Vacuum 161 (2019) 1–4

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Vacuum
journal homepage: www.elsevier.com/locate/vacuum

A study of corrosion protection efficiency of silica nanoparticles acrylic T

coated on mild steel electrode
R. Rajkumara,b, C. Vedhic,d,∗
a
Research Scholar (Reg. No. 12052), PG and Research Department of Chemistry, V.O.Chidambaram College, Tuticorin, 628008, India
b
Assistant Professor, PG Department of Chemistry, Aditanar College of Arts and Science, Tirruchendur, 628216, India
c
Assistant Professor, PG and Research Department of Chemistry, V.O.Chidambaram College, Tuticorin, 628008, India
d
Affiliated to Manonmaniam Sundaranar University, Abishekapatti, Tirunelveli, 627012, Tamilnadu, India

A R T I C LE I N FO A B S T R A C T

Keywords: Silica nanoparticles (SNPs) were synthesized using rice husk by eco-friendly method. The physico-chemical
Silica nanoparticles characterization of SNPs was investigated by Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction
Rice husk (XRD), Scanning electron microscopy (SEM) and Energy Dispersive X-Ray Spectroscopy (EDS). FT-IR spectrum
Acrylic coating shows the main characteristic peak of SieOeSi at 468 cm−1 indicating the formation of SNPs. The XRD pattern
Anticorrosion performance
revealed the formation of crystalline SNPs and the particle grain size value were found to be 5 nm. The surface
morphology was observed by SEM. EDS result showed that the composition of silicon and oxygen in SNPs is
found to be 47.54% and 28.24%, respectively. Acrylic coating containing SNPs was directly coated on the mild
steel surface and the anticorrosive behavior was examined by polarization curve and electrochemical impedance
spectroscopy in 1% HCl and 3.5% NaCl solution. It was found that silica/acrylic coating showed better corrosion
protection efficiency as compared to that of pure acrylic coating. Silica/acrylic coating acted as good antic-
orrosive behavior for 3.5% of NaCl solution.

1. Introduction
Mild steel is an important alloy of iron used in various industries
and it is relatively low cost as compared to other iron alloys [1]. Several
chemical compounds have been investigated as corrosion inhibitors for
mild steel in acid and neutral media [2]. Corrosion is a chemical phe-
nomenon which is related to metals. Corrosion is one of the most in-
teresting fields of electrochemistry. The process of corrosion is slow and
it occurs only at the surface of metals. According to electrochemical
theory, any corrosion process may be regarded as an electrochemical
process, in which cathode and anode are formed on the surface of metal
and an electrolyte which may be water, acid or salt solution, must be
present to allow the flow of electron to form the corrosion products. The
most common and effective method of protecting metals from corrosion
is employing organic coatings [3].
Rice Husk is an agricultural by-product material obtained in the
paddy field. Their chemical compositions include cellulose, lignin and
silica. Rice husk ash is obtained from rice husk when it is burnt in
controlled temperature below 700 °C. After burning, cellulose and
lignin can be removed from rice husk leaving behind silica ash. In re-
cent years several attempts have been made to produce nano silica
powder from rice husk [4,5]. Silica (SiO2) is prepared by eco-friendly
method, low cost and non-toxic compound and it shows excellent cor-
rosion inhibitor properties.
In the present investigation, silica nanoparticles were synthesized
from agricultural waste, rice husk. The structure, morphology and
formation of SNPs were characterized by various techniques including
FT-IR, XRD and SEM-EDS analysis. The electrochemical studies were
carried out in 1% HCl and 3.5% NaCl solution using SNPs with acrylic
coating on mild steel surface.
2. Experimental procedure
2.1. Materials
Rice Husk (RH) was collected from rice mills in Tuticorin,
Tamilnadu, India. Acrylic resin was purchased from Merck.
2.2. Preparation of silica (SiO2) nanoparticles (SNPs)
Collected rice husks were washed well with deionized water and
dried at vacuum condition. The purified rice husk was initially calcined

∗
Corresponding author. PG and Research Department of Chemistry, V.O.Chidambaram College, Tuticorin, 628008, India
E-mail address: vedhi.che@voccollege.ac.in (C. Vedhi).

