limited information available on the Zn-Ni alloy and
Zn-Ni-nanoTiO2 composite coating deposited from ammonium cit-
rate baths, which helps to stabilize the bath and exhibits uniform
corrosion resistant coatings.
Pure zinc and zinc-nickel alloy exposed to the corrosive environ-
ment transformed the alloy into the dealloying and dezincification
(Stein et al., 1998; Sriraman et al., 2013). Dealloying is the selective
corrosion of one and more than one component of the material in
the alloy, and dezincification is the selective removal of zinc from
the alloy. One of the main reasons to increase the anti-corrosion
performance of the coated sample while immersing it in the cor-
rosive solvents is the formation of corrosion products. This was
evidence that the corrosion products act as a barrier against dif-
367
fusion, leading to a decrease in the corrosion rate of the coated
sample. The composition of the corrosion products layer has a sig-
nificant impact on the corrosion resistant properties of the Zn-Ni
alloys. The principal corrosion products in moisture environments
are zinc oxide (ZnO) and zinc hydroxide (Zn(OH)2 ) (Friel, 1986).
Moreover, due to the standard components of carbon dioxide in
the air, the appearance of smithsonite (ZnCO3 ) and hydrozincite
(Zn5 (CO3 )2 (OH)6 ) was feasible. Simonkolleite (Zn5 (OH)8 Cl2 .H2 O)
was the most favorable component formed in the hydrophilic
solution, and it contains high chloride (Cl− ) contents. However,
simonkolleite was thought to be an active-passive layer (Sriraman
et al., 2013; Bučko et al., 2011). Similarly, Anwar et al. Anwar
et al. (2020) reported the pitting corrosion mechanism of Zn-Ni
alloy exhibited several species, i.e. Zn2+ , ZnCl+ , Zn(OH)Cl, ZnO,
and Zn5 (OH)8 Cl2 may exist under present experimental condi-
tions. However, it could be the formation of a multilayer texture
of the passive layer on the sample surface. It was affirmed that the
corrosion resistant properties of Zn-Ni alloy electroplating were
dependent on the formation of corrosion products. Hence, it was
required to do the analysis and observe the corrosion product pro-
cess and the restraining effect of their film during the corrosion
mechanism.
As seen from the literature, several experimental analyses have
been carried out on Zn-Ni alloy and Zn-Ni-TiO2 with different oper-
ating settings. Few studies found systematically conducting the
Zn-Ni alloy and Zn-Ni-TiO2 composite coating deposited from an
ammonium citrate bath, which stabilizes the bath as a complex-
ing agent at optimum TiO2 molar concentration. Additionally, the
challenge of suppressing HER to enhance the corrosion resistant
performance of the coating has not been explored. This study also
considers the formation of corrosion products on the coated sam-
ples. Therefore, to fulfil this knowledge gap, research was needed
to find the optimum conditions for the Zn-Ni alloy and Zn-Ni nano-
sized titania TiO2 electrodeposited from an ammonium citrate bath.
2. Experiment details
Zn-Ni alloy and Zn-Ni-nanoTiO2 electroplated samples were
prepared at (20o C) room temperature in a 200 ml electrolyte
bath. A steel plate with the dimensions of 2.5cm × 4.0cm was
used as a working electrode. Before electrodeposition, the sub-
strate was ground with emery paper and polished with diamond
paste. The steel plates before electroplating were degreased by 10
% hydrochloric acid and 10 % sodium hydroxide for 5 min and then
rinsed with alcohol/acetone for a few seconds. The electroplating
current density ranged from 30−50 mA/cm2 for 15 min and agi-
tation speed was from 350−700 rpm. The auxiliary electrode was
graphite plate with dimensions of 2.5cm × 10cm, and a saturated
calomel electrode (SCE) (Hg/Hg2 Cl2 ) was used as a reference elec-
trode. After the electrodeposition, the samples were rinsed with
tap water and dehydrated with dry ambient air. The electrochemi-
cal and corrosion behaviour measurements were carried out in the
three-electrode cell setup in a glass cell employing ASTM G5-94
standards (Designation, 1999).
The nano-TiO2 size can be suspended stably in an aqueous Zn-Ni
salt electrolyte due to nano particles; if the particle size is larger, it
tends to sedimentation, and it is not easy to deposit uniform com-
posite films. The electroplating bath composition of Zn-Ni alloy and
Zn-Ni-nanoTiO2 composite coatings are shown in Table 1.
The purpose of the exploration tests was to make the factors and
levels approach an optimum electroplating condition. There were
four samples plated on same conditions, of which two samples
were used for morphology and two for electrochemical analysis,
to attain the redundancy and accuracy of the results. The electro-
chemical and corrosion measurements were accomplished using an
368 S. Anwar et al. / Process Safety and Environmental Protection 141 (2020) 366–379
Table 1
Bath compositions of citrate-based baths for the electrodeposition of Zn-Ni alloy and Zn-Ni-nanoTiO2 composite coatings.
Bath Compositions
Zinc Chloride (ZnCl2 )
Nickel (II) Chloride hexahydrate (NiCl2 .6H2 O)
Boric Acid (H3 BO3 )
Ammonium Chloride (NH4 Cl)
Sodium dodecyl sulfate (SDS)
Ammonium Citrate tribasic (N3 (C6 H17 O7 ))
Sodium chloride (NaCl)
Titanium dioxide (TiO2 )
