Combustio n synthesis of Ni doped SnO2 nanoparticles for applications in Zn-composite coating on mild steel

Journal of Science: Advanced Materials and Devices 3 (2018) 412e418

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Journal of Science: Advanced Materials and Devices
journal homepage: www.elsevier.com/locate/jsamd

Original Article

Combustion synthesis of Ni doped SnO2 nanoparticles for applications
in Zn-composite coating on mild steel
K. Deepa, T.V. Venkatesha*
Department of Studies in Chemistry, School of Chemical Sciences, Kuvempu University, Shankaraghatta, 577451, Shimoga, Karnataka, India

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 3 June 2018
Received in revised form
14 November 2018
Accepted 18 November 2018
Available online 24 November 2018

Zinc (Zn)-composite coatings are still in demand as good corrosion barrier coatings to protect steel
substrates from corrosion environment. In this article, the Ni doped SnO2 nanoparticles were synthesized
and used as a composite additive for Zn-coating. The synthesis was carried out by the combustion
method using citric acid as a fuel. The Zn-Ni doped SnO2 composite coating was produced on mild steel
by an electroplating technique. The surface characterization and elemental analysis of the coated samples
were examined by X-ray diffraction spectroscopy (XRD), scanning electron microscopic images (SEM)

followed by energy dispersive spectroscopy (EDAX). The surface morphology of Zn-Ni doped SnO2
composite before and after corrosion showed a more compact surface structure with respect to the pure
Zn-coat. The corrosion resistance property of the Zn-Ni doped SnO2 composite coating was studied by
Tafel polarization and electrochemical impedance spectroscopy.
© 2018 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi.
This is an open access article under the CC BY license ( />
Keywords:
Ni doped SnO2 nanoparticles
Zn-composite coating
Corrosion behavior
Tafel polarization
EIS

1. Introduction
The steel materials have diverse applications throughout the
world in various fields because of the ease of production, availability,
low-price and better mechanical strength. The main drawback of
these materials is ‘corrosion’ in their applications which leads to
economic problems. The diversity in applications of steel made it so
important to protect from corrosion process [1e3]. The study on the
protection of steel substrates from corrosion phenomena was an
interesting research topic since many years. Considering the corrosion problem of steel metals, investigations were focused on the
development of protective layers on the surface of a steel substrate
by an electrochemical process [4,5]. The electroplating technique
has been widely applied to the surface treatment of steel substrates
to achieve better corrosion resistance properties of steel [6,7]. The
deposition of metallic layers on steel substrates involved the electrolysis of certain metals like Zn, Ni, Cu, Sn etc., provided a good
corrosion protection under aggressive atmosphere [8e10]. Indeed,
the chrome coating provided an excellent corrosion passivation for
the steel surface from the surrounding environment thereby

corrosion resistance of the steel metal was sacrificial. The chrome
passivation, however, has been prohibited due to the toxicity
* Corresponding author. Fax: þ91 08282 256255.
E-mail address: (T.V. Venkatesha).
Peer review under responsibility of Vietnam National University, Hanoi.

towards the environment. Thus, it is of essential to develop nontoxic and longer life spanned surface coating for steel surface protection [11,12]. Among various coatings, zinc coating found much
importance because of its broad range of applications in the automobile industry, construction platforms and also marine applications thanks to cost friendly and good mechanical property. The
presence of the salinity in the marine environment causes the
deterioration of Zn-coated steel substrates which affects the service
life of the Zn-coating [13]. In recent years, efforts have been moved
on to Zn-composite coatings due to their better corrosion resistance
property compared to pure Zn-coating. The extensive research on
composite materials for Zn-composite coating was focused on the
utilization of metal oxides [14], carbides [15], nitrides [16], polymers
[17]. These coatings improved the corrosion resistance properties of
Zn-coating with respect to the pure Zn-coating in the presence of a
corrosive atmosphere. Amongst, the metal oxide nanoparticles
received more attention due to their availability and low cost of
preparation [18,19].
Nowadays, doped metal oxides and mixed metal oxides exhibit
remarkable physical and chemical properties. Practically, Zn-1%
Mn-doped TiO2 composite coating on the steel substrate has been
studied by Kumar et al [20]. They obtained a better corrosion
resistance property in comparison to the Zn-composite coating. The
corrosion resistance property and tribological properties of ZnAl2O3-CrO3-SiO2 have been reported by Malatji et al. [21]. The
observed results signified the enhanced anticorrosive property of

/>2468-2179/© 2018 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi. This is an open access article under the CC BY license
( />

