Arabian Journal of Chemistry (2020) 13, 3301–3318

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Corrosion performance of mild steel and galvanized

iron in clay soil environment
Subbiah Karthick, Srinivasan Muralidharan, Velu Saraswathy *

Corrosion and Materials Protection Division, CSIR-Central Electrochemical Research Institute, Karaikudi 630 003, Tamil
Nadu, India

Received 9 September 2017; accepted 4 November 2018

Available online 13 November 2018

KEYWORDS Abstract Clay is a naturally occurring material, and it has been utilized for many industrial pro-
Clay; cesses. In this study, two types of clay namely white clay (WC) and black clay (BC) was used for this
Mild steel; investigation. The corrosion performance of the clay samples was carried out using mild steel and
Galvanized steel; galvanized pipes under a buried condition in the field and laboratory exposure studies were carried
Corrosion; in the clay extracts. Generally mild steel (MS) and galvanized iron (G.I) are being used as an encas-
Electrochemical studies ing material for earthing applications. In some places, the soil was enriched with acidic clay, and it
causes corrosion of the MS and G.I and it needs periodic replacement of pipes. In this context, a
detailed study has been carried out to evaluate the relative corrosion performance of the MS and
G.I exposed to the clay environment. Electrochemical corrosion behavior of MS and G.I in clay
medium were carried out by using electrochemical impedance spectroscopy (EIS) and potentiody-
namic polarization. The corrosion product formation was characterized by X-Ray Diffraction and
Carbon Hydrogen Nitrogen Spectrum analysis. The surface morphology of MS and G.I after the
exposure was characterized by Scanning Electron Microscopy (SEM) studies. The results proved
that G.I in clay soil was severely affected by corrosion. The reason may be attributed to the insuf-
ficient thickness of the zinc coating and the presence of microbes which enhanced the G.I corrosion.
Ó 2018 Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction rate of corrosion depends on external and internal factors.

The corrosion of ferrous metals in soil is a major problem in
oil and water transported pipeline, storage tank, cooling water
pipeline distribution systems (Cole and Marney, 2012). The
* Corresponding author.
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
The external factors include temperature, humidity, soil salin-
ity/pH/porosity existing in the soil environment etc. Internal
factors include: presence of oxygen content, flow rate, pressure
existing inside the pipe, type of the fluid/gas flowing, tempera-
ture, type of the material used (Verink and Heidersbach, 1972).
Coating controls he external corrosion of oil-carrying pipeline,
cathodic protection to avoid the effect of soil corrosion
(Javaherdashti et al., 2013). The pipelines buried under soil
are subjected to various forms of corrosion such as: localized,
pitting, crevice and uniform corrosion (Li et al., 2012; Wu
et al., 2013). It has been reported that the metallic materials

https://doi.org/10.1016/j.arabjc.2018.11.005
1878-5352 Ó 2018 Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
3302
are subjected to corrosion due to the soil microbial activity,
and the corrosion behavior of soil depends on the presence
of sulphate reducing bacteria. The bacterial species enhances
the corrosion of pipeline material via either through reduction
or oxidation of the metal; SRB species generates H2S which
accelerates the corrosion of mild steel (Borenstein, 1994;
Maslehuddin et al., 2007; El-Shamy et al., 2009; Choi et al.,
2011, Tang et al., 2010; Das, 2014). Studies revealed that the
presence of sulfur-oxidizing bacteria converts the sulphide to
sulphate through sulphideoxidizing enzyme and the iron- and
sulfur-oxidizing bacteria of the genus thiobacillus are active
only under acidic conditions. It has been reported that the nat-
ure of soils is affected by moisture content, pH, resistivity,
redox potential, chloride, and sulfate contents (EI-Shamy
et al., 2015). The investigation of these soil parameters is con-
sidered as very important because the corrosive soil can cause
failure of buried pipeline. The effect of moisture content acts as
an electrolyte, which allows the ion transfer and reduction in
resistivity of the soil by making the soil more corrosive (EI-
Shamy et al., 2015). Galvanized products are widely used in
transmission towers, telecommunication equipment, road
safety and civil construction. In transmission tower footings,
galvanized structures are under partially or wholly buried con-
ditions. The corrosion of these structures depends on the
aggressiveness of the soil environment (Padilla et al., 2013;
Costa Pereira et al., 2015). The transmission tower structures
consisting of mild steel and galvanized structures buried under
the soil is susceptible to severe corrosion, and it needs periodic
replacement of the materials. Hence, the present study focused
on the clay soil, mild steel rod and galvanized pipes collected
from the site and the evaluation was carried out in the labora-
tory under simulated conditions.
In the present study, the mild steel (MS) and galvanized
iron (G.I) were exposed to two types of clay collected from
the site and the performance evaluation was carried out in sim-
ulated soil extract medium and under the buried condition in
clay soil medium. The relative corrosion performance is mon-
itored through weight loss, open circuit potential, potentiody-
namic polarization and electrochemical impedance
spectroscopy. Many authors adopted advanced techniques to
characterize the materials (Yan et al., 2016a,b, 2018). The clay
was characterized by EDAX, and the corrosion products were
analyzed through X-Ray diffraction (XRD), X-ray photoelec-
tron spectroscopy (XPS) and carbon hydrogen nitrogen spec-
trum (CHNS). All the experiments were carried out at an
exposure period of 90 days. The surface morphology before
and after the exposure was characterized by scanning electron
microscopy (SEM) and the results were discussed.
2. Materials and method
2.1. Materials used
The two clay samples available locally were used and it is
named as white clay (WC) and black clay (BC) by the nature
of the color. The photographic image of WC and BC samples
were given in Fig. 1. The materials such as MS and G.I pipes
are considered for this study. The nominal composition of MS
and G.I used for the investigation is given in Table 1. The lump
of clay samples collected from the site was powdered, and the
fine particles passing through 45m sieve was taken and dried in
S. Karthick et al.
the oven for 24 h to get rid of moisture content and used for
further evaluation studies. The chemical composition and
physical properties of the two clay samples are given in Tables
2 and 3, respectively.
2.2. Characterization technique
The chemical composition of WC and BC samples were iden-
tified by using EDAX - TESCAN Model VEGA-3. The clay
samples and corrosion product of the MS and G.I specimens
were retrieved from the clay soil after the exposure period
and the composition/formation of corrosion products were
analyzed using XRD PAN analytical X’PERT PRO system
in Bragg-Brentano geometry using Cu Ka1 (1.540 Å) radiation.
The powder diffraction covered the 10° < 2h > 80°range with
0.0170° steps. Identification of peaks were made by employing
the ‘‘Peak-search” and search match progress built in software
(X-pert-High score plus). The CHNS analysis for clay and cor-
rosion products formed on the surface of the MS and G.I was
identified by CHNS analyzer and the percentage of sulphur
content was calculated. The corrosion products were identified
by X-ray photoelectron spectroscopy (XPS, Thermo, ESCA-
LAB 250Xi, USA).
2.3. Total viable bacteria count
The clay samples are collected from the earth pit, and the bac-
terial count of the samples are estimated as per the procedure
mentioned below: The collected samples were stored in an ice
box and transported to the laboratory. The sample prepara-
tion and enumeration of bacterial species were done by pour
plate technique (Selvam et al., 2012). 1 g of soil sample was dis-
persed with 99 ml of sterile deionized water. It was subjected to
serial dilution and plated by using nutrient agar, Mn agar base,
isolation medium for iron bacteria, Thiobacillus agar by pour
plate method and for sulphate reducing bacteria (SRB) med-
ium by using most probable number technique. The plates
are incubated at 37 °C for 24–48 h and 22 days for SRB. The
total viable bacterial counts were enumerated, and the bacte-
rial population is expressed as colony forming units per gram
(CFU/g).
2.4. Corrosion studies
2.4.1. Preparation of the clay extract and metal sample
preparation – Laboratory study
MS and G.I specimens of 1 cm2 size was cut and the wire was
soldered and sealed with epoxy for electrochemical studies. MS
was given mechanical polishing to remove the superficial rust
and subsequently polished with different grades (0/0, 1/0,
2/0, 3/0 and 4/0) of emery papers and finally degreased with
acetone solvent before use. But the G.I specimens were cleaned
with acetone without damaging the galvanizing coating on the
surface. Both WC and BC samples were crushed and sieved
through 45m sieve to remove the coarse particles. The extracts
were prepared by the sieved clay powder with distilled water in
1:1 ratio and shaken well in a mechanical shaker for 1 h. Then
the extracts were collected by filtration method and used for
immersion studies. The pH of the WC and BC extracts were
2.03 and 2.07 respectively.
Corrosion performance of mild steel and galvanized iron 3303

