Anda di halaman 1dari 7

Corrosion Science 50 (2008) 22322238

Contents lists available at ScienceDirect

Corrosion Science
journal homepage:

Development of nano cerium oxide incorporated aluminium alloy sacricial

anode for marine applications
S.M.A. Shibli a,*, S.R. Archana a, P. Muhamed Ashraf b

Department of Chemistry, University of Kerala, Thiruvananthapuram, Kerala 695 581, India

Central Institute of Fisheries Technology, Cochin, Kerala 682 029, India

a r t i c l e

i n f o

Article history:
Received 17 December 2007
Accepted 9 June 2008
Available online 21 June 2008
A. Aluminium
A. Alloy
C. Cathodic protection

a b s t r a c t
Aluminiumzinc alloy sacricial anodes are extensively used for cathodic protection. The performance of
the sacricial anodes can be signicantly improved by incorporation of microalloying elements in the
aluminium matrix. In the present work nano cerium oxide particles of different concentrations, ranging
from 0 to 1 wt% were incorporated for activating and improving the performance of the anode. The electrochemical test results revealed the increased efciency of the anode. The electrochemical impedance
spectroscopy revealed the information that the presence of nano cerium oxide in the anode matrix
caused effective destruction of the passive alumina lm, which facilitated enhancement of galvanic performance of the anode. Moreover, the biocidal activity of cerium oxide prevented the bio accumulation
considerably which enables the anodes to be used in aggressive marine conditions.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
Cathodic protection using sacricial anode is an effective technique for corrosion control. Aluminium sacricial anodes are
widely used in cathodic protection of steel structures due to its
merits such as low density, large electrochemical equivalent, availability and reasonable cost. Pure Al is not suitable for galvanic anodes because it exhibits a relatively noble potential in sea water
due to the formation of passive oxide lm on the surface. The success of the Al anode depends upon the alloying of certain metals
whose role is to prevent the formation of a continuous adherent
and protective oxide lm on the alloy, thus permitting continuous
galvanic efciency. In order to promote activation, Al is usually alloyed with small quantities of elements such as Zn, Hg, In, Sn, Bi, Ti
and Mg [15]. Most of the works in this eld were carried out on Al
rich Zn sacricial anodes and the concentration of Zn in Al alloy
sacricial anodes has been optimized to 5 wt% due to high
improvement in metallurgical and electrochemical properties of
the alloy through the formation of b-phase [6].
Modication of Al+5%Zn alloy anode is essential due to its noncolumbic loss and low galvanic efciency. Moreover the surface of
the anode may attack by microbial fouling if the anode is in contact
with aqueous environments containing microorganisms [7]. The
inclusion of metal oxides can signicantly improve the metallurgi-

* Corresponding author. Tel.: +91 471 2418782 (Off.), +91 92498 63611 (Res.).
E-mail address: (S.M.A. Shibli).
0010-938X/$ - see front matter 2008 Elsevier Ltd. All rights reserved.

cal characteristics of the anodes. Literature reports that ZnOAl2O3

mixed oxide composite has been used for this purpose [8]. In this
context nano cerium oxide (CeO2) was selected for the present
work to develop reinforced Al alloy sacricial anodes. Cerium oxide
has long been considered as one of the most important oxide
materials because of its desirable properties such as high refractive
index, good transmission, adhesion, high stability against mechanical abrasion and catalytic activity [9]. The biocidal activity of Cerium oxide has been reported elsewhere [10,11]. Yan Yanping et al.
developed a cerium-containing sacricial anode of Al alloy of multiple elements for marine applications [12]. But no work has yet
been reported regarding nano cerium oxide incorporation for the
activation of Al alloy sacricial anodes. Hence the present work
can be benecially considered for developing a sacricial anode
with high efciency and biocidal activity for effective use in marine

2. Experimental details
2.1. Synthesis of nano cerium oxide
Nano crystalline cerium oxide powder was synthesized by the
precipitation method [13]. Ammonia solution of pH 8 was added
to cerium nitrate (Ce (NO3)3  6H2O) solution, heated at 80 C under
constant stirring. Then the mixture was kept at that temperature
for 2 h. The precipitate was collected by ltration, washed and nally calcined at 350 C in a mufe furnace for 2 h in presence of


S.M.A. Shibli et al. / Corrosion Science 50 (2008) 22322238

To study about the stability of the crystalline phase of nano cerium oxide, the particles were heated to 720 C for 2 h in the mufe
furnace in presence of air and then subjected to X-ray diffraction
analysis using Cu Ka radiation. The average particle size was determined from the broadening of the XRD line. The size of the particles, DXRD was calculated using Scherrer equation [14].