K. Deepa, T.V. Venkatesha / Journal of Science: Advanced Materials and Devices 3 (2018) 412e418

Zn-mixed metal oxides composite coating. A good improvement
was reported for Zn-TiO2-WO3 composite coating [22].
The present effort focused on increasing the service life of Zncoating with the reinforcement of Ni doped SnO2 nanoparticles as
a composite additive in the Zn-matrix. The tin metal and its oxides
have many applications in various fields because of its better
thermal stability and good mechanical property. SnO2 is a n-type
semiconductor metal oxide having a bandgap of 3.6 eV [23,24]. The
research on SnO2 metal oxide nanoparticles as a composite material
in zinc coating has been investigated by Fayomi et al. [25]. They
found that the anticorrosive and tribological properties of Zn-AlSnO2 composite coating were satisfactorily good compared with
that of Zn-Al alloy coating. To our best knowledge, no work has
been found regarding incorporation of Ni doped SnO2 nanoparticles
as a composite additive in Zn-coating for corrosion protection of
steel.

413

papers and acetone. Finally, plates were rinsed with distilled water
and used. The zinc sheets were plunged in 5% HCl to activate the
surface of the anode material each time [29]. The bath solution
prepared for Zn-Ni doped SnO2 composite coating has been stirred
for 10 h to prevent the agglomeration of nanoparticles. Scheme 2
demonstrates the experimental setup carried out for generation
of the Zn-Ni doped SnO2 composite coating.
The fabricated Zn and Zn-Ni doped SnO2 coatings were subjected to electrochemical corrosion studies of Tafel and electrochemical impedance spectroscopy (EIS) using potentiostat CHI660C
electrochemical workstation. The EIS studies were executed at the
open circuit potential (OCP) with frequency ranging from 0.1 Hz to

10 kHz and amplitude of 5 mV. The morphology and composition of
the deposits were scrutinized by XRD, scanning electron microscopic images and energy dispersive spectral investigation.
3. Results and discussion

2. Experimental
3.1. XRD analysis
2.1. Materials and synthesis methods
Nickel (II) chloride heptahydrate (NiCl2$7H2O) was supplied
from Himedia Laboratories Pvt. Ltd. Mumbai. Tin (II) chloride
dihydrate (SnCl2$2H2O) was received from Merck Life Science Pvt.
Ltd. Mumbai. Citric acid anhydrous was arrived from Merck Specialties Pvt. Ltd. Mumbai and Millipore water. In a typical synthesis
of Ni doped SnO2 nanoparticles, salt precursors of SnCl2$2H2O,
NiCl2$7H2O and citric acid as a fuel were taken as 1:1 ratio and
completely dissolved in a dilute HNO3 solution to get a combustion
mixture. Afterward, the solution mixture was heated on a hotplate
with constant stirring until a solution mixture converted into a gel
form [26e28]. The gel was transferred into a quartz crucible and
kept into a preheated furnace maintained at 400  C. Within a few
seconds, precursor gel gets boiled and ignited. Then the crucible
was taken out and kept for cooling for few minutes at atmospheric
temperature. The product was finely grounded in an agate mortar
and calcined for 2 h at 500  C. Scheme 1 illustrated the experimental steps involved during the synthesis of Ni doped SnO2
nanoparticles.
The crystallite size of Ni doped SnO2 was determined by
Powder x-ray diffraction analysis (PANalytical X'pert pro powder
diffractometer, lKaCu ¼ 1.5418 Å). The surface morphology and
percentage composition of the prepared products were studied by
scanning electron microscopic photographs (FESEM-Carl ZEISS,
Supra 40 VP) followed by energy dispersive spectroscopy.

Fig. 1 depicts the XRD patterns of as-prepared Ni doped SnO2
nanoparticles. The characteristic peaks corresponding to Miller
indices at (110), (101), (200), (111), (210), (211), (220), (002), (310),
(112), (301), (202) and (321) confirmed that the prepared product is
a tetragonal structured SnO2 [30e32]. No impurity peaks were
appeared indicating the formation of a single phase tetragonal
shaped Ni doped SnO2. The DebyeeScherer equation was applied to
calculate the crystallite size of the particles:

D¼

Kl
bCos q

(1)

where D is the diameter of the crystallite size, l is the wavelength of
the radiation source, K is the shape factor (0.9), q is the Bragg's angle
and b is the angular peak width at half maximum intensity
(FWHM). The calculated average crystallite size was found to be
27.70 nm.
3.2. SEM with EDAX studies
The surface morphology and elemental analysis of the prepared
nanoparticles were displayed in Fig. 2. As can be seen that the particles appeared like agglomerated spherical shaped flakes like
morphology of Ni doped SnO2 nanoparticles. The elemental composition showed that the presence of Ni, Sn and O with the percentage
of constituents and there was no foreign elements were observed.

