Indian Journal of Chemical Technology

Vol. 16, May 2009, pp. 216-220

Characterization of corrosion resistance properties of sol-gel alumina coating in

mine water environment
G Ruhi, O P Modi, A K Jha & I B Singh*
Advanced Materials and Processes Research Institute, CSIR, Hoshangabad Road, Bhopal 462 026, India
Email: ibsingh58@yahoo.com
Received 11 August 2008; revised 6 February 2009
Sol-gel alumina coating was developed on mild steel surface by using dip coating technique. Prior to the sol-gel coating,
the substrate was treated with zinc-phosphating solution to improve the bonding of the coating. The corrosion resistance
properties of the sol-gel alumina coated, uncoated and surface pre-treated substrates were evaluated in an artificial mine water
solution. Electrochemical measurements like OCP variation with time, partial polarisation and electrochemical impedance
analysis were carried out to evaluate corrosion resistance properties of the coatings. The microstructure and compositional
analysis of the sol-gel coated specimens were investigated by SEM and XRD, respectively. The experimental results exhibited a
significant improvement in the corrosion resistance of the sol-gel coated specimens as compared to the uncoated and surface
pre-treated specimens. The SEM micrographs showed the presence of a compact coating of thickness 20 micron (approx). The
XRD spectrum of the sol-gel coated specimens suggested the presence of -alumina phase in the coating.
Keywords: Mild steel, X-Ray diffraction, SEM, Sol-gel alumina coating

Mine water found in coal mines is highly corrosive

because of its complex and corrosive nature1,2. It is
generally acidic (pH=2.5) and contains a very high
concentration of sulphate (SO42-) and chloride (Cl-)
ions. Due to low pH of mine water, the hydrogen
evolution reaction becomes more pronounced leading
to an increase in the corrosion phenomena. The
presence of sulphate and chloride ions in mine water
further aggravates the aggressiveness of this
environment.
Because of good machinability and low cost, mild
steel is extensively used as a structural material for
different machineries employed during the
exploration of coal from the coal mines. However, the
service life of these machines reduces substantially in
this particular environment due to aggressiveness of
the environment. Application of corrosion resistant
barrier coatings on corrosion prone metals like mild
steel play a significant role in their protection from
corrosive environments3-5. Sol-gel based anti
corrosive coatings is one of them6,7. Sol-gel based
corrosion resistant coatings have been applied
successfully on various steels to protect them from
different corrosive environments8-15. To the best of
our knowledge, no scientific information is available
in the literature on the development of sol-gel alumina
coating for the protection of mild steel substrate in
mine water environment.

In view of above, an attempt has been made in the

present study (i) to develop sol-gel alumina coating
on mild steel substrate and (ii) to investigate its
corrosion resistance behavior in mine water. Prior to
the sol-gel coating development, the substrate has
been pre-treated in zinc-phosphating solution to
improve the adherence of sol-gel coating. The
detailed description of zinc-phosphate treatment is
given elsewhere16. An artificial mine water solution
was prepared in the laboratory as reported in the
literature1. Open circuit potential (OCP) variation
with time, Tafel measurement and impedance
analyses were carried out to evaluate the corrosion
resistance of the coated and uncoated test specimens.
The microstructure of the sol-gel alumina coating was
examined by SEM.
Experimental Procedure
Sample preparation

The substrate used in the present study was hot

rolled coil (HRC) mild steel (0.1%C) sheet of
thickness 3 mm. The test specimens were fabricated
by cutting to a dimension of 30 x 10 mm from the
mild steel (MS) sheet. Thereafter, the specimens were
polished with emery paper of grit size 400, 600 and
800 and then finally polished with alumina suspension
(3 m) to give a mirror finish. Afterwards, specimens
were shot peened with steel shots (0.3 mm diameter)

RUHI et al.: CORROSION RESISTANCE PROPERTIES OF SOL-GEL ALUMINA COATING IN MINE WATER

to get a surface roughness ~ 10 m. The main purpose

of the shot peening was to improve surface roughness
for better mechanical interlocking of the coating to its
substrate16. The shot peened specimens were
degreased with acetone and dried in air.
Surface pre-treatment

Zinc-phosphating solution (pH ~ 3) was prepared

and heated to 40-45C. Then the dried test specimens
were dipped in this solution for one minute followed
by flushing in excess of water. In the next step, the
specimens were dried with hot air blower. Specimens
were weighed before and after zinc-phosphating
treatment. The weight gain was found between 3.23.9 g/m2 (approx) for each specimen.
Synthesis of boehmite [AlO(OH)] sol