Fig. 1 Photographic image of the clay (a). White clay and (b). Black clay.

Table 1 Nominal chemical composition of MS and G.I.

Material Chemical composition (wt%)
Fe C Mn Si P S V/Al
MS 98.06 0.09 1.53 0.29 0.013 0.002 0.02
G.I (240 g/cm2) Balance 0.40 0.05 0.40 0.045 0.02

Table 2 Chemical composition of the WC and BC.

Clay Chemical composition (wt%)
Al2O3 SiO2 Fe2O3 SO3 TiO2 K2O Na2O
WC 39.17 51.02 1.23 5.31 1.04 0.07 2.18
BC 32.17 54.02 2.42 6.38 0.59 2.90 1.52

2.4.2. Earth excavation studies and metal sample preparation –
Field study
Earth excavation studies were carried out by using polished
MS and surface cleaned G.I specimens packed in the respective
clay (WC and BC) and excavated in the earth to a depth of 1 m
below ground level. The soil was initially packed under 100%
saturated condition. The whole system was subjected to natu-
ral weathering conditions for an exposure period of 90 days.
MS cylindrical rod of 32 mm dia., with 450 mm length and
G.I cylindrical pipe of 38 mm inner dia., 42 mm outer dia.,
with 450 mm length was taken for the earth excavation studies.
A grove is made, and the wire was soldered in both MS and G.
I and sealed with epoxy, and the connection was taken from
one end of the specimen for potential measurements. Both
the ends of the MS and GI were also sealed with epoxy. Dupli-
cate specimens were used for this study. The photographic
image and the schematic diagram of the earth excavation stud-
ies were given in Fig. 2.
2.5. Electrochemical studies
Open circuit potential measurements were made for MS and
G.I in clay extract medium and earth excavation medium.
But the EIS and potentiodynamic polarization studies were
carried out for the MS and G.I in extract medium only.
2.5.1. Open circuit potential (OCP) measurements
The OCP of MS and G.I specimens exposed to WC and BC
extracts and earth excavation studies are monitored as per
ASTM C 876 at regular intervals and potential vs. time graph
was plotted for 90 days exposure period. The saturated calo-
mel electrode (SCE) is used for this measurement.
2.5.2. Electrochemical impedance spectroscopy (EIS)
EIS measurements were carried out for the MS and G.I in WC
and BC extracts using Gill A.C. Instruments, UK. The mea-
3304 S. Karthick et al.

Table 3 Physical properties of WC and BC.

S. no Properties White clay (WC) Black clay (BC)
1 Color of clay Yellowish white Brownish black
2 Color of extract Light yellowish Dark yellowish orange
3 pH 2. 30 2.07
4 Free chloride ppm – –
5 Sulphate content (%) 5.813 7.019
6 Moisture content (%) 9.23 21.60
7 LOI % 19.69 47.26
8 Conductivity (mS/cm) 6.58–6.4 7.2–7.4
9 Resistivity (Ohm-m) 1.519–1.506 1.388–1.351

surement was made using the three-electrode cell assembly at a
temperature of 30 ± 2 °C. Three electrode cell assemblies were
used for carrying out the experiments. The working electrode
was MS/G.I of 1 cm2 area and the rest of the area is covered
with lacquer. A platinum foil is used as a counter electrode,
SCE as a reference electrode and the both clay extract were
used as an electrolyte. Time intervals of 30–45 min. was given
for each of the systems to attain a steady state i.e. until it
reaches the stable potential and a typical graph between the
real part (Z0r ) and imaginary part (Z00i ) was obtained for var-
ious frequencies ranging from 30 kHz to 10 mHz. This instru-
ment itself is having the provisions for programs to evaluate
the impedance parameters values such as (Icorr, Rct, and Cdl)
by curve fitting method.
2.5.3. Potentiodynamic polarization
The similar electrochemical setup and instrument mentioned
above were used for carrying potentiodynamic polarization
measurement, using which anodic and cathodic polarization
curves were recorded. This instrument itself is having the pro-
vision for programs to evaluate the corrosion kinetic parame-
ters such as Icorr, Ecorr, ba and bc, where ba and bc are the
anodic and cathodic slope of the polarization curve. The
potentiodynamic condition corresponds to a potential sweep
rate of 0.1 mV sec1 and the potential ranges of 200 mV to
+200 mV from the OCP. All the experiments were carried
out at a constant temperature of 30 ± 2 °C. Corrosion current
density was obtained from Rp and the slope of polarization
curve is obtained by using the relation mentioned elsewhere
(Saraswathy and Song, 2007a,b).

Fig. 2 Earth excavation studies (a). Photographic image of WC and BC and (b). Schematic diagram.
Corrosion performance of mild steel and galvanized iron 3305

2.6. Weight loss measurements

2.6.1. In clay extract-laboratory study

Circular MS and G.I pipe (electrodes) was cut from the bulk
specimens. The size of the sample taken was about 30 mm
dia. and 25 mm (MS), 38 mm inner dia., 42 mm outer dia.,
with 25 mm length (G.I) for weight loss measurements. The
MS was given mechanical polishing and degreased with ace-
tone before use. G.I. was just degreased with acetone. Then
both the MS and G.I specimens were initially weighed and
kept immersed in clay extracts. The weight loss experiment
was carried out for 30 and 90 days at room temperature. At
the end of the exposure period the specimens were taken out
and visual observation was made. Then the specimens were
washed with distilled water, dried and final weights are taken.
From the loss in weight, corrosion rate was calculated using
the relationship mentioned elsewhere (Saraswathy and Song,
2007a,b). Fig. 4 EDAX result of BC.