IM6 electrochemical workstation (Zahner, Germany). The surface
morphological structures of the coatings were studied by SEM inte-
grated with EDS (FEI MLA 650 F). The topographical structures of
the coatings were inspected by AFM (Asylum research MFP 3D). The
crystal phase texture and peaks were investigated by XRD (Rigaku
Ultima IV X-ray diffractometer with a copper x-ray source) and a
material database was used to match the generated peaks by using
pdf # 03-065-5310 (Johansson et al., 1968) and pdf # 00-004-0831
(Nover and Schubert, 1980) RDB Minerals and ICDD.
The Debye-Scherrer equation was used to calculate the average
crystallite size of the coated samples from the peak width at the
half maximum of the crystal peaks (␤) (Patterson, 1939);
0.94
t =
ˇ.Cos
where t = crystallite size,
␭= wavelength of the XRD (␭ = 1.5406A◦ ),
␪ =Bragg’s angle of the peak and,
␤ = angular width of the peak at full width at half maximum
(FWHM).
2.1. Establishment of stable baths for Zn-Ni alloy and Zn-Ni
composite coatings
The negative reduction potential of the Zn/Zn2+ electrode is
more of a challenge for zinc to be electroplated than hydrogen
gas (Faid et al., 2017). The reduction potential of zinc is (EZn/Zn 2+
= -0.762 V) and hydrogen (E2H/H2 = 0.000 V). The H+ ions in the
electrolyte solution will be deposited before zinc, as H+ ions have
a more positive reduction potential under the standard state. To
overcome and modify this problem, the higher pH bath electroplat-
ing is preferable. Generally, a high pH bath (alkaline) is not stable.
Therefore, most of the electroplating is developed as an acidic bath.
The major problem of using an acidic bath is the hydrogen evolu-
tion reaction occurring in the electrolyte and that lead to developed
non-uniform less corrosion resistant coatings. To electrodeposit
Zn coatings with suitable composition and microstructure leads to
ideal corrosion resistance and mechanical properties. The develop-
ment of a stable plating bath with relatively high pH is vital. Alkalis
and complexing agents such as acetate, EDTA, and citrate were used
to stabilize the electroplating bath and suppress the hydrogen evo-
lution process on the cathode. These complexing agents were added
to the baths for pure Zn, Zn-Ni alloy and Zn-Ni composite coatings
to improve the anti-corrosion property, homogeneity, thickness,
compactness, and mechanical properties of the electroplated films
(Faid et al., 2017; Tomić et al., 2010; Jiang et al., 2005; Silva et al.,
2010; Garcia et al., 2014; Conde et al., 2011). The images for Zn-Ni
electrolyte prepared from non-citrate and citrate baths are shown
in Fig. 1. The electroplating bath prepared from non-citrate showed
precipitation and instability; the bath made from citrate showed
non-precipitation and uniformity throughout the electroplating
process. It increases the homogeneity and grain size and form a
Molar Concentration mol/l or M
Bath-1 Bath-2 Bath-3
0.550 0.550 0.550
0.105 0.105 0.105
– 0.161 0.161
0.46 0.46 0.46
0.00017 0.00017 0.00017
– 0.0816 0.163
0.171 0.171 0.171
– 0.0033, 0.0066, 0.0125
Bath pH = 2.0 Bath pH = 3.5 Bath pH = 4.0−4.5
denser deposition on substrate. Adding citrate also suppresses the
hydrogen evolution reaction and improves Zn-Ni corrosion resis-
tance behaviour. The Zn-Ni electroplating bath without citrate has
pH = 2.0, while the Zn-Ni bath with citrate has pH = 4.5. Increas-
ing the pH from 2.0 to 4.5 decreases the hydrogen concentration
in plating bath up to a hundred times. Thus, increasing the pH of
the electroplating baths will cause the suppression of the hydro-
gen evolution process on the working electrodes (Zn-Ni alloy and
Zn-Ni-nanoTiO2 composite).
2.2. Electrochemical and corrosion behaviour analysis
The electrochemical measurements and corrosion behaviour
analysis of the coated samples were conducted in the three-
electrode glass cell. The electroplated sample was a working
electrode, a graphite plate was an auxiliary electrode and a sat-
urated calomel electrode (SCE) was a reference electrode. At the
beginning of the analysis, the open circuit potential (OCP) was mea-
sured. The polarization curves were measured to be in the range of
−1.5 V to 0.5 V at a scan rate of 5 mV/s after 12 h, 24 h and 48
h immersion, respectively. An EIS was measured at the frequency
range of 105 Hz to 10−2 Hz with the amplitude of 10 mV. The coated
samples were immersed in lab scale seawater at the pH of 7.93 at
20 ◦ C for 12 h, 24 h and 48 h, respectively, and then electrochemi-
cal impedance spectroscopy (EIS) was carried out. The impedance
data was fitted using Thales simulation software and two similar
electroplated samples were measured for each level of the film.
The corrosion mechanism and the process of the zinc-nickel alloy
corrosion products compositions were discussed.
3. Results and discussion
3.1. Cyclic voltammetry (CV) analysis
The electrochemical behaviour of Zn-Ni alloy and Zn-Ni-
nanoTiO2 composite coatings were studied using a cyclic
voltammetry technique (shown in Fig. 2). The CV of the Zn-Ni
deposits was characterized by the presence of three peaks (a1 , a2
and a3 ) in an anodic scan and two peaks (c1 and c2 ) in a cathodic
scan. The positive scale of the potential corresponds to the anodic