b cos h

where k is the wavelength of radiation, h is diffraction angle and b is

the full width half maximum in radians. The average particle size
was also conned by TEM using 2000FX-11, Transition Electron
Microscope. JEOL, Japan.
2.2. Anode casting
Commercially available Al (99.75%) and Zn (99.95%) ingots were
used for casting Al+5 wt% Zn alloy. This combination favors the formation of b-phase of the crystallographic state during casting. The
alloy ingots were cut, weighed and melted in a clay-graphite crucible in a mufe furnace at temperature of 720 C. Different amounts
of nano CeO2 particles were added into the melt and stirred using a
SiC rod to homogenize it. The melt was again kept in the mufe
furnace for another 15 min at the same temperature and then
poured into a preheated graphite die of dimension 5.5  3.5 
0.5 cm.
2.3. Physico-chemical evaluation
The anodes were subjected to Vickers micro indentation hardness test as per ASTM-E 384-05 using a Shimadzu HMV-2000
instrument. For the present study the test load applied was 50 gf
for an indentation time of 14 s at 25.5 C. The microscopic structures such as grain size and grain boundaries of the anodes were
characterized by scanning electron microscope of Hitachi S-2400.
The electrodes were polished by using different grades of emery
paper down to 1000, rinsed with dilute NaOH and distilled water.
SEM micrographs at different magnications were compared to
analyze the morphological characteristics.
2.4. Electrochemical characterization
2.4.1. Polarization
Linear sweep voltammetry was carried out using an Autolab 80
plus FRA2 corrosion system. The electrolyte used was aerated in
3.5% NaCl solution. Ag/AgCl, Pt and the coupon having 1 cm2 exposed area were used as reference, counter and working electrodes, respectively. The coupons were polished with different
grades of emery paper up to 1000, degreased with acetone and
rinsed with distilled water. The coupons were then immersed in
3.5% NaCl for 1 h prior to polarization studies at a scan rate of
0.005 V/S at 30 2 C.
2.4.2. Galvanic efciency
The test anode and a steel cathode having surface area 1 cm2
and 10 cm2, respectively were coupled and immersed in 3% NaCl
solution at 30 2 C for a period of 1 month. The current owing
inbetween the mild steel cathode and sacricial anode was continuously measured as a function of time, by using a zero resistance
ammeter. For this purpose the galvanic couple was provided with
a parallel connection having an ammeter and then the original circuit was disconnected prior to the measurements in each time. The
actual current produced by the anode was determined from the
plot of current vs. time. The area under the graph should be exactly
proportional to the actual charge delivered by the anode. The
weight of the anode before and after immersion of the respective

galvanic couple was determined after cleaning the anode by following a standard procedure (ASTM G 31). From the weight loss
measured, the theoretical current to be produced by the anode
was calculated as

Galvanic efficiency A=B  100;

where A is the actual current produced by the anode and B is the
theoretical current to be produced by the system as per Faradays
2.4.3. Self-corrosion
The anodes were immersed in 3% NaCl solution for a period of
30 days. The electrolyte was kept stagnant at 30 2 C. The anodes
were cleaned using a hot mixture of 20 g potassium dichromate
and 50 ml phosphoric acid in 1 l water. The anodes were rinsed
with distilled water, dried and then weighed. The difference in
weight of the metal before and after immersion was measured
and used to calculate the self-corrosion rate as given below

Corrosion rate

Weight loss g cm2 h

Surface area  time

2.4.4. OCP and CCP variation

The open circuit potential (OCP), the potential difference between the test anodes with respect to standard calomel electrode
(SCE) was continuously monitored for a period of 1 month commencing from introduction of the anode into the electrolyte (3%
NaCl kept at 30 2 C). The closed circuit potential (CCP) of the test
anodes was monitored after coupling with mild steel cathodes having the surface area in the ratio 1:10. The current density generated
at the anode surface was maintained constant during CCP measurements using a controlled variable resistance.
2.4.5. Electrochemical impedance characteristics
Electrochemical impedance spectroscopy (EIS) was carried out
by using an electrochemical analyzer [Autolab PG STAT 30 plus
FRA 2]. The electrolyte used was 3.5% NaCl. Ag/AgCl, Pt and the
anode having 1 cm2 exposed were used as reference, counter
and working electrodes, respectively. The impedance analysis
was carried out at the frequency range of 1 MHz to 0.1 Hz with
reference to OCP after 30 min exposure of the coupons in the
2.5. Bio analysis
The anodes were evaluated for biological corrosion by immersing in marine water. The coupons, having different percentages of
nano cerium oxide, were immersed in subsurface water of Vizhinjam Port. After 3 days, the anodes were taken out from the sea for
determining the bio accumulation. The marine condition was
maintained by keeping the anodes in a pool of simulated sea water
till they were transferred to the laboratory. The total viable count
of the biolm formed was determined by standard plate count
method. This was done simultaneously with coupon retrieved.
Sterilized cotton swabs were employed to remove the surfacial
growth from the anodes and the same was