2.6.2. Earth excavation – Field study

Both MS and G.I specimens were weighed before excavation
for corrosion rate measurements. At the end of the exposure
period, the specimens were taken out, and visual observation
was made. Then the specimens were washed with distilled
water, dried and final weights of the specimens are taken.
From the loss in weight corrosion rate was calculated using
the relationship mentioned elsewhere (Saraswathy and Song,
2007a,b).
2.7. Surface examination of MS and G.I
2.7.1. Visual examination
After the exposure period, MS and G.I specimens were exam-
ined visually for corrosion products like red rust, pits formed
on the surface was identified through a magnifying lens.
2.7.2. Scanning electron microscopy (SEM) analysis
SEM images were obtained using HITACHI Model S-3000H
at various magnifications to study the surface morphology of
the MS and G.I in both the clay medium after the exposure
period.
3. Results and discussions
3.1. Characterization technique
3.1.1. EDAX
Figs. 3 and 4 shows the EDAX spectra of the WC and BC sam-
ples. The spectra of both the clay samples contain peaks corre-
sponding to compositional elements such as Ca, C, O, N, Fe,
S, Si, Al. From the weight percentage, it is evident that sulphur
content of 13.07 and 12.48% are observed in the WC and BC.
WC and BC have the Fe content of 12.03 and 23.93% respec-
tively. The iron oxide present in the clay produces certain def-
inite colour dependent on the amount of oxide present. The
colouring effect arises due to the mixed presence of carbon
and iron found in the clay (Goldberg, 1989). When compared
to WC, BC has approximately two times higher percentage of
Fe content and the carbon content is also slightly higher
(0.7%) than the WC. Due to the presence of high iron content
and carbon content the colour of the clay sample is black in
colour. In the WC, the presence of alumina and silicon is evi-
denced from Fig. 3 which gives the white colour of the sample
(Goldberg, 1989), whereas Fig. 4 has no proof of silicon. There
is a small amount of calcium (1.17% and 1.68%) present in
WC and BC and a high degree of sulphate content is evidenced
from the EDAX spectrum of both the clay samples, which is a
prominent causative factor for accelerated corrosion damage
under acidic conditions. This observation was complemented
by the CHNS and XRD studies.

3.1.2. Total viable bacteria count

The bacterial counts of the clay samples were present in the
range from 102 to 106 CFU/g of soil which is given in Table 4.
The higher bacterial counts of acid producing bacteria (sul-
phur oxidizing) and sulphate reducing bacteria are noticed
from the counts. It favoured the production of sulphuric acid
by Thiobacillus species and enhanced the sulphate production
Fig. 3 EDAX result of WC. in both the clay samples. This sulphate ion was utilized by
3306
Table 4 Total viable bacterial counts of WC and BC.
Clay Total viable bacterial counts (CFU/g)
HB IOB
WC 3.2  10 2
3.5  104
BC 1.2  102 4.5  103
*Note: CFU/g-Colony forming units (viable cells), HB - Heterotrophic bacteria, IOB-Iron oxidizing bacteria, MnOB- Manganese oxidizing
bacteria, APB-Acid producing bacteria (Thiobacillus sp), SRB- Sulphate reducing bacteria.
Fig. 5 Potential-time behavior of MS and G.I in clay extract (a) WC and (b) BC.
the sulphate reducing bacteria to generate H2S in the clay
which made the clay, more acidic.
3.2. Electrochemical studies
3.2.1. Open circuit potential
Open circuit potential of MS and G.I in WC and BC extracts
(Fig. 5) studies were monitored for an exposure period of
90 days. Initially MS (Fig. 5a) showed an average potential
of 450 mV vs. SCE in both the WC and BC extracts. After
15 days of exposure the potential was shifted to the active
direction of 570 mV. Further at the 30th day again the poten-
tial was shifted to more active potential of 650 mV. After the
30th day the potential of MS gets stabilized and it remains
same up to 90 days. It indicates, corrosion was initiated within
a week and after that MS was entirely corroded and showed a
more negative potential up to the end of the exposure period.
Fig. 5b indicates that the potential of G.I is 1050 mV at the
initial stage. After an exposure period of 15 days, the potential
was shifted to -1000 mV. After 30 days, the potential was
shifted to 750 mV. This potential shift was due to the disso-
lution of the zinc coating in the organic nature of the soil.
After the 30th day, the G.I has shown a stabilized potential
of 650 mV and it remains saturated until the 90th day. G.I
was coated with zinc to protect mild steel and it has shown
the potential of 1050 mV vs. SCE during the initial period.
After that, the entire zinc layer was dissolved and reached
the steel potential of 650 mV in both the clay extracts. This
is due to the destruction of the coating layer accompanied by
the rapid corrosion of the underlying steel in the organic nat-
ure of the clay soil.
S. Karthick et al.
MnOB APB SRB
2.2  102
4.3  106
1.0  102
2.6  104 6.5  104 1.2  102
Fig. 6a and b depicts the potential-time behavior of MS and
G.I exposed to WC and BC clay earth medium. From the
Fig. 6a, it is observed that within 15 days of exposure the
potential of M.S was shifted to the more active direction
(670 mV) and it reached the steady state potential and
remains stable until the end of the exposure period. G.I has ini-
tially shown a potential of 980 mV and suddenly the poten-
tial was shifted to 725 mV within 6 days and during the 9th
day it reached the potential of 650 mV and after that, the
potential remains stable until the end of the exposure period.
From Fig. 6b it is evident that M.S has shown an initial poten-
tial of 520 mV vs. SCE and after 15 days of exposure the
potential is shifted to the active direction of 650 mV and
after that it remains stable until the end of the exposure period
in the BC clay medium. The same trend was observed for G.I.
also. Initially G.I has shown a potential of 990 mV vs. SCE
and 2nd day the potential is shifted to 800 mV and from 5th
day onwards the potential was shifted to 660 mV and it
remains stable until the end of the exposure period. It is
observed that the clay medium has shifted the potential of
MS and G.I to the active direction at a faster rate than the
extract medium. This is due to the presence of microbes pre-
sent in the organic soil which reacts with both MS and G.I
and accelerated the corrosion. The same observation was
noticed by Denison and Romanoff (1952). From the results,
it is seen that G.I was corroding at a faster rate (by exposing
the base metal) than M.S in both the clay environments due
to the insufficient zinc coating thickness provided on the G.I.
metal surface (Denison and Romanoff, 1952).
Corrosion performance of mild steel and galvanized iron 3307

Fig. 6 Potential-time behavior of MS and G.I in earth medium (a).WC and (b). BC.