Aluminium iso-propoxide (precursor) is mixed

with excess of water (r = 100) at 80C for the
complete hydrolysis of the alkoxide. A nucleophilic
addition of water followed by proton transfer from the
attacking molecule to the aluminium iso-propoxide
occurs in the first stage of reaction. This results into a
subsequent removal of the protonated species as
alcohol. The product formed as aluminium hydroxide
precipitates are called as fibrillar boehmite. The
aluminium
hydroxide
precipitate
undergoes
peptization (pH ~ 4) in the presence of a catalyst
(HNO3) yielding a stable boehmite [AlO(OH)] sol
which was used as a coating solution in the present
study. A detailed mechanism of the synthesis of
boehmite sol is reported by Yoldas et al.17,18.
Coating deposition and heat treatment

The
surface
pre-treated
(zinc-phosphated)
specimens were coated with boehmite sol by a simple
dip coating method at a constant withdrawal rate of
1 cm/min. Thereafter, the sol-gel coated specimens
were heat-treated at 400C for 1 h in muffle furnace
in air. A few zinc-phosphated specimens were kept as
such (without sol-gel treatment) for a comparative
study. The specimens are designated as: (i) MS (the
mild steel); (ii) SP (the surface pre-treated mild steel
specimen); and (iii) CMS (the sol-gel coated mild
steel specimen).
Microscopy and XRD analysis

The surface morphology and cross-sectional views

of the sol-gel alumina coated specimens were
examined using Scanning Electron Microscope
(JEOL, Japan make JSM 5600). The compositional

217

analysis of the sol-gel coated specimen was carried

out by computer controlled X-ray diffractometer (D8
Bruker model) under CuK radiation.
Electrochemical measurements

The electrochemical measurements like variation

of electrode potential under open circuit potential
(OCP) condition with respect to time, Tafel plots and
electrochemical impedance analysis were carried out
in freshly prepared mine water solution of
composition (100 mL H2O + 0.5 mL HCl + 0.4 mL
H2SO4; pH 2.5) using a computer controlled Solatron
1280 Z corrosion system equipped with software
Corrware and Zplot. An electrochemical cell (capacity
200 mL) having a saturated calomel electrode as
reference electrode, platinum foil (surface area 2 cm2)
as auxiliary electrode and test specimen as working
electrode was used for electrochemical measurements.
All the electrochemical tests were performed at room
temperature (30+2C). The working area of the test
specimens was kept as 1 cm2. Tafel plots were
obtained by carrying partial polarisation at a constant
scan rate of 1 mV/s by sweeping the potential
between + 150 to 150 mV from OCP. Impedance
measurements were carried out in a frequency range
of 20 KHz to 0.01 Hz at OCP by applying a sine
potential signal of 10 mV. The different parameters
related to polarisation and impedance measurements
were derived by curve fitting method using Corrview
and Zview software respectively. Each experiment
has been repeated three to four times in order to
maintain the reproducibility of the test results.
Results and Discussion
Microstructural and compositional analysis

The surface morphology of the sol-gel coated

specimen is demonstrated in Fig. 1a. Figure clearly
shows a roughened surface. The roughness of the
surface is due to the combined effect of shot-peening
and zinc-phosphating treatment. The cross-sectional
view of the coated specimen is presented in Fig. 1b
depicting the presence of a compact coating of
thickness ~ 30 micron. The compositional analysis of
the coated specimen carried out by XRD, is presented
in Fig. 2. XRD analysis confirmed the presence of
alumina (corundum) in the coating because of the
emergence of different correponding peaks (at 2
value 35.39 and 45.30 along 113 and 104 planes,
respectively). Observation of low intensity peaks of
the XRD generally indicates the presence of less

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INDIAN J. CHEM. TECHNOL., MAY 2009

Fig. 3Open circuit potential versus time curves for the sol-gel
coated specimen (CMS), surface pre-treated specimen (SP) and
bare mild steel (MS) in mine water at 30+2C.

at a 2 value of 38.34 corresponds to aluminium. The

presence of free Al13 ions has also been reported in the
boehmite sol19.
Electrochemical measurements
OCP versus time

Fig. 1SEM micrograph of surface morphology (a) crosssectional view (b) of sol-gel coated specimen.

The OCP versus time curves (Fig. 3) show

different trends of variation of potential for all the
three test specimens (CMS, SP and MS) under open
circuit potential condition. The value of OCP for the
mild steel (MS) attained a steady state within few
minutes of immersion. In case of the specimen SP, a
distinct shift of OCP in the cathodic potential region
was observed till 5 min of immersion. Afterwards
OCP was noticed to be shifted towards anodic
potential region and attained the steady state. The
trend of the variation of OCP for the specimen CMS
was also observed to be shifted in the cathodic region
till the 10 min of immersion. Thereafter, it attained a
steady state. The steady state values of OCP for all the
three test specimens are summarised in Table 1. From
the above trends, one can assume the dominance of
anodic reaction for the surface pre-treated specimen
(SP) as its OCP occurs more positive as compared to
the OCP obtained for the other two specimens.
Partial polarisation (Tafel plots)

Fig. 2XRD spectra of sol-gel coated specimen. Observed peaks

are of -alumina (), aluminium () and iron (*).