dissolution of the electroplated samples (electrochemical oxida-
tion) in which the anodic peaks are seen, whereas the negative
scale of the potential represents the cathodic reduction of the elec-
troplated samples in which the cathodic peaks are seen. A ␥-phase
with the BCC textures are the most needed Zn-Ni alloy phase for
increasing the anti-corrosion properties of the coating in a high
percentage of chlorine containing saline seawater. There are three
anodic peaks for Zn-Ni alloy and Zn-Ni-nanoTiO2 deposits, corre-
sponding to the constituents of two-phase at ı-phase (Ni3 Zn22 )
and ␥-phase (Ni2 Zn11 ). The first and second anodic peaks con-
sist of the dissolution of zinc, starting from the ␦ and ␥-phase,
respectively. The third peak matches the dissolution of Ni from
 S. Anwar et al. / Process Safety and Environmental Protection 141 (2020) 366–379
Fig. 1. Electroplating bath images for (a) Zn-Ni from non-citrate and (b) Zn-Ni from citrate.
Fig. 2. Cyclic voltammogram of Zn-Ni and Zn-Ni-nanoTiO2 composite coating
deposited at a scan rate of 5 mV/s.
their phases (Basavanna and Naik, 2009; Kus et al., 2007; Tozar
and Karahan, 2014). Therefore, the voltammetry behaviour of the
coatings affirms the characteristics of the components and the tex-
ture of the deposited phase (Tozar and Karahan, 2014). The anodic
current density of Zn-Ni alloy coating is 4 mA/cm2 , while the Zn-
Ni-nanoTiO2 composite coating is 2 mA/cm2 . Therefore, Zn-Ni alloy
coating increases the dissolution rate in comparison to Zn-Ni-TiO2
deposits.
3.2. Atomic Force Microscopy (AFM) images
The topographical 3D images of the Zn-Ni alloy and composites
electroplated samples’ (a), (b), (c), (d) and (e) surfaces obtained by
AFM measurements are shown in Fig. 3. The cathodic deposition
of sample (a) is non-uniform, heterogeneous with a rough surface,
and a broad peak with large crystal grain size equal to 54.40 nm is
formed. In contrast, Zn-Ni alloy deposited from citrate bath exhibits
a uniform and more homogeneous surface with smaller grain size,
equal to 45.09 nm. Furthermore, the surfaces of the Zn-Ni-nanoTiO2
composite coatings are less rough than those of the Zn-Ni alloy
coatings. It can also be seen that the Zn-Ni-TiO2 coating deposited
from a citrate bath contains a regular surface, is less coarser, and
has a more compact and stronger nanosized uniform coating of
25.84 nm grain size, in comparison to the non-composite Zn-Ni
alloy coating, demonstrating that the Zn-Ni alloy with a citrate bath
shows smoothing ability with the addition of TiO2 nano-composite
particles. The TiO2 nanoparticles are adsorbed on the surface of the
zinc-nickel matrix and inhibit the depositions. Therefore, uniform
369
and smooth deposits can be observed (Hosseini et al., 2008). The
surface of the deposits shifts from a rough to a smooth surface, due
to the addition of composites particles and the inhibiting effects
during electroplating. In contrast, the surface roughness of Zn-Ni
alloy coating deposited from the non-citrate bath is greater than
that of the Zn-Ni alloy and Zn-Ni-nanoTiO2 composite coating from
citrate baths.
3.3. X-Ray diffraction (XRD) analysis
The XRD pattern of the Zn-Ni films prepared from three different
baths is shown in Fig. 4. It is noticed from the graphs that mainly
Zn-Ni coatings contain three dominant peaks, ␥-NiZn3 , Ni3 Zn22 and
␥-Ni2 Zn11 . The prominent peaks of the pure Zn-Ni coating with and
without citrate bath comprise 38, 43, 52 and 75 degree matches to
the ␥-NiZn3 , ␥-Ni2 Zn11 and Ni3 Zn22 ones the Zn-Ni+0.0033TiO2
and Zn-Ni+0.0066TiO2 have the highest intensity of the ␥-phase
(␥-Ni2 Zn11 ) with (330) plane orientation. Moreover, the peak value
of the ␥-phase with (330) plane orientation is superior to that of
other ␥-phases, e.g. ␥-NiZn3 ; however, the phase texture of an
alloy and composite coatings possessing a ␥-phase with (330) plane
orientation plays a determined role in the corrosion resistance per-
formance (Boonyongmaneerat and Saenapitak, 2009; Feng et al.,
2015a, b). Peak intensity of the ␥-Ni2 Zn11 of samples (c) and (d) is
high in comparison to that of samples (a) and (b). The crystal peak
intensities illustrate the evidence concerning the number of phases,
and the relative amount of zinc-nickel in the deposits (Mansfeld
et al., 1993). Therefore, coating with a higher-intensity of a ␥-phase
with (330) plane positioning decreases the corrosion rate. Similar
results were found by Anwar et al. Anwar et al. (2019b). The TiO2
peaks on the X-ray diffraction patterns are usually very wide, flat
and difficult to identify due to the nanosized of the particle; how-
ever, this XRD pattern did not show any other TiO2 peaks except
␤-Ti (220) phase orientation because this phase is more stable hav-
ing body-centered cubic structure. Generally, the formation of Ti
alloys containing ␤ phase tend to demonstrate significantly lower
elastic modulus values than ␣ and ␣ + ␤ alloys.
3.4. Surface morphology and chemical compositions of corrosion
products
Scanning electron microscopy (SEM) was used to observe the
surface characterization and texture of the Zn-Ni alloy and com-
posite films electrodeposited at a different molar concentration of
370 S. Anwar et al. / Process Safety and Environmental Protection 141 (2020) 366–379