https://doi.org/10.1016/j.vacuum.2018.12.005
Received 18 July 2018; Received in revised form 25 October 2018; Accepted 2 December 2018
Available online 10 December 2018
0042-207X/ © 2018 Elsevier Ltd. All rights reserved.
R. Rajkumar, C. Vedhi
Fig. 1. Plate of Rice husk, rice husk ash and silica obtained from the rice husk.
in air in a silica dish and then carbonized in the electrical furnace for
5 h at 700 °C to form SNPs as shown in Fig. 1.
2.3. Characterization technique
The FT-IR spectra of SNPs were recorded on Nicolet iS5 FT-IR
spectrometer in the KBr pellet technique at room temperature in the
range of 4000–400 cm−1. X-ray diffraction pattern of SNPs were taken
using a XPERT-PRO diffractometer with CuKα radiation in the range of
10°–90°. The surface morphology of SNPs was observed by scanning
electron microscopy (SEM, JSM-5610) attached with energy dispersive
spectrometer (EDS).
2.4. Preparation of the coatings
The mild steel specimen with 5 cm × 1 cm dimensions were used
for corrosion studies. The mild steel were polished using 320 and 600
grade emery papers, followed by rinsing with ethanol and acetone and
then air-dried at room temperature before use. The silica/acrylic
coatings were directly coated onto the steel substrates and dried at
vacuum condition. Pure acrylic coating was used as reference sample in
comparison with the anticorrosion performance of silica/acrylic
coating.
Fig. 2. (a) FT-IR spectra and (b) XRD pattern of SiO2 nanoparticles.
2
Vacuum 161 (2019) 1–4
2.5. Electrochemical studies
The electrochemical corrosion studies of coated steel samples were
carried out in 1% HCl and 3.5% NaCl solution using CHI 650C elec-
trochemical analyzer. A conventional three-electrode system was used
with platinum gauze as the counter electrode, the uncoated and coated
steel specimens with an exposed area of 1 cm2 were used as the working
electrodes and saturated calomel electrode (SCE) as the reference
electrode.
Polarization curves were used to measured over a range of −1.2 to
−0.2 V (vs. SCE) at scan rate of 5 mV/s. The corrosion protection ef-
ficiency (% P.E.) was determined from the measured Icorr values by
using the following relationship.
% P.E. = [(I0corr – Icorr)/I0corr] x 100 (1)
EIS measurements were recorded at a frequency range from 100 kHz
to 10 mHz with an AC amplitude of 10 mV and the impedance data
were analyzed. The inhibition efficiency of SNPs was calculated from
the charge transfer resistance values using the following equation.
I.E% = [(Rct - Rcto)/Rct] x 100 (2)
Where Rcto and Rct are the charge transfer resistance in the absence and
presence of SNPs. The surface coverage values (θ) were calculated from
the Cdl values according to the equation
Surface coverage (θ) = (Cdlo - Cdl)/Cdlo (3)
o
Where Cdl and Cdl are the capacitance double layer in the absence and
presence of SNPs.
3. Results and discussion
3.1. FT-IR spectrum
Fig. 2a shows the FT-IR spectrum of SNPs after calcination at 700 °C
temperature. The strong absorption peak at 468 cm−1 and 800 cm−1
are the SieO symmetric stretching and bending vibration respectively.
The peak at 1103 cm−1 was due to the SieOeSi antisymmetric
stretching vibration [6].
3.2. XRD pattern
XRD pattern of SNPs (Fig. 2b) showed the strong broad peak cen-
tered at 22.45° due to the formation of crystalline form of silica [7]. The
R. Rajkumar, C. Vedhi Vacuum 161 (2019) 1–4

Fig. 3. (a) SEM and (b) EDS image of SiO2 nanoparticles.

Fig. 4. Nyquist plots in (a) 1% HCl and (b) 3.5% NaCl solution after immersion SNPs.

Table 1
Electrochemical Impedance Data for SNPs in 1% HCl and 3.5% NaCl solution.
Coating Samples 1% HCl 3.5% NaCl

2
Rct(Ω cm ) Cdl(mF) I.E.% Surface Coverage (θ) Rct(Ω cm2) Cdl(mF) I.E.% Surface Coverage (θ)

Pure Acrylic 16.70 0.1648 – – 12.97 0.1173 – –

SiO2/acrylic 36.22 0.0900 45.38 0.53 35.61 0.0261 77.75 0.63

Table 2 structure. This was in good agreement with the previous reported stu-
Polarization measurements for SNPs in 1% HCl and 3.5% NaCl solution. dies [8]. EDS result showed that the composition of Si and O elements
Coating Samples 1% HCl 3.5% NaCl
in SNPs are found to be 47.54 and 28.24% respectively as shown in
Fig. 3b. It was further confirmed the formation of SNPs.
Ecorr Icorr I.E.% Ecorr Icorr I.E.%