Fig. 7 Nyquist plots for MS and G.I in WC and BC extract medium (a). MS-1st day of exposure; (b). G.I-1st day of exposure; (c).MS-
after 90 days of exposure; (d). G.I- after 90 days of exposure.

3.2.2. Electrochemical impedance spectroscopy
EIS measurements for the MS and G.I were carried out in WC
and BC extract media. Fig. 7a and b depict the Nyquist plots
taken for MS and G.I during the 1st day of exposure and
Fig. 7a and b after 90 days of exposure respectively. The impe-
dance parameters derived from the curves were presented in
Table 5. In WC extract, the Icorr value of MS and G.I during
the 1st day of exposure was found to be 0.174 and
0.446 mA/cm2 respectively. After 90 days of exposure Icorr
value was increased to 0.500 and 1.121 mA/cm2 for MS and
G.I respectively. Rct values observed for MS and G.I. during
the initial exposure was 149 and 58 O cm2 and after 90 days
the Rct value was found to be 52 and 23 O cm2 respectively.
The corrosion rate measured for MS and G.I was 2.025 and
3308 S. Karthick et al.

Table 5 AC-impedance parameters for MS and G.I in clay extract.

Clay Material Initial exposure (1st day) After 90 days of exposure
Rct (O cm2) Icorr (mA cm2) Corrosion rate (mmpy) Rct (O cm2) Icorr (mA cm2) Corrosion rate (mmpy)
WC MS 149 0.174 2.025 52 0.500 5.802
G.I 58 0.446 7.780 23 1.121 12.990
BC MS 80 0.326 3.779 26 0.985 11.430
G.I 45 0.696 6.601 21 1.220 14.140

7.780 mmpy during the initial days of exposure and after
90 days of exposure the corrosion rate values are increased
to 5.802 and 12.990 mmpy for MS and G.I respectively.
Whereas in BC extract the corrosion rate for MS and G.I
was observed to be 3.779 and 6.601 mmpy during the initial
exposure and it was increased to 11.43 and 14.14 mmpy after
90 days of exposure respectively. Rct values found for the
MS and G.I during the initial period of exposure was 80 and
45 O cm2 and it was reduced to 26 and 21 O cm2 after 90 days
of exposure respectively. The Icorr values measured for MS and
G.I was 0.326, 0.696 mA/cm2 and 0.985 and 1.22 mA/cm2 dur-
ing the initial period and after 90 days of exposure respectively.
An appreciable decrease in Rct values and increase in Icorr val-
ues indicates the severity of corrosion of both the metals in the
clay extracts. The capacitive loop formed at the high frequency
shows the resistance and capacitance generated by the penetra-
tion of ions into the metal surface forming a corrosion product
on the surface of the metal (Tang and Davenport, 2007;
Okeoma et al., 2012).
3.2.3. Pontentiodynamic polarization
Potentiodynamic polarization measurements carried out for
the MS and G.I steel in WC and BC clay extract medium.
Fig. 8 depicts the typical polarization curves for MS and G.I
in both the clay extracts during the initial exposure (Fig. 8a–
b) and (Fig. 8c–d) after 90 days of exposure. The corrosion
kinetic parameters obtained from the curves were given in
Table 6. It can be seen that the corrosion rate increases with
an increase in the exposure period. Initially G.I was showing
a potential of 982 and 1008 mV vs. SCE in WC and BC

Fig. 8 Potentiodynamic polarisation curves for MS and G.I in WC and BC extract medium (a). MS-1st day of exposure; (b). G.I-1st day
of exposure (c). MS- after 90 days of exposure; (d). G.I- after 90 days of exposure.
Corrosion performance of mild steel and galvanized iron 3309

Table 6 Polarization parameters for MS and G.I in clay extract.

Clay Material Initial exposure (1st day) After 90 days of exposure
Ecorr (mV vs. Icorr (mA/ Corrosion rate Ecorr (mV vs. Icorr (mA/ Corrosion rate
SCE) cm2) (mmpy) SCE) cm2) (mmpy)
WC MS 534 0.004 0.054 652 0.122 1.141
G.I 982 0.010 0.117 640 0.343 3.986
BC MS 624 0.072 0.840 652 0.213 2.478
G.I 1008 0.105 1.227 656 0.400 4.637

Fig. 9 Photographic image of MS (a&c) and G.I (d&b) specimens after electrochemical studies.

environment respectively. But after 90 days of exposure G.I
was showing a potential of 640 and 656 mV vs. SCE in
WC and BC environment, which indicated that galvanized
coating was dissolved completely in the exposed environment
and the bare metal was exposed showing the potential of
MS. The same observation was noticed in the OCP measure-
ments also. Further, the corrosion rate obtained was higher
than that of the weight loss measurements. This is visually seen
in Fig. 9 that; severe corrosion product is observed on the sur-
face of MS and G.I specimens. It indicates that a significant
amount of metal is lost at the end of the exposure period.
When comparing the performance of MS and G.I, G.I has cor-
roded at a faster rate than MS due to the dissolution of the
zinc layer in both (WC and BC) clay extract media (Denison
and Romanoff, 1952).
3.3. Characterization of MS and G.I
3.3.1. XRD
The XRD pattern of both the clay samples and corrosion
products of are presented in Figs. 10 and 11. It can be seen
that, the XRD peaks for the clay samples are similar, with
peaks at 12.03°, 20.18°, 24.8°,26.9°, 34.5°, 35.4° and 38.5° cor-
responding to the crystal planes of zeolite, SiO2, Fe4(CO)13C,
kaolinite, FeSO4, FeS2 and CaCO3 respectively. The presence
of FeSO4, FeS2 and CaCO3 crystal phases is a causative factor
for accelerated corrosion. Fe2O3, FeO, FeSO4, Fe2S and Fe
(OH)3 are noticed on the electrode surface of mild steel
exposed to WC and BC medium. In the case of G.I, it is
observed that the increase in iron oxide peak at 26.9° and zinc
oxide peaks at, 45.7° and 50.2° respectively. G.I pipes are
3310 S. Karthick et al.

Fig. 12 CHNS analysis of WC, BC and corrosion products of

MS and G.I.

3.3.2. CHNS analyzer

CHNS analysis is conducted in to compare the sulphate con-
Fig. 10 XRD pattern for: (a) WC; (b) corrosion products of MS; tent present in the WC, BC and MS and G.I electrode surface
(c) G.I. and the data are presented in Fig. 12. It is seen from the figure
that the sulphur content found in the corrosion products of
MS and G.I were 10.5 and 11.6% and the sulphur content pre-
sent in the WC was 4.8% respectively. The sulphur content
found in MS and G.I in BC is found to be 12.5% and
13.5% respectively. The presence of sulphur content in both
MS and G.I are higher than the WC and BC. The sulphate
ions reacted with the metal iron and thereby plenty of corro-
sion products is deposited on MS and G.I pipes. Moreover,
the presence of Thiobacillus species enhanced the sulphuric
acid and sulphate formation on the electrode surface. Similar
results were observed in BC also. When comparing the two
clay samples, the sulphate content was higher in BC than
WC. When comparing MS and G.I, G.I is having higher sul-
phate content.