2.2. Fabrication of Zn and Zn-Ni doped SnO2 composite coatings
3.3. Characterization of the coatings
The electroplating bath composition and parameters were listed

in Table 1. Steel substrates with dimensions of 4 Â 4 Â 0.1 cm3 were
used as cathode substrates and zinc sheets of the same dimension
were used as anode materials. Before electroplating experiment,
the surface cleaning of steel plates was carried out using emery

The XRD patterns of the Zn and Zn-Ni doped SnO2 coatings are
represented in Fig. 3. The crystallite size was calculated using Debye
Scherer equation and the obtained size for zinc coating was 33.88 nm
and for Zn-composite coating it was 28.48 nm. The characteristic

Scheme 1. Experimental sequence for synthesis of Ni doped SnO2 nanoparticles.


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K. Deepa, T.V. Venkatesha / Journal of Science: Advanced Materials and Devices 3 (2018) 412e418

Table 1
Bath composition and operating parameters.
Bath constituents
1(a)

1(b)

ZnSO4-200 g/L
Na2SO4-40 g/L
NaCl-15 g/L
H3BO3-12 g/L
SLS-0.5 g/L
1(a)þ Ni doped

1(a)þ Ni doped
1(a)þ Ni doped
1(a)þ Ni doped

Deposit code

ZO

SnO2 0.5 g/L
SnO21 g/L
SnO2 1.5 g/L
SnO2 2 g/L

ZI
ZII
ZIII
ZIV

Operating parameters
Anode: zinc plate (99.99% pure)
Cathode: mild steel plate
Current density: 3 A/dm2
Plating time: 10 min
Stirring speed: 300 rpm pH: 3
Temperature: 303 K

Scheme 2. Electroplating setup for the Zn-Ni doped SnO2 composite coating.

surface leads to a compact structured surface and less number of
surface pores.

SEM photographs of pure Zn coatings and Zn-Ni doped SnO2
composite coatings were represented in Fig. 4. The pure zinc deposit
was accompanied with some gaps and micro holes on its surface as
displayed in Fig. 4(a). These micro-holes were greatly reduced and
nearly absent in the Zn-Ni doped SnO2 composite deposit, which
exhibited fine compact structured surface morphology as shown in
Fig. 4(b) [35,36]. It can be seen that the reduced grain size leads to the
formation of tiny Zn fibers like compact surface morphology in the
case of Zn-Ni doped SnO2 composite coated steel surface compare to
pure Zn deposit. The energy dispersive spectrum demonstrated in
Fig. 5 indicates the presence of Ni doped SnO2 nanoparticles in the
Zn-composite matrix.
3.4. Electrochemical corrosion studies

Fig. 1. XRD patterns of Ni doped SnO2 nanoparticles.

peaks at (102) and (103) planes showed the highest intensity in case
of pure Zn-coating and they are decreased for Zn-Ni doped SnO2
composite coating. This finding indicated that the presence of Ni
doped SnO2 nanoparticles inhibited the crystal growth thereby
reduced the grain size [33,34]. The reduction in grain size on the zinc

3.4.1. Tafel
The Tafel plots were recorded for the study of the corrosion
resistance property in terms of the polarization resistance behavior
of the electrodeposited samples in 3.65% NaCl solution as corrosion
media. In order to measure the corrosion resistance property of the
deposits, the electrolytic cell was used, in which the platinum wire
is served as an auxiliary electrode, calomel electrode as a reference
electrode and coated specimens as the working electrodes. Initially,

the coated samples were dipped in the corrosive electrolyte solution to attain the OCP. The potential varies with respect to the time


K. Deepa, T.V. Venkatesha / Journal of Science: Advanced Materials and Devices 3 (2018) 412e418

415

Fig. 2. SEM image with EDAX analysis of Ni doped SnO2 nanoparticles.

and attained a steady state potential (referred to as OCP) [37,38].
The electrode potential of the working electrode was polarized in
the range of þ200 mV anodically and À200mv cathodically with
respect to their OCP. The Tafel plots are depicted in Fig. 6. The
electrochemical parameters such as Ecorr (corrosion potential), Icorr
(corrosion current), Rp (polarization resistance) were recorded and

Fig. 3. XRD patterns of Zn and Zn-Ni doped SnO2 deposits.