Fig. 3. 3D images of Zn-Ni and Zn-Ni-nanoTiO2 composite coating electrodeposited at (a) Zn-Ni from non-citrate, (b) Zn-Ni from citrate, (c) Zn-Ni+0.0033 mol/l of TiO2 from
citrate, (d) Zn-Ni+0.0066 mol/l of TiO2 from citrate, (e) Zn-Ni+0.0125 mol/l of TiO2 from citrate.

Fig. 4. XRD patterns for Zn-Ni and Zn-Ni-TiO2 composite coating electrodeposited at (a) Zn-Ni from non-citrate, (b) Zn-Ni from citrate, (c) Zn-Ni+0.0033 mol/l of TiO2 from
citrate, (d) Zn-Ni+0.0066 mol/l of TiO2 from citrate.

TiO2 nanoparticles. The deposited Zn-Ni alloy coating is developed
regarding its homogeneity, and crystal grain size by changing TiO2
concentration deposited from citrate and non-citrate baths. Zn-Ni
from non-citrate bath (Fig. 5(a)) shows discontinuity, heterogene-
ity and swelling with larger grain sizes, found due to the HER, and
the bath is not stable. However, Zn-Ni coating from a citrate bath
(Fig. 5(b)) exhibits more uniform and smaller grain sizes with fewer
holes and cracks on the coatings, due to the stability of the bath
solution and the occurrence of fewer hydrogen evolution reactions.
It can be observed from the Zn-Ni coating with embedded TiO2 ,
nanoparticles (Fig. 5(c)–(e)) change the crystalline structure of the
metal deposits and formation of a stabilized bath, which decreases
the grain size and shape. The structure of the metal electrodeposi-
tion is changed by adding the TiO2 nanoparticles, which are mostly
subtle and small particles since the nanoparticles provide more
nucleation sites and delay the Zn-Ni matrix growth. TiO2 nanoparti-
cles also fill defects and improve corrosion resistance and hardness.
By increasing the mol/l of TiO2 in the electrolyte, the nanoparti-
cles showed a specific susceptibility to forming agglomerates on
the coated surface. The large amount of TiO2 enhances the surface
 S. Anwar et al. / Process Safety and Environmental Protection 141 (2020) 366–379
Fig. 5. The SEM images of Zn-Ni and Zn-Ni-nanoTiO2 composite coating electrodeposited at (a) Zn-Ni from non-citrate, (b) Zn-Ni from citrate, (c) Zn-Ni+0.0033 mol/l of TiO2
from citrate, (d) Zn-Ni+0.0066 M mol/l of TiO2 from citrate, (e) Zn-Ni+0.0125 mol/l of TiO2 from citrate.
energy and escalates the interactions among the particles (Praveen
and Venkatesha, 2008; Vlasa et al., 2010). These agglomerates are
incorporated and disperse all over the plating surface (Fig. 5(d) and
(e)) and their dimensions increase, as the TiO2 content increases.
Figs. 6–8 demonstrated that the surface morphologies of Zn-
Ni alloy and Zn-Ni-nanoTiO2 composite coatings immersed in lab
scale seawater after 12 h, 24 h and 48 h, respectively. The images
are taken at identical magnification; smaller images are at 2200
and bigger images are at 10,000 magnifications. The Zn-Ni alloy
with and without citrate after 12 h of immersion has corrosion
products, and it is covered with white islands, observed at low
magnification images (Fig. 6(a)). Zn-Ni+0.003TiO2 immersed for
12 h exhibits similar morphology as pure Zn-Ni immersed at 12
h (Fig. 6(c)). Some white cloud like structures are observed at some
parts of the surfaces due to the active properties of the coating.
The EDS results reveal that these islands and clouds are enriched
with C, O and Cl, which is related to the aggregation of corrosion
products. A similar result has been achieved and reported by Feng
et al. (2016a). Although TiO2 concentration increases, the surface
shows the cracks and solid corrosion products as observed in the
large magnification images (Fig. 6(d) and (e)).
Zn-Ni alloy with and without citrate after 24 h of immersion
has corrosion products, porosity, cracks, and holes, and is also cov-
ered with white islands, observed at larger magnification images.
Zn-Ni+0.003TiO2 immersed after 24 h exhibits smaller and intact
corrosion products with some white clouds (Fig. 7(c)). White cloud
like structures are observed at some parts of the surface due to
the active properties of the coating. As the TiO2 concentration
increases, the surface develops more cracks and pits, and solid cor-
rosion products have appeared in the large magnification images
(Fig. 7(d) and (e)).
The plating surface thoroughly covers the corrosion products,
and most of the layer becomes loosened and porous as the immer-
sion time increases, especially after a long exposure such as 48 h,
as shown in Fig. 8. This may signify the reduction in the corrosion
resistance properties of the electroplated samples. Larger islands
and big clouds are seen at low magnification. Similar results have
been reported by Feng et al. (2016a, b) and Gomes et al. Gomes
et al. (2012). Sample (a) is covered with flake and lamellae structure
corrosion products (Fig. 8(a)). Moreover, sample (d) is completely
371
covered with cloudy corrosion products with holes, as appears in
the image (Fig. 8(d)). Nonetheless, the corrosion products layer
formed on Zn-Ni+0.0033TiO2 sample (c) (Fig. 8(c)) reveals that
fewer cloudy and compact structures are seen, in comparison to
other samples.
The EDS analysis also determined the presence of TiO2 on the
composite coatings. For deposits obtained from Zn-Ni with TiO2 in
the plating bath, EDS spectroscopy revealed the presence of Tita-
nium (Ti), indicating the occurrence of TiO2 nanoparticles in the
Zn-Ni coating (Fig. 9(b)).
The EDS investigation of the corrosion products composition
(Zn, C, O Cl and Ni) of Zn-Ni alloy and Zn-Ni-nanoTiO2 samples at
after 12 h, 24 h, and 48 h of immersion time is shown in Table 2. It
is observed from the EDS data, as the immersion time increase, the
corrosion product layer is also increasing. This is demonstrated by
the enhancement of the oxygen and chlorine on the coated surface
and by the dissolution of Zn and Ni contents. Though, all the sam-
ples, the amount of Cl content is high at 12 h of immersion time
except sample (a). The Zn content in the coating is decreased for
all samples as the immersion time increase showed the dezincifi-
cation. However, for sample (a), the Zn content decreased at 24 h
(21.55 %) and then increase at 48 h (25.14 %). It is observed from
Table 2 that the Zn-Ni+0.003TiO2 samples exhibit higher Zn and
lower Cl contents after the immersion test.
3.5. Development of corrosion mechanism
At exposure to the air, there is a formation of natural oxide layers
on the surface of electroplated samples (Feng et al., 2015a). How-
ever, the oxide layers are loose and porous, and cannot control the
penetration of Cl− ions; therefore, the Zn-Ni exposed surface is cor-
roded. Accordingly, through the anodic oxidation of zinc and nickel
(Eqs. (1 and 2)), the anions and cations discharge into the elec-
trolyte, and the reduction reaction occurs at the working electrode
(Zn-Ni alloy samples) (Eq. (3)), respectively.
Zn → Zn2+ +2e− (1)
Ni → Ni2+ +2e− (2)
−
O2 +2H2 O + 4e → 4OH- (3)
372 S. Anwar et al. / Process Safety and Environmental Protection 141 (2020) 366–379

Fig. 6. The SEM images of corroded Zn-Ni and Zn-Ni-nanoTiO2 composite coating electrodeposited at (a) Zn-Ni from non-citrate, (b) Zn-Ni from citrate, (c) Zn-Ni+0.0033
mol/l of TiO2 from citrate, (d) Zn-Ni+0.0066 mol/l of TiO2 from citrate, (e) Zn-Ni+0.0125 mol/l of TiO2 from citrate after 12 h of immersion time.