3.4. Weight loss measurements

3.4.1. In clay extract

The corrosion rate of MS and G.I pipe in WC and BC extracts
for the exposure period of 30 and 90 days were given in Table 7.
From the Table 7, it was observed that the extent of corrosion

Fig. 11 XRD pattern for: (a) BC; (b) corrosion products of MS;
(c) G.I. Table 7 Corrosion rate of MS and G.I in WC and BC extracts
by weight loss measurements.
Clay Steel Corrosion rate (mmpy)

coated with zinc to protect mild steel in the aqueous environ- 30 days of exposure 90 days of exposure
ment. The zinc coating gets dissolved when it was exposed to WC MS 0.394 0.410
the acidic environment over a longer duration. The dissolution G.I 0.417 0.468
of zinc coating increased the corrosion of GI in acidic (organic) BC MS 0.479 0.487
soil environment (Denison and Romanoff, 1952). G.I 0.569 0.579
Corrosion performance of mild steel and galvanized iron 3311

Fig. 13 Photographic image of MS (a-c) and G.I (d-f) before and after exposure in clay extract.

3.5. Surface examination studies

Table 8 Corrosion rates of MS and G.I in WC and BC 3.5.1. Visual observation

exposed to earth excavation studies by weight loss Fig. 13 shows the MS and G.I samples before and after 90 days
measurements. of exposure in WC and BC extract medium. Both the MS and
Clay Steel Exposure period (90 days) G.I samples are fully covered with severe corrosion products
on the exposed surface. When comparing both the clays, the
Weight loss (g) Corrosion rate (mmpy)
samples exposed to BC was severely attacked and showing red-
WC MS 2.260 0.538 dish brown corrosion products, and in MS samples blistering
G.I 4.310 0.587 and severe corrosion products are visible on the exposed sur-
BC MS 3.350 0.761 face. In G.I the galvanizing coating is completely disappeared,
G.I 4.680 1.130 and the exposed surface is completely changed into brownish
red colour due to the reaction with the acidic nature of the
extract and the base metal was exposed.
Fig. 14 shows the MS and G.I to WC and BC after 90 days
of exposure under buried condition. From the figure, it is
observed that, G.I was severely affected by the bulk volume
is more in the case of G.I when compared to MS. It is noted
of corrosion products (ZnO) which was well evidenced by
that an average of 10% increase in corrosion rate is observed
the XRD results. The galvanized coating was completely eaten
in both the clay extracts after 90 days of exposure due to the
away by the acid present in the clay. In the case of MS also the
corrosion process. This was supported by Fig. 13 that, the sur-
surface of the samples was entirely covered with blackish
face of MS and G.I was damaged due to the severe corrosion
brown Fe(OH)3, Fe2O3 and Fe3O4 rust products.
and severe rust products are observed on the surface of MS
and G.I after 90 days of exposure.
3.5.2. SEM analysis
3.4.2. In clay medium – Field exposure studies The SEM microstructure of bare MS and G.I surface before
the exposure is given in Fig. 15a and b. It shows the smooth
Table 8 shows the corrosion rate of MS and G.I specimens
surface of MS and G.I, indicating there is no corrosion formed
buried in clay medium for an exposure period of 90 days. G.
on the surface of MS and G.I. The Fig. 16a and c shows the
I specimen showed more weight loss than MS. The corrosion
SEM images at various magnifications (500, 1.0 k and
rate of MS is 0.538 and 0.761 mmpy and the corrosion rate
5.0 k) of MS surface in WC after the exposure period of
of G.I is 0.5870 and 1.130 for WC and BC respectively.
90 days. From the microstructure, it is seen that a rough sur-
3312 S. Karthick et al.

Fig. 14 Photographic images of MS (a&b) and G.I (c&d) after exposure in earth excavation medium.

Fig. 15 SEM micrographs of polished (a). MS and (b). G.I.

face is observed with severe corrosion spots in different shapes
is exhibited in Fig. 16a. It is due to the acidic nature of the WC
which leads to the formation of corrosion products on MS sur-
face. The corrosion products are evidenced from Fig. 16b. A
closer view of a corrosion product is magnified and depicted
in Fig. 16c. From Fig. 16c it can be observed that the spot
was filled with spongy like crystalline layers of corrosion prod-
ucts on the surface of the MS.
Fig. 16d–f shows the SEM microstructure of G.I surface at
various magnifications in WC clay after the exposure period of
90 days. From the SEM image, it is observed that severe dete-
rioration of the smoothness of the G.I surface is noticed. This
may be due to the reason that the acidic nature of WC which
disintegrated the coating, and the top layer of the coating gets
completely damaged forming the corrosion products on the
surface of the steel. Fig. 16d shows the deposits of white rust
products (ZnO) is spread over the surface due to the aggressive
attacks of the corroding medium on the G.I surface. After
increasing the magnification (Fig. 16e–f), the zinc metal was
partially dissolved to form zinc oxide. The dissolution of zinc
oxide created micro voids and micro cracks in the intergranu-
lar zones due to the insufficient coating thickness and poor
adhesion of the coating (Okeoma et al., 2012).
Fig. 17a–c shows SEM microstructure of MS surface in BC
at various magnifications after 90 days exposure period. It is
seen that the unusual structure of iron corrosion formation
on the MS surface along with many pits with different shapes
are observed in Fig. 17a. When increasing the magnification of
Corrosion performance of mild steel and galvanized iron
Fig. 16 SEM micrographs-after 90 days of exposure in WC medium (a–c). MS and (d–f). G.I.
a pit, irregular and rod-shaped microorganisms, as well as cor-
rosion products, are found in the pit which is clearly evidenced
from Fig. 17b–c (De Lima-Neto et al., 2007). Fig. 17 d-f show
the SEM microstructure of G.I in BC at various magnifica-
tions after the exposure period. From the Fig. 17d, unusual
delaminated deposits of corrosion products are observed on
the surface of G.I. Severe corrosion product and cracks are vis-
ible on the surface of G.I. With increasing magnification, GI
surface has shown a cracked zinc layer and symptoms of inter-
granular corrosion running along the grain boundaries
observed from Fig. 17e–f (Urgell et al., 2007; Srivastava and
Balasubramaniam, 2005).
3.5.3. XPS analysis
XPS spectra of corrosion products are presented in Fig. 18a–b.
From this figure the C1s, Fe2p and O1s were observed in MS
and G.I electrode surface, while a new peak of Zn2p (1021 eV)
was detected on G.I electrode surface, as shown in Fig. 18b.
These results confirmed the rapid dissolution of zinc in a clay
medium over a longer duration (Denison and Romanoff,
1952).
Figs. 19 and 20 illustrate the high-resolution XPS spectra of
C1s, Fe2p and O1s obtained from the corrosion products of
MS and G.I electrode surface, respectively. It is seen from
Fig. 19a and 20a that the C1s spectra is composed of two peaks
at 284.8 eV and 288.97 eV, which is corresponds to CAC and
3313
CAO species respectively (Angellier et al., 2005; Rindlav-
Westling and Gatenholm, 2003), which may be present in clay.
Fe2p spectra of corrosion products of MS and G.I on the elec-
trode surface are shown in Fig. 19b and 20b, respectively. The
high-resolution spectra of Fe2p peaks at 711.9 eV (Fe2p3/2)
and 724.11 eV (Fe2p1/2) may be associated with FeOOH
and Fe2O3, respectively (Zhou et al., 2011; Graat and
Somers, 1996). The peaks of Fe2p1/2 was detected at about
727.42 eV indicating the formation of mixed oxides of Fe(II)
and Fe(III), such as Fe3O4. The peaks of 714 eV further con-
firm the formation of Fe3O4 (Changjing et al., 2014). Further,
the peaks at 719.1 eV and 732.26 eV were corresponding to
shake up satellite features of Fe2p3/2 and Fe2p1/2 respectively
(Sharan et al., 2015). Fig. 19c shows the O1s peaks of MS elec-
trode surface, it is composed of the two peaks at 529.78 eV and
532.08 eV; the first peak is corresponding to the binding energy
of the O2 and OH ions, which is in agreement with the pres-
ence of the iron oxide/hydroxide layer as detected in the
Fe2p3/2 spectrum (Ochoa et al., 2013). The signals at 532.08
also corresponds to CAO and OACAO species (Liu et al.,
2015), which may be present in the clay.
Further, in Fig. 20d shows the Zn2p spectra of the corro-
sion product of G.I surface. The two peaks at about 1021 eV
and 1023.08 eV, which is corresponding to the Zn and ZnO
respectively (Zhang et al., 2017). These results confirm the fact
that dissolution of zinc coating, when exposed to the acidic
environment over a longer duration. Fig. 20c shows the O1s
3314 S. Karthick et al.