crystallinity of the coating. The high intensity peaks

occur at 2 value of 40.13 and 44.66 which
corresponds to base metal (-Fe). The peak positioned

In order to estimate corrosion rate in terms of

corrosion current density (Icorr) of all the test
specimens, Tafel plots were recorded by carrying out
partial polarisation measurement (150 mV from Ecorr)
in the mine water solution. The corresponding plots are
shown in Fig. 4. Different electrochemical parameters
like corrosion current (Icorr), anodic (a) and cathodic
Tafel constant (c) derived from the Tafel plots, are
summarised in Table 1. From the above data, one can
find a substantial reduction in the value of corrosion

RUHI et al.: CORROSION RESISTANCE PROPERTIES OF SOL-GEL ALUMINA COATING IN MINE WATER

219

Table 1Different electrochemical parameters obtained by Tafel

extrapolation and impedance analysis
Electrochemical
parameters

MS

SP

CMS

OCP (mV)
Icorr (A/cm2)
a (mV/decade)
c (mV/decade)
Rct (cm2 )
Cdl (F/cm2)
Rs (cm2)

-635
2.1 x 10
93
83.2
91.7
1.8 x 10-4
41.4

-575
1.07 x 10
89.1
96
240.6
3.8 x 10-5
45.9

-600
3.7 x 10-5
97
119.8
575.8
1.3 x 10-5
292.8

current (Icorr) for the sol-gel coated specimen as

compared to the rest of the specimens (SP and MS).
After surface treatment, a slight increase in corrosion
resistance was observed for the specimen SP as
compared to MS since nearly three to four times lower
Icorr value was found for the specimen SP. After the solgel coating treatment, the Icorr was reduced by more
than one order of magnitude than Icorr measured for MS.
Above observations clearly indicate the efficiency of
sol-gel alumina coating in improving the corrosion
resistance of the substrate (MS) in mine water
environment. Measurement of comparatively a very
high value of a and c for CMS specimen attributes to
the existence of anodic and cathodic controlled
reactions. These factors are ultimately responsible for
the increase of corrosion resistance of sol-gel coated
specimens.

Fig. 4Tafel plots for the sol-gel coated specimen (CMS),

surface pre-treated specimen (SP) and bare mild steel (MS) in
mine water at 30+2C.

Electrochemical impedance spectroscopy (EIS)

The impedance spectra of the test specimens (CMS,

SP and MS) were recorded in terms of Bode plots as
shown in Fig. 5. Bode plots are quite informative in
investigating the change in the electrochemical
behaviour of the test specimens. It presents the
variation of impedance and phase angle with respect to
frequency. Figure 5 can be distinguished into three
distinct frequency regions namely high (> 103 Hz),
middle (1-103 Hz) and low (<1 Hz) frequency regions.
The high frequency region determines the properties of
reference electrode and solution resistance Rs, the
medium frequency region shows the capacitive
behaviour and the low frequency region explains the
charge transfer process occurring at solution/coating
interface. The different parameters related to
impedance analysis derived after curve fitting method
are summarised in Table 1. The value of charge
transfer resistance (Rct) for the surface pre-treated
specimen (SP) is observed to be two times more than
that of MS. Further, a significant improvement in the
corrosion resistance is observed for the specimen (CMS)

Fig. 5Bode plots for the sol-gel coated specimen (CMS),

surface pre-treated specimen (SP) and bare mild steel (MS) in
mine water at 302C.

as the value of Rct is found to be five times higher than

the MS. The occurrence of a low value of double layer
capacitance (Cdl) for the specimen CMS (an order of
magnitude less than MS) further supports the presence
of an insulating nature of the sol-gel alumina coating.
The measurement of phase angle at low frequency
region is quite important in order to estimate
compactness of the coating20. The occurrence of the
lowest value of phase angle (2) for the sol-gel coated
specimen as compared to the other two test specimens
(Fig. 5) clearly demonstrates the existence of a compact
coating. On the other hand, the measurement of a
comparatively higher value of phase angles (-6 and -9
for SP and MS, respectively) suggests the presence of
porosity in the surface film.

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INDIAN J. CHEM. TECHNOL., MAY 2009

Conclusions
The present investigation has led to following
conclusions.
The sol-gel alumina coating developed on the
surface pre-treated mild steel surface makes a
significant improvement in the corrosion resistance
properties of the metal in corrosive mine water
environment. The electrochemical measurements show
an order of magnitude less value of Icorr for the sol-gel
coated specimens as compared to the bare metal. The
microstructural analysis reveals a compact coating of
thickness ~ 20 m. The XRD spectrum confirms the
presence of -alumina phase in the coating.
Acknowledgement
Authors are thankful to the Director, AMPRI,
CSIR, Bhopal for granting permission to publish this
research work. One of the authors (Gazala Ruhi) is
thankful to Council of Scientific and Industrial
Research (CSIR) for (SRF-NET) scholarship.
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