Fig. 7. The SEM images of corroded Zn-Ni and Zn-Ni-nanoTiO2 composite coating electrodeposited at (a) Zn-Ni from non-citrate, (b) Zn-Ni from citrate, (c) Zn-Ni+0.0033
mol/l of TiO2 from citrate, (d) Zn-Ni+0.0066 mol/l of TiO2 from citrate, (e) Zn-Ni+0.0125 mol/l of TiO2 from citrate after 24 h of immersion time.

The corrosion mechanism and the electrochemical process of 5Zn2+ +8OH− +2Cl- → Zn5 (OH)8 Cl2 (5)
the Zn-Ni coated alloy constitute the dissolution of zinc and nickel,
which is equalized by the reduction of O2 at the working elec- The carbonate ions formed through the dissolution of carbon
trode (cathode); subsequently, zinc hydroxide (Zn(OH)2 ) and nickel dioxide (Eqs. (6)–(8)). Subsequently, The OH− ions and Zn2+ ions
hydroxide (Ni(OH)2 ) is formed, and it can desiccate to form zinc produced by Eqs. (1) and (3) combines with CO3 -2 ions to generate
oxide (ZnO) and nickel oxide (NiO) (Eqs. (3 and 4)). In the pres- hydrozincite precipitation (Eq. (9)). The occurrence of hydrozincite
ence of a saline solution, Na+ moves toward the cathode, while signifies the formation of active sites on the Zn-Ni alloy (Fürbeth
Cl− migrates toward the anodic sites saturated with dissolved zinc; and Stratmann, 2001)
therefore, simonkolleite forms, according to Eq. (5). CO2 +H2 O → H2 CO3 (6)
2+
Zn +O2 +H2 O → Zn(OH)2 → ZnO + H2 O (3) H2 CO3 +H2 O → H2 CO3 − +H3 O+ (7)

Ni 2+
+O2 +H2 O → Ni(OH)2 → NiO + H2 O (4) H2 CO3 −
+H2 O → CO3 -2 +H3 O+ (8)
 S. Anwar et al. / Process Safety and Environmental Protection 141 (2020) 366–379 373

Fig. 8. The SEM images of corroded Zn-Ni and Zn-Ni-nanoTiO2 composite coating electrodeposited at (a) Zn-Ni from non-citrate, (b) Zn-Ni from citrate, (c) Zn-Ni+0.0033
mol/l of TiO2 from citrate, (d) Zn-Ni+0.0066 mol/l of TiO2 from citrate, (e) Zn-Ni+0.0125 mol/l of TiO2 from citrate after 48 h of immersion time.

Fig. 9. EDS peaks of Zn-Ni alloy and Zn-Ni-nanoTiO2 composite coating electrodeposited (a) Zn-Ni without TiO2 , (b) Zn-Ni with TiO2 .

Table 2
Corrosion products composition of Zn-Ni and Zn-Ni-nanoTiO2 composite coatings.

Samples Compositions (at%)

Immersion time (h) Zn C O Cl Ni

12 34 25 32 8 1
(a) Zn-Ni alloy from
24 22 29 40 10 0
non-citrate bath
48 25 27 39 9 0
12 34 18 33 15 0
(b) Zn-Ni alloy from
24 27 28 38 9 0
citrate bath
48 25 28 38 9 0
12 35 22 31 11 1
(c) Zn-Ni+0.0033TiO2
24 30 26 36 7 1
from citrate bath
48 29 24 37 10 1
12 27 29 32 11 1
(d) Zn-Ni+0.0066TiO2
24 26 27 35 11 1
from citrate bath
48 25 28 30 16 1
12 32 25 36 7 1
(e) Zn-Ni+0.0125TiO2
24 30 23 34 12 1
from citrate bath
48 26 23 35 15 1