Fig. 17 SEM micrographs - after 90 days of exposure in BC medium (a–c). MS and (d–f). G.I.

Fig. 18 XPS survey spectra for corrosion products of (a). MS and (b). G.I.
Corrosion performance of mild steel and galvanized iron 3315

Fig. 19 XPS spectra for corrosion products of MS (a). C1s; (b). Fe2p and (c). O1s.

spectra for corrosion product of G.I electrode, these three of 20–45 °C, and it is active at a pH of 0.5–6.0. It uses sulphur
peaks at the binding energy of 529.92 eV, 531.32 eV and as its primary energy source, and both the bacteria are abun-
532.43 can be attributed to FeO or Fe2O3 or ZnO, FeOOH dant in natural environments associated with pyritic ore bod-
or ZnOOH respectively (Zhang et al., 2017). XPS spectra con- ies, commonly found in clay soil, sewer pipes, coal deposits,
firmed the oxidation state of corrosion products namely FeO, and their acidified drainages (Al-Judaibi and Al-Moubaraki,
Fe2O3, FeOOH and ZnO. 2013, Ozgowicz et al., 2012; Rohwerder et al., 2003;
Gonzalez-Toril et al., 2003).
3.6. Mechanism The following reactions take place in MS and G.I pipes
during the earth excavation studies. The ferric ion reacts with
The following mechanism for the corrosion of MS and GI the FeS2 (pyrite) leading to the dissolution of ferrous iron. This
pipes in buried clay soil environment is as follows: is further oxidized by ferric iron to produce sulphate. The reac-
Fig. 21 shows the graphical representation, which depicts tion generates more acid (Davis et al., 2000; Schippers and
the corrosion damage of MS and GI pipe (zinc coated mild Sand, 1990; Steudel, 1996; Hackl et al., 1995; Hansford and
steel) in acidic clay soil. The compounds present in the soil Vargas, 2001).
such as FeS2, Fe2SO4 and CaCO3, etc. are converted to sulfuric þ
FeS2 þ 6Fe3þ þ 3H2 O ! 7Fe2þ þ S2 O2
3 þ 6H ð1Þ
acid and sulphate by Thiobacillus species such as T. ferrooxi-
dans and T. thiooxidans. thiobacillus is a gram-negative bac- þ
3 þ 8Fe
S2 O2 þ 5H2 O ! 8Fe2þ þ 2SO2
4 þ 10H ð2Þ
3þ
terium generally gains energy from the oxidation of reduced
sulfur compounds present in the soil environment. T. ferroox- The dissolution of pyrite by ferric iron along with oxidation
idans is an autotrophic bacteria and it is more active under the of the ferrous iron constitutes a cycle of dissolution of pyrite.
pH 1.5–2.5, and temperature 15–25 °C. This type of bacteria Ferric iron precipitates as hydrated iron oxide as follows:
derives energy from the oxidation of ferrous to ferric ion and Fe3þ þ 3H2 O $ FeðOHÞ3 þ 3Hþ ð3Þ
reduces sulphur compounds to sulphuric acid. T. thiooxidans
is a mesophilic bacteria which grows in moderate temperature FeðOHÞ3 ! Fe2 O3 ð4Þ
3316 S. Karthick et al.

Fig. 20 XPS spectra for corrosion products of G.I (a). C1s; (b). Fe2p and (c). O1s & Zn2p.

Fig. 21 Graphical abstract for corrosion of MS in clay medium.