Pure Acrylic −0.6515 0.1637 – −0.6744 0.1014 – 4. Electrochemical corrosion studies

SiO2/acrylic −0.5902 0.0912 44.28 −0.5696 0.0235 76.82
4.1. Electrochemical impedance measurements

average particle size of the SNPs was determined and it was found to be
5 nm.
3.3. SEM-EDS analysis
SEM images were used to determine the morphology of the nano-
particles. It is clear that SNPs exhibited non spherical and agglomerated
The EIS was used to evaluate the anticorrosion performance of the
coated mild steel samples with pure acrylic resin and SiO2/acrylic
composites. Fig. 4 shows the EIS plots of uncoated and coated steel
samples immersed in different media of 1% HCl and 3.5% NaCl solu-
tion. Generally, the impedance (Z) depends on the solution resistance
(Rs), charge transfer resistance (Rct), and double layer capacitance (Cdl).
These parameters were used to calculate the inhibition efficiency (%)

3
R. Rajkumar, C. Vedhi
Fig. 5. Tafel plots in (a) 1% HCl and (b) 3.5% NaCl solution after immersion SNPs.
and surface coverage (θ) [9]. It is seen that introduction of SNPs in
acrylic system increased the value of Rct and reduces the Cdl. The charge
transfer resistance (Rct) value for pure acrylic coated steel specimen in
1% HCl and 3.5% NaCl solution are 16.70 and 12.97 (Ω cm2) while the
SiO2/acrylic coated steel sample are exhibit to be higher values. Here
the decrease in Cdl is attributed to increase in thickness of electronic
double layer [10]. The increase in Rct value is attributed to the for-
mation of the protective film of metal oxide/solution interface. The
inhibition efficiency of SiO2/acrylic coated specimen in the selected
corrosive medium of 1% HCl and 3.5% NaCl solution are 45.38% and
77.75% respectively. The charge transfer resistance (Rct) and the in-
terfacial double layer capacitance (Cdl) derived from these curves
without and with SNPs coated steel electrode are given in Table 1.
4.2. Polarization measurements
The polarization behavior of mild steel in 1% HCl and 3.5% NaCl
solution without, and with SNPs coated mild steel electrode are shown
in Table 2. The polarization measurements were carried out from
cathodic potential and anodic potential with respect to the open circuit
potential at a scan rate 50 mV/s to study the effect of SNPs on mild steel
corrosion. Polarization measurements showed that the corrosion cur-
rent values (Icorr) were found to be 0.0912 mA in 1% HCl and
0.0235 mA in 3.5% NaCl solution on SiO2/acrylic coated mild steel
electrode. The inhibition efficiency of SNPs in the selected corrosive
medium of 1% HCl and 3.5% NaCl solution are 44.28% and 76.82%
respectively. By comparison, it can be found that the EIS data are
consistent with the Tafel curves of SNPs acrylic coated mild steel
electrode in Fig. 5.
5. Conclusions
Silica nanoparticles were successfully synthesized by eco-friendly
method. The agricultural waste, rice husk can be converted into valu-
able silica products. The structure and morphology were characterized
by FT-IR, XRD and SEM-EDS analysis. The XRD studies and SEM-EDS
images, shows the formed SNPs to be in crystalline nature having si-
licon and oxygen as the major components in the SNPs. In EIS result, it
is clear that the protection efficiency for SiO2/acrylic is 45.38% in 1%
HCl and 77.75% in 3.5% NaCl solution. Polarization curves shows that
the inhibition efficiency of SNPs is 44.28% in 1% HCl and 76.82% in
3.5% NaCl solution. The anticorrosion behavior studied in the selected
two corrosive media, 1% HCl and 3.5% NaCl solution showed that the
Vacuum 161 (2019) 1–4
SiO2/acrylic coating gave a poor protective behavior in 1% HCl
medium and good behavior in 3.5% NaCl solution on mild steel elec-
trode. This was confirmed through polarization and EIS measurements.
Acknowledgement
The authors are thankful to Department of Science and Technology
(FAST TRACK) New Delhi for using electrochemical workstation and
UGC New Delhi for FTIR spectroscopy at V.O. Chidambaram College.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.vacuum.2018.12.005.
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