Fig. 5. Energy dispersive spectrum of Zn and Zn-Ni doped SnO2 composite deposits.

Fig. 4. SEM images of (a) Zn-deposit (b) Zn-1.5 g/L Ni doped SnO2 composite deposit.


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K. Deepa, T.V. Venkatesha / Journal of Science: Advanced Materials and Devices 3 (2018) 412e418

results were tabulated in Table 2. It can be observed that the Ecorr
value of Zn-coating was À1.138 V and it was slowly reduced with
the addition of Ni doped SnO2 nanoparticles in Zn-coat (concentration varying from 0.5 to 2 g/L). Among Zn-Ni doped SnO2 composite coatings, the Zn-1.5 g/L Ni doped SnO2 composite coating

posses less Ecorr via À1.121 V, indicating the less response of a Zncomposite coated steel metal surface towards corrosion atmosphere. Similarly, the corrosion current (Icorr) was higher for pure
Zn deposit and it gradually reduced for Zn-composite deposits. The
optimum composite coating has been achieved at 1.5 g/L nanoparticles concentration. The corrosion rate (CR) of the respective
coatings was calculated by the following equation.

CRðmpyÞ ¼

0:13 Icorr ðEq:wtÞ
d

(2)

The Zn-coating at Zn-1.5 g/L of Ni doped SnO2 nanoparticles
concentration yields a good corrosion resistance property
compared to the all other concentrations. The increased amount of
nanoparticles caused the reduced polarization resistance behavior.
This is due to the fact that the agglomeration of nanoparticles at
higher concentration leads to the poor adhesion on the surface and
slows down the deposition process [39,40]. Hence the further
addition of nanoparticles in Zn-coating was stopped after the Zn-2
g/L Ni doped SnO2 deposition.

are tabulated in Table 3. The circuit was composed of the coating
resistance (Rcoat), the coating capacitance (Qcoat), the double layer
capacitance (Qdl) and the charge transfer resistance (Rct). The
capacitance was replaced by a constant phase element to achieve
good results of the fitted circuit with experimental EIS plots. The
constant phase element (CPE) implies the departure from the ideal
capacitance behavior of the working electrode thanks to the surface
inhomogeneity and micro-roughness [41,42]. The impedance obtained by CPE was given by

Àn
ZCPE ¼ Y À1
0 ðiuÞ

(3)

where Y0 is CPE constant, i2 ¼ À1, an imaginary number, u is the
angular frequency and n represents the component of CPE which
provides the details regarding the degree of the inhomogeneity of
the metal surface, micro-roughness and porosity [43].
The Qdl and Qcoat values of a pure Zn-coating was higher
compared to that of the Zn-Ni doped SnO2 composite coating. The
presence of Ni doped SnO2 nanoparticles in the Zn-composite provided a more stability for coated surface and formed a strong
corrosion barrier under corrosive atmosphere. The lower Rct value

3.4.2. Electrochemical impedance spectroscopy
The corrosion resistance property of the prepared coated samples was examined by EIS test carried out in 3.65% NaCl solution at
OCP value of the respective coated sample. EIS measurements were
recorded as Nyquist and bode plots at the frequency range of
0.1 Hze10 kHz with amplitude of 5 mV as shown in Figs. 7 and 9.
Noted that the measured Nyquist plots shown in Fig. 7 was
matched with the suitable equivalent circuit model using Z-simp
win 3.21 software given in Fig. 8. The obtained experimental data

Fig. 7. Nyquist plots of Zn and Zn-Ni doped SnO2 composite coatings.

Fig. 6. Tafel plots of Zn and Zn-composite coatings.

Fig. 8. Equivalent circuit model matched with Nyquist plots.

Table 2
Tafel parameters.
Samples

Ecorr (V vs SCE)

Icorr  10À5 (A/cm2)

ZO
ZI
ZII
ZIII
ZIV

À1.13
À1.12
À1.11
À1.09
À1.10

3.49
2.83
1.88
9.88
1.24

Â
Â
Â
Â

Â

10À5
10À5
10À5
10À6
10À5

ebc (VÀ1 dec)

ba (VÀ1 dec)

LP (U cm2)

Corrosion rate  10À5 (g/h)