Corrosion performance of mild steel and galvanized iron
Fe(OH)3 precipitate leads to the formation of yellow,
orange or red deposits on the surface (Figs. 9 and 13) of the
MS and GI. It further oxidized to form Fe2O3 (brown rust).
4. Conclusions
The following conclusions can be drawn from the present
investigation:
 The relative corrosion performance of MS and G.I was car-
ried out in WC and BC.
 Chemical analysis confirmed that both the clays are acidic
in nature. The acidic clays were often associated with high
levels of organic matter.
 Weight loss measurements indicated that G.I has corroded
at a faster rate than MS in both the clay extracts due to the
rapid dissolution of the coating which is due to the reduced
thickness of the zinc coating layer.
 Earth excavation studies showed that the presence of
Thiobacillus bacteria induced the acidic nature of the soil
and enhanced the corrosion of MS and GI pipes.
 Open circuit potential measurements revealed that the
entire zinc coating was dissolved in G.I within 10 days of
exposure and showed a mild steel potential of -650 mV in
both the clay extracts. The destruction of the coating was
accompanied by a rapid corrosion of the underlying steel
due to the lesser coating thickness.
 Polarization measurements indicated severe corrosion prod-
ucts on the surface of MS and G.I specimens at the end of
the exposure period showing the significant amount of
metal loss.
 An appreciable decrease in Rct values and increase in Icorr
values indicated the severity of corrosion of metals (MS
and G.I) in both the clay extracts.
 The XRD and CHNS results showed that the sulphur con-
tent present in corrosion products MS and G.I are found to
be higher than the WC and BC.
 G.I used in this study was having a coating weight of (240 g/
cm2). Due to the lesser coating weight G.I corroded at a fas-
ter rate than MS in both WC and BC. This is to the insuf-
ficient coating thickness given to the G.I. The minimum
layer thickness required as per ASTM A 123 is 35m micron
(245 g/cm2) minimum and a maximum of 100 m (705 g/cm2)
is required for underground buried structures.
 From the study, it is further concluded that, if the structure
was exposed to the aggressive environment, some precau-
tionary measures should be undertaken to ensure the coat-
ing thickness of the zinc layer.
Acknowledgements
Authors thank Director, CSIR-CECRI, Karaikudi, India for
his kind permission to publish this paper.
References
Al-Judaibi, A., Al-Moubaraki, A., 2013. Microbial analysis and
surface characterization of SABIC carbon steel corrosion in soils
of different moisture levels. Adv. Biol. Chem. 3, 264–273. https://
doi.org/10.4236/abc.2013.32030.
3317
Angellier, H., Molina-Boisseau, S., Belgacem, M.N., Dufresene, A.,
2005. Chemical surface modification of waxy maize starch
nanocrystals. Langmuir 21, 2425–2433. https://doi.org/10.1021/
la047530j.
Borenstein, S.W., 1994. Microbiologically Influenced Corrosion,
Handbook. Woodhead publishing Ltd., Cambridge UK.
Changjing, Fu, Zhao, Guogang, Zhang, Haijun, Li, Shuang, 2014. A
facile route to controllable synthesis of Fe3O4/graphene composites
and their application in lithium-ion batteries. Int. J. Electrochem.
Sci. 9, 46–60 http://www.electrochemsci.org/papers/vol9/90100046.
pdf.
Choi, Y.S., Nesic, S., Ling, S., 2011. Effect of H2S on the CO2
corrosion of carbon steel in acidic solutions. Electrochemi. Acta 56,
1752–1760. https://doi.org/10.1016/j.electacta.2010.08.049.
Costa Pereira, R.F., Dantas de Oliveira, E.S., Gomes de Andrade
Lima, M.A., Cezar Brasil, S.L.D., 2015. Corrosion of galvanized
steel under different soil moisture contents. Mater. Res. 18, 563–
568. https://doi.org/10.1590/1516-1439.341714.
Cole, I.S., Marney, D., 2012. The science of pipe corrosion: A review
of the literature on the corrosion of ferrous metals in soils. Corr.
Sci. 56, 5–19. https://doi.org/10.1016/j.corsci.2011.12.001.
Das, G.S., 2014. Influence of hydrogen sulfide on CO2 corrosion in
pipeline steel. Int. J. Eng. Res. Technol. 3, 2224–2228. ISSN: 2278-
0181.
Davis, R.A., Welty, A.T., Borrego, J., Morales, J.A., Pendon, J.G.,
Ryan, J.G., 2000. Rio Tinto estuary (Spain): 5000 years of
pollution. Environ. Geol. 39, 1107–1116. https://doi.org/10.1007/
s002549900096.
De Lima-Neto, P., Correia, A.N., Colares, R.P., Araujo, W.S., 2007.
Corrosion study of electrodeposited Zn and Zn-Co coatings in
chloride medium. J. Br. Chem. Soc. 18, 1164–1175. https://doi.org/
10.1590/S0103-50532007000600010.
Denison, I.A., Romanoff, M., 1952. Corrosion of galvanized steel in
soils. J. Res. Natl. Bureau Standards 49, 299–314 http://nvlpubs.
nist.gov/nistpubs/jres/049/5/v49.n05.a02.pdf.
El-Shamy, A.M., Soror, T.Y., El-Dahan, H.A., Ghazy, E.A., Eweas,
A.F., 2009. Microbial corrosion inhibition of mild steel in salty
water environment. Mater. Chem. Phys. 114, 156–159. https://doi.
org/10.1016/j.matchemphys.2008.09.003.
EI-Shamy, A.M., Shehata, M.F., Ismail, A.I.M., 2015. Effect of
moisture contents of bentonitic clay on the corrosion behavior of
steel pipelines. Appl. Clay Sci. 114, 461–466. https://doi.org/
10.1016/j.clay.2015.06.041.
Goldberg, S., 1989. Interaction of aluminum and iron oxides and clay
minerals and their effect on soil physical properties: A review.
Commun. Soil Sci. Plant Analy. 20, 1181–1207. https://doi.org/
10.1080/00103629009368144.
Gonzalez-Toril, E., Llobet-Brossa, E., Casamayor, E.O., Amann, R.,
Amils, R., 2003. Microbial ecology of an extreme acidic environ-
ment. The Tinto River Appl. Environ. Microbiol. 69, 4853–4865.
https://doi.org/10.1128/AEM.69.8.4853-4865.2003.
Graat, P.C., Somers, M.A.J., 1996. Simultaneous determination of
composition and thickness of thin iron-oxide films from XPS Fe 2p
spectra. Appl. Surf. Sci. 100 (101), 36–40. https://doi.org/10.1016/
0169-4332(96)00252-8.
Hackl, R.P., Dreissinger, D.B., Peters, E., King, J.A., 1995. Passiva-
tion of chalcopyrite during oxidative leaching in sulfate media.
Hydrometallurgy 39, 25–48. https://doi.org/10.1016/0304-386X(95)
00023-A.
Hansford, G.S., Vargas, T., 2001. Chemical and electrochemical basis
of bioleaching processes. Hydrometallurgy 59, 135–145. https://doi.
org/10.1016/S0304-386X(00)00166-3.