5Zn2+ +2CO3 −2 +6OH- → Zn5 (CO3 )2 (OH)6
5ZnO(s) +5CO2(g) +3H2 O → Zn5 (CO3 )2 (OH)6(s)
The formation of simonkolleite before the precipitation of
hydrozincite reveals that enough Cl− is present in the Zn-Ni alloy
during immersion. However, the formed hydrozincite may be
(9) unstable in the strong solution of Cl- ions and can disintegrate into
simonkolleite, corresponding to Eq. (11). The research observed
(10) by Odnevall et al. (Odnevall and Leygraf, 1994) and reported that
in an appropriate condition, the hydrozincite, simonkolleite and
zinc oxide layered structure converts from one phase to another.
As the immersion time increase, this leads to an increase in the
374 S. Anwar et al. / Process Safety and Environmental Protection 141 (2020) 366–379
Table 3
Polarization data for the Zn-Ni and Zn-Ni-nanoTiO2 composite coating.
Samples Ecorr (V vs SCE) Icorr (␮A/cm2 )
(a) Zn-Ni alloy from non-citrate −1.00 732
bath
(b) Zn-Ni alloy from citrate bath −1.02 494
(c) Zn-Ni+0.0033 mol/l of TiO2 −0.90 176
from citrate bath
active anodic species on the coating surface and produces signifi-
cant amount of zinc oxide. Consequently, the presence of ZnO and
NiO increases the pH of the electrolyte. The abundance of zinc oxide
and nickel oxide can also be related with the possibility of hydroz-
incite (Eq. (12)). Similarly, Wasekar et al. (Wasekar et al., 2015)
reported the formation of compact ZnO corrosion products on the
Zn coated surface, and this provides extra strength to enhance the
corrosion-resistant properties of the coating. Zn(OH)2 and Ni(OH)2
is the primary corrosion product; however, it will become ZnO and
NiO in the dry condition. This is because ZnO and NiO is a more
consistent and stable corrosion product (Tano and Huguchi, 1985).
Zn5 (CO3 )2 (OH)6 +2Cl− +2OH- → Zn5 (OH)8 Cl2 +CO3 -2 (11)
−
Zn5 (CO3 )2 (OH)6 +2OH → 5ZnO + 5HCO3 - + 3H2 O (12)
As seen from the surface morphological images and corroded
composition tests, the formation of corrosion products on the Zn-
Ni+0.0033TiO2 samples is fully dispersed, compact and strong. This
will lead to formation of the protective layer on the surface of the
sample from the corrosive environment.
3.6. Characteristics of corrosion products
The characterization of the Zn-Ni alloy corrosion products was
measured by X-ray diffraction and is shown in Fig. 10. As seen
from Fig. 4, XRD graphs without immersion tests shows a sin-
gle ␥-phase at 43 degrees. After 24 h of immersion, the peaks
at 43 degrees indicate the appearance of both ␥-NiZn3 and ␥-
Ni2 Zn11 . The sharp intensity of NiZn3 and Ni2 Zn11 indicates that
Zn-Ni alloy cannot completely dissolve after 24 h of immersion
in a lab scale 3.5 % NaCl solution. Corrosion products such as
simonkolleite (Zn5 (OH)8 Cl2 .H2 O), hydrozincite (Zn5 (CO3 )2 (OH)6 ),
zinc oxide/zincite (ZnO), smithsonite (ZnCO3 ) and zinc hydrox-
ide wulfingite (Zn(OH)2 ) are found in Zn and Zn alloys and are
visible in the immersion test (Friel, 1986; Sriraman et al., 2013;
Bučko et al., 2011; Mouanga and Berçot, 2010; Ortiz et al., 2009;
Feng et al., 2016a). Simonkolleite and hydrozincite have well-
crystallized forms and many intense reflections appear at the peaks.
Moreover, the majority of the hydrozincite overlaps on the peaks
of simonkolleite. Far away from these peaks, there are also rare
appearances and indications of Zn(OH)2 , ZnO, and Zn(CO)3 . Note
that the intensity of hydrozincite, smithsonite, and zinc oxide
peaks is often a broadened reflection, and some peaks are super-
imposed with simonkolleite, forming a weak crystallized form of
these phases.
3.7. Electrochemical measurement analysis
The potentiodynamic polarization curves are used to determine
the electrochemical measurement of Zn-Ni alloy and Zn-Ni-
nanoTiO2 composite film at room temperature and shown in Fig. 11.
The polarization values are evaluated at their OCP’s readings of dif-
ferent electroplating samples and corrosion current densities (Icorr )
and corrosion potentials (Ecorr ) are computed from the intercepts
on the Tafel slopes by extrapolation, and tabulated in Table 3. The
Ecorr values are more negative corresponding to the steel (Ecorr =
−0.66 V) (Feng et al., 2016a) over the entire immersion time for
the Zn-Ni alloy (Abibsi et al., 2017) and Zn-Ni-nanoTiO2 (Punith
Kumar et al., 2012) samples, suggesting the sacrificial property on
the steel specimen. The corrosion activity of the Zn-Ni alloy coat-
ing in corrosion media is directly related to corrosion potentials.
The corrosion resistance performance of the electroplated sample
is mainly related to their structural morphologies, chemical com-
positions and phase compositions (Mansfeld et al., 1993).
It is observed from Fig. 11 and Table 3 that the corrosion current
(Icorr ) of Zn-Ni coating deposited from a citrate bath (0.08 mol/l of
ammonium citrate) without immersion is lower (494 ␮A/cm2 ) than
the non-citrate bath Zn-Ni coating (732 ␮A/cm2 ). It is also notice-
able that the Zn-Ni alloy coating deposited from the citrate bath
exhibits less negative corrosion potential (Ecorr ) than the coating
deposited from the non-citrate bath. Moreover, the Zn-Ni specimen
from the non-citrate bath shifts more negative corrosion potential
and maximum corrosion current, leading to the formation of holes,
cracks and non-uniformity on the coated surface, due to the hydro-
gen reduction on the cathode forming the hydrogen bubbles on the
coated sample during electroplating.
The anodic and cathodic polarization behaviour of Zn-Ni-
nanoTiO2 deposited from the citrate bath (0.16 mol/l of ammonium
citrate) at a different molar concentration of TiO2 nanoparticles
without immersion, embedded in the Zn-Ni matrix, is also pre-
sented and analyzed in Fig. 11 and Table 3. As can be seen from
Table 3, except for the case of Zn-Ni+0.0033 mol/l of TiO2 , the cor-
rosion potential (Ecorr ) values of the composite coating are more
negative than those of the other Zn-Ni alloy, indicating that Zn-
Ni+0.0033 mol/l of TiO2 composite coatings are more active than
pure Zn-Ni and other Zn-Ni-nanoTiO2 composite coatings. The
presence of TiO2 particles in the Zn-Ni alloy matrix have emerged as
a uniform passive layer, decrease the coefficient of friction, increase
the wear resistance properties leading to an increase in the cor-
rosion resistance and mechanical properties of the coating (Vlasa
et al., 2010). Similar results were obtained by Vlasa et al. (Vlasa
et al., 2010), Praveen et al. (Praveen and Venkatesha, 2011), Kumar
et al. (Punith Kumar et al., 2012), Karimzadeh et al. (Karimzadeh
et al., 2019) and Gomes et al. (Fustes et al., 2008).
3.8. Electrochemical impedance spectroscopy (EIS) analysis
The electrochemical kinetics and corrosion mechanism of
the Zn-Ni alloy and Zn-Ni-nanoTiO2 samples can potentially be
measured using the EIS method. Moreover, it can estimate the
characteristics and kinetics of the electrochemical process occur-
ring at the interface of the coating and corrosive media (Punith
Kumar et al., 2012; Fashu et al., 2015). The impedance measure-
ment of Zn-Ni alloy and Zn-Ni-nanoTiO2 composite coatings at
room temperature are displayed in the form of Nyquist plots and
shown in Fig. 12. The open circuit potential (OCP’s) range of fre-
quency is 10 mHz to100kHz. The shape of the impedance modulus
is a semicircle (Mansfeld et al., 1993; Tozar and Karahan, 2014).
The Nyquist plots of the coated samples consist of clearly-defined
capacitive arcs, and at the high frequency of the plot is thought to
be the corrosion products. In contrast, at the low-level frequency,
the electrical equivalent circuit is considered as the electric dou-
ble layer (Winiarski et al., 2016; Feng et al., 2016a), respectively.
The EIS measurement of Zn-Ni-nanoTiO2 sample shows maximum
impedance values in comparison to other coated samples. Further
impedance measurements carried out for Zn-Ni alloy deposited
from the citrate bath show more impedance modulus in compari-
son to Zn-Ni alloy from non-citrate coating. This means that after
the addition of 0.0033 mol/l of TiO2 with citrate bath, better cor-
rosion resistance performance of the coating is exhibited. Gomes
et al. Gomes et al. (2012) and Vlasa et al. (Vlasa et al., 2010) have
observed the analogous result. This indicates the significant influ-
ence of TiO2 nanoparticles inclusion on the kinetics of both cathodic
 S. Anwar et al. / Process Safety and Environmental Protection 141 (2020) 366–379 375