7.55
4.99
5.97
7.22
4.69

16.17
14.43
17.55
21.66
20.18

524
790

980
1522
1399

3.55
2.87
1.91
1.00
1.26


K. Deepa, T.V. Venkatesha / Journal of Science: Advanced Materials and Devices 3 (2018) 412e418

417

for Zn-Ni doped SnO2 composite coating compared to pure Zncoating indicated a reduced number of surface active pores which
are the cause of corrosion reactions. The incorporation of Ni doped
SnO2 nanoparticles in Zn-coating accumulates the surface pores and
thereby slows down the corrosion reactions at the interface of the
metal surface and electrolyte in aggressive media [36,44]. The
corrosion resistance property was satisfactory at the Zn-1.5 g/L Ni
doped SnO2 composite coating. Further increase of the Ni doped
SnO2 concentration in the zinc matrix results in a decreased
impedance of the deposit. Hence, the 1.5 g/L concentration of the Ni
doped SnO2 composite additive has been considered as an optimum
concentration for the good Zn-composite coating. The polarization
resistance (RP) was given by the sum of the resistances of Rcoat and
Rct. The Zn-Ni doped SnO2 composite coating has higher RP value in
view of more corrosion resistance property compared to pure zinc
coating. Similar results have been observed in bode plot and bode

phase angle plot as displayed in Fig. 9a,b in which higher modulus
impedance was observed for the Zn-1.5 g/L Ni doped SnO2 composite coating and it was lesser for pure Zn-coating. Also, a
maximum phase angle was attained for the Zn-Ni doped SnO2
composite coating due to the more homogeneous surface with good
corrosion resistance property of Zn- Ni doped SnO2 composite
coating.

Fig. 9. Bode magnitude plot (a) and Bode phase angle plot (b) of Zn and Zn-Ni doped
SnO2 composite coatings.

3.4.3. Corrosion morphology
The SEM images depicted in Fig. 10 shows that the corroded
surface morphology captured after corrosion studies in 3.65% NaCl
solution. The surface of pure Zn coated specimen was highly
deteriorated and some cracks were also observed in Fig. 10(a).
This indicates the poor corrosion resistance property under corrosive environment. The Zn-1.5 g/L Ni doped SnO2 composite
coated surface exhibited a little effect on the corrosion reactions
as shown in Fig. 10(b). Here, less deterioration and no cracks were
appeared on the surface. The presence of Ni doped SnO2 nanoparticles in Zn-matrix provided a strong corrosion barrier in
corrosion media.

Table 3
EIS parameters.
Samples
ZO
ZI
ZII
ZIII
ZIV

Qcoat (Sn UÀ1 cmÀ2)
3.46
8.75
9.31
1.25
9.91

Â
Â
Â
Â
Â

À3

10
10À4
10À5
10À5
10À5

n
0.8
0.7
0.7
0.8
0.8

Qdl (Sn UÀ1 cmÀ2)
2.89

1.25
3.72
1.90
5.41

Â
Â
Â
Â
Â

À4

10
10À4
10À4
10À5
10À5

n
0.8
0.8
0.8
0.8
0.8

Cdl (F/cm2)
1.65
6.75
3.07

8.58
2.94

Â
Â
Â
Â
Â

À4

10
10À5
10À4
10À6
10À5

Fig. 10. SEM images of corroded (a) Zn deposit (b) Zn-1.5 g/L Ni doped SnO2 composite.

RP¼(Rcoat þ Rct) (U cm2)
364.2
669.6
1241
2151
1617


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K. Deepa, T.V. Venkatesha / Journal of Science: Advanced Materials and Devices 3 (2018) 412e418

4. Conclusion
The Ni doped SnO2 nanoparticles were prepared by combustion
method. The Zn-Ni doped SnO2 composite coating was fabricated
by an electroplating technique. X-ray-diffraction study revealed the
nano size of the Ni doped SnO2 particles. Surface morphology of Ni
doped SnO2 showed the spherical nanoflakes structure. The EDAX
analysis confirmed the percentage composition of the prepared
nanoparticles. The Zn-Ni doped SnO2 composite coating exhibited
an improved surface texture. The incorporation of the Ni doped
SnO2 particles in the Zn-composite coating was confirmed by the
EDAX analysis. The Tafel and electrochemical impedance studies
proved that the presence of the Ni doped SnO2 in Zn-coating
increased the corrosion resistance property of Zn-deposit as
compared to pure Zn-deposit.

Acknowledgments
The authors gratefully acknowledge the Department of Chemistry, Kuvempu University, Jnana Sahyadri, Karnataka, India for lab
facilities to complete the present work and also UGC-New Delhi,
Government of India for providing UGC-BSR Fellowship (Order No.
F, 25-1/2013-14(BSR) 7-229/2009).

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