Javaherdashti, R., Nwaoha, C., Tan, H., 2013. Corrosion and
materials in the oil and gas industries. In: Cathodic Protection in
the Oil and Gas Industry. CRC Press, Tailor & Francis Group,
London, p. 489. ISBN 9781466556249.
Li, W., Zhou, Y.J., Yan, X., 2012. Corrosion behavior of 110S tube
steel in environments of high H2S and CO2 content. J. Iron Steel
3318
Res. Int. 19, 59–65. https://doi.org/10.1016/S1006-706X(13)60033-
3.
Maslehuddin, M., Al-Zahrani, M.M., Ibrahim, M., Al-Methel, M.H.,
Al-Idi, S.H., 2007. Effect of chloride concentration in soil on
reinforcement corrosion. Constr. Build. Mater. 21, 1825–1832.
https://doi.org/10.1016/j.conbuildmat.2006.05.019.
Okeoma, K.B., Owate, I.O., Oguzie, E.E., Mejeh, I.M., 2012. Impacts
of heat treatment on the electrochemical properties of AA3003
expose to 0.1M hydrochloric acid media. Am. J. Mater. Sci. 2, 51–
58. https://doi.org/10.5923/j.materials.20120201.10.
Ochoa, N., Bello, M., Sancristobal, J., Balsamo, V., Albornoz, A.,
Britoc, J.L., 2013. Modified cassava starches as potential corrosion
inhibitors for sustainable development. Mater. Res. 16 (6), 1209–
1219 http://www.scielo.br/pdf/mr/v16n6/aop_1613.pdf.
Ozgowicz, W., Kurc-Lisiecka, A., Grajcar, A., 2012. Corrosion
behaviour of cold-deformed austenitic alloys. In: Benjamin Valdez
(Ed.), Environmental and Industrial Corrosion - Practical and
Theoretical Aspects. InTech, DOI: 10.5772/53590. Available from:
https://www.intechopen.com/books/environmental-and-industrial-
corrosion-practical-and-theoretical-aspects/corrosion-behaviour-
of-cold-deformed-austenitic-alloys
Padilla, V., Ghods, P., Alfantazi, A., 2013. Effect of de-icing salts on
the corrosion performance of galvanized steel in sulphate contam-
inated soil. Constr. Build. Mater. 40, 908–918. https://doi.org/
10.1016/j.conbuildmat.2012.09.077.
Rindlav-Westling, A., Gatenholm, P., 2003. Crystallinity and mor-
phology in films of starch, amylose and amylopectin blends.
Biomacromolecules 4, 166–172 https://pubs.acs.org/doi/abs/10.
1021/bm010114i.
Rohwerder, T., Gehrke, T., Kinzler, K., Sand, W., 2003. Bioleaching
review part A: progress in bioleaching: fundamentals and mecha-
nisms of bacterial metal sulfide oxidation. Appl. Microbiol. Biotech-
nol. 63, 239–248. https://doi.org/10.1007/s00253-003-1448-7.
Saraswathy, V., Song, H.W., 2007a. Corrosion monitoring of rein-
forced concrete structures-A review. Int. J. Electrochem. Sci. 2, 1–
28 http://pdf.easechem.com/pdf/07/2010001.pdf.
Saraswathy, V., Song, H.W., 2007b. Improving the durability of
concrete using inhibitors. Build. Environ. 42, 464–472. https://doi.
org/10.1016/j.buildenv.2005.08.003.
Schippers, A., Sand, W., 1990. Bacterial leaching of metal sulfides
proceeds by two indirect mechanisms via thiosulfate or via
polysulfides and sulfur. Appl. Environ. Microbiol. 65, 319–321
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC91023/pdf/
am000319.pdf.
Selvam, A., Challaraj Emmanuel, E.S., Anand kumar, B., Marutha-
muthu, S., Palaniswamy, N., 2012. Studies on the distribution of
bacterial isolates in rare earth environment. J. Environ. Biol. 33,
143–148. ISSN: 0254-8704.
Liu, Sen, Wang, Ziying, Zhang, Yong, Dong, Zhuo, Zhang, Tong,
2015. Preparation of zinc oxide nanoparticle–reduced graphene
oxide–gold nanoparticle hybrids for detection of NO2. RSC Adv. 5,
91760–91765 https://pubs.rsc.org/en/content/articlepdf/2015/ra/
c5ra18680c.
S. Karthick et al.
Sharan, C., Khandelwal, P., Poddar, P., 2015. The mechanistic insight
into the bio milling of goethite (a-FeO(OH)) nanorods using the
yeast Saccharomyces cerevisiae. RSC Adv. 5, 91785–91794 https://
pubs.rsc.org/en/content/articlehtml/2015/ra/c5ra16951h.
Srivastava, A., Balasubramaniam, R., 2005. Microstructural charac-
terization of copper corrosion in aqueous and soil environments.
Mater. Characteriz. 55, 127–135. https://doi.org/10.1016/
j.matchar.2005.04.004.
Steudel, R., 1996. Mechanism for the formation of elemental sulfur
from aqueous sulfide in chemical and microbiological desulfuriza-
tion processes. Ind. Eng. Chem. Res. 35, 1417–1423. https://doi.
org/10.1021/ie950558t.
Tang, J., Shao, Y., Guo, J., Zhang, T., Meng, G., Wang, F., 2010. The
effect of H2S concentration on the corrosion behaviour of Carbon
steel at 90°C. Corr. Sci. 52, 2050–2058. https://doi.org/10.1016/
j.corsci.2010.02.004.
Tang, Y.C., Davenport, A.J., 2007. Magnetic field effects on the
corrosion of artificial pit electrodes and pits in thin films. J.
Electrochem. Soc. 154, C362–C370. https://doi.org/10.1149/
1.2736662.
Urgell, O.M., Rangel, E.R., Gomezyanez, C., 2007. Reaction bonding
of zinc oxide (RBZO) toproduce ZnO-based varistors. Azo J.
Mater. Article ID 3842.
Verink Jr. E.D., Heidersbach Jr, R.H., 1972. ASTM STP -516,
American Society for Testing and Materials, pp. 303–322.
Wu, Q.L., Zhang, Z.H., Dong, X.M., Yang, J.Q., 2013. Corrosion
behavior of low-alloy steel containing 1% chromium in CO2
environments. Corros. Sci. 75, 400–408. https://doi.org/10.1016/
j.corsci.2013.06.024.
Yan, Y., Li, B., Guo, W., Pang, H., Xue, H., 2016a. Vanadium based
materials as electrode materials for high performance supercapac-
itors. J. Power Sources 329, 148–169. https://doi.org/10.1016/j.
jpowsour.2016.08.039.
Yan, Y., Gu, P., Zheng, S., Zheng, M., Pang, H., Xue, H., 2016b.
Facile synthesis of an accordion-like Ni-MOF superstructure for
high-performance flexible supercapacitors. J. Mater. Chem. A 2016
(4), 19078–19085 https://pubs.rsc.org/en/content/articlepdf/2016/
ta/c6ta08331e.
Yan, Y., Luo, Y., Ma, J., Li, B., Xue, H., Pang, H., 2018. Facile
synthesis of vanadium metal-organic frameworks for high-perfor-
mance supercapacitors. Small 14, 1801815–1801823. https://doi.
org/10.1002/smll.201801815.
Zhang, Y., Xiao, Z., Zhao, Y., Li, Z., Xing, Y., Zhou, K., 2017. Effect
of thermo-mechanical treatments on corrosion behavior of
Cu15Ni-8Sn alloy in 3.5 wt% NaCl solution. Mater. Chem. Phys.
199, 54–66. https://doi.org/10.1016/j.matchemphys.2017.06.041.
Zhou, J.S., Song, H.H., Ma, L.L., Chen, X.H., 2011. Mag-
netite/graphene nanosheet composites: interfacial interaction and
its impact on the durable high-rate performance in lithium-ion
batteries. RCS Adv. 1, 782–791 https://pubs.rsc.org/en/content/
articlehtml/2011/ra/c1ra00402f.