Fig. 10. XRD patterns of Zn-Ni sample after 24 h of immersion.

Fig. 11. Polarization curve in logarithmic scale for Zn-Ni and Zn-Ni-nanoTiO2 composite coating.

Fig. 12. Nyquist plot for Zn-Ni and Zn-Ni-nanoTiO2 composite coating.

and anodic reactions of Zn-Ni coatings. It is also apparent from the
Nyquist plot that the Zn-Ni alloy coating without TiO2 , deposited
from the non-citrate bath, showed the least impedance modulus,
due to the un-stabilized and without the presence of TiO2 nanopar-
ticles on the Zn-Ni matrix. It also increases the active surface area
on the Zn-Ni coated specimen. Thus, the worst coating with the
minimum impedance modulus is found for Zn-Ni from the non-
citrate bath and without the addition of TiO2 nanoparticles, shown
in Fig. 12, and this is related to a minimal arc at high frequencies,
forming the oxide film in the air (Volovitch et al., 2009).
The impedance spectroscopy analysis with the fitted electrical
alternative circuit data assists in identifying the complete electro-
376 S. Anwar et al. / Process Safety and Environmental Protection 141 (2020) 366–379

Fig. 13. Nyquist plot for Zn-Ni and Zn-Ni-nanoTiO2 composite coating immersed at 12 h, 24 h and 48 h for (a) Zn-Ni from non-citrate, (b) Zn-Ni from citrate, (c) Zn-Ni+0.0033
mol/l of TiO2 from citrate, and (c) Zn-Ni+0.0125 mol/l of TiO2 from citrate.

chemical activity existing on the coated surface when it contacts the

corrosive environment. However, the shape of the spectroscopy is
significantly influenced by the electrochemical process at the sur-
face and with the geometric components of working electrodes
(Punith Kumar et al., 2012; La Mantia et al., 2008). The authors have
fit the experimental impedance spectroscopy data (Nyquist plots)
to the various arrangements of resistors (R) and the constant phase
element (C). The electrical circuits are shown in Fig. 14, where Rs
represents the solution resistance. R1 and C1 are the resistance and
capacitance of the corrosion product layers’ interface underneath
the pores, connected with the charge transfer resistance. R2 and C2
represent the resistance and capacitance associated with the charge
transfer resistance and electric double-layer capacitance.
The mathematical equation for the impedance of the constant
phase element (CPE) is given below (Mansfeld, 1981; Brug et al.,
1984):
Z(Q) = y −1
0
(jw)−˛
where y0 is the coefficient of the constant phase element, j2 =−1
imaginary constant, w is the frequency, and  is the exponential of
CPE.  = 0 represents the full resistor,  =−1 represents the induc-
tor,  = 1 represents ideal capacitor, and  = 0.5 represents Warbug
impedance (Mansfeld, 1981; Brug et al., 1984).
Zahner Thales software integrated with an IM6 electrochemical
workstation was used to measure the impedance values. The cal-
culated fitted data of the electrical equivalent circuit of Zn-Ni alloy
and Zn-Ni-nanoTiO2 composite coating are shown in Table 4. The
impedance measurement data of the simulated electrical circuit
shows the best fit with the Nyquist and Bode experimental values.
The relative error of each parameter is less than 8%. Fig. 13 shows
the Nyquist plot for Zn-Ni alloy and Zn-Ni-nanoTiO2 composite
coating immersed at 12 h, 24 h and 48 h for four different coatings.
As seen from Fig. 13(a), (b), and (c), the Zn-Ni-nanoTiO2 deposited
from the citrate bath at different immersion times has maximum
impedance modulus values in comparison to the other coated sam-
Fig. 14. Electrical equivalent circuit modelling used for the simulation of EIS data
of Zn-Ni alloy and Zn-Ni-nanoTiO2 composite coating.
ples. It is also observed that the immersion time increases lead to an
increase in the impedance modulus, due to the deposition of com-
pact and durable corrosion product components on the surface of
the coated samples.
The C1 and R1 values changes over the complete immersion
time. R1 values increases significantly after 12 h of immersion time
for the Zn-Ni alloy and Zn-Ni-nanoTiO2 composite coatings, indi-
cating that the corrosion resistance properties of the deposited
sample increases. This behaviour is due to the strong corrosion
products layer formed on the coated surface and inhibit the cor-
rosive solution to penetrate on the corrosion product layer during
immersion tests. This is evident from the increase in C1 values. The
value of R1 at 48 h is high for all the samples. However, the maxi-
mum value is 700.1 cm2 for Zn-Ni+0.003TiO2 coating leading to
an anti-corrosion performance to the coated sample. Zn-Ni coat-
ing from the non-citrate bath at 12 h of immersion test has the
least charge transfer resistance (Rct ) in comparison to other coated
samples with and without the addition of TiO2 nanoparticles due
to the un-stabilized bath coatings, and defects are formed due to
the absence of TiO2 nano-particles. The Zn-Ni-nanoTiO2 compos-
ite coating deposited from 0.033 mol/l of TiO2 at 12 h exhibited
 S. Anwar et al. / Process Safety and Environmental Protection 141 (2020) 366–379 377

Table 4
Optimum EIS fitting parameters of Zn-Ni alloy and Zn-Ni-nanoTiO2 deposits with various immersion time.

Samples Immersion time (h) Rs R1 Rct C1 ␣ C2 ␣

(cm2 ) (cm2 ) (cm2 ) (s−␣ cm2 ) (s−␣ cm2 )

Zn-Ni alloy deposited from non-citrate bath 12 47.8 194.9 45.4 40.8 0.80 5.0 0.80
24 62.3 318.5 81.4 57.4 0.84 17.8 0.78
48 54.0 453 90.6 303.9 0.89 39.9 0.56

Zn-Ni alloy from citrate bath 12 51.2 139.3 59.9 70 0.70 5.9 0.52
24 59.8 374.9 148.6 127.4 0.65 8.4 0.66
48 59.9 434.4 180.1 216.2 0.64 6.5 0.67

Zn-Ni+0.0033 mol/l of TiO2 from citrate bath 12 52.7 530.9 180.1 97.5 0.71 3.4 0.65
24 79.4 359.9 77.5 366.4 0.70 2.7 0.54
48 62.1 700.1 80.8 149.6 0.80 11.3 0.55

Zn-Ni+0.0125 mol/l of TiO2 from citrate bath 12 42.5 209.9 50.0 57.5 0.69 5.4 0.64
24 59.4 448.1 124.4 242.8 0.69 4.0 0.57
48 46.9 390.6 185.8 395.3 0.81 5.7 0.53

higher Rct value than other coatings. Therefore, the addition of
0.033 mol/l of TiO2 in Zn-Ni coatings is improved their corrosion
resistant behaviour than Zn-Ni alloy coatings. For Zn-N+-0.003TiO2
samples, the C2 values slightly decrease at 24 h immersion time
and increase at 48 h. This is evident that there is the possibility of
non-uniformity and sponginess of the corrosion product layer.
The least values of R1 at 12 h of immersion indicate that the cor-
rosive solution easily reaches on the surface of the Zn-Ni alloy and
Zn-Ni composite samples. At 24 h of immersion test, the R1 value
increases for all samples demonstrate the formation of a compact
corrosion product layer leads to provide protection from corrosion.
The values of R1 and Rct at 48 h of immersion test is higher than
the 24 h for all samples. This behaviour is related to a decrease
of the corrosion rate on the coated surface; it can also be associ-
ated with the formation of uniform, denser and compact corrosion
product layers. Similar behaviour has been seen for all the coated
samples, such as pure Zn-Ni, Zn-Ni, and Zn-Ni-TiO2 samples exhibit
the same behaviour values of R1 is increases after 12 h of immer-
sion test. Feng et al. (2016a, b), Gomes et al. Gomes et al. (2012)
and Vlasa et al. (Vlasa et al., 2010) also reported a similar result and
revealed that the addition of complexing agents and the addition
of titanium dioxide leads to an increase in the corrosion resistance
performance of the Zn-Ni alloy coated samples.
4. Conclusions
This study focuses on the deposition of Zn-Ni alloy and Zn-
Ni-nanoTiO2 films to enhance the anti-corrosion performance and
mechanical properties of the coated samples. The polarization
result revealed that a stable citrate bath helped to deposit a uniform
coating with decreased hydrogen evolution reaction. The least Icorr
values and small grain or crystal size, compactness and uniform
texture exhibited better anti-corrosion properties. The important
conclusions of electrochemical and corrosion behaviour of coatings
are:
• The potentiodynamic polarization results reveal that the Zn-
Ni+0.0033 mol/l of TiO2 coating deposited from the citrate bath
possesses a lower Icorr value and more positive corrosion poten-
tial. The lower Icorr reasonable for the stable citrate bath Zn-Ni
with decreased HER. This exhibited uniform and higher corrosion
resistance, and the SEM images showed the formation of denser
and more uniform coating.
• The crystalline phase texture of the Zn-Ni alloy deposits from the
citrate bath has the maximum intensity of the ␥-phase ␥-NiZn3
(815), ␥-Ni2Zn11 (330) (631), and the Ni3Zn22 plane orientation.
These orientations support the corrosion resistance performance
of the coating.
• The impedance measurement of the Zn-Ni+0.0033 mol/l of
TiO2 coating deposited from the citrate bath increased the
impedance modulus. The most effective coating with the max-
imum impedance modulus was Zn-Ni+0.0033 mol/l of TiO2 . It
exhibited compact and robust corrosion products after a 48 h
immersion test.
• The electrical circuit data showed that the Zn-Ni-nanoTiO2 com-
posite coating deposited from 0.033 mol/l of TiO2 at 12 h
exhibited a higher R1 and Rct than other coatings. The addition of
TiO2 and complexing agent in the bath is an effective process for
corrosion resistance and an increase in the mechanical properties
of the coating.
• Increasing the immersion time led to an increase in the com-
position of simonkolleite and zinc oxide (ZnO). The corrosion
resistance performance decreased at 12 h of immersion time, due
to the formation of the maximum amount of ZnO. This was also
accompanied by the growth of porous corrosion products. Fur-
thermore, the corrosion resistance increased at 24 h and 48 h,
due to the disposition of robust and compact corrosion product
layers.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgements
The authors express gratitude to the financial commitment pro-
vided by the Natural Science and Engineering Council of Canada
(NSERC) through Discovery Grant and the Canada Research Chair
(CRC) Tier I Program in offshore safety and risk engineering. The
authors are also thankful to Dr. Erika Merschrod’s for the use of
atomic force microscopy (AFM) in Dr. Merschrod’s lab at the Depart-
ment of Chemistry, Memorial University of Newfoundland, NL,
Canada.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in
the online version, at doi:https://doi.org/10.1016/j.psep.2020.05.
048.
378 S. Anwar et al. / Process Safety and Environmental Protection 141 (2020) 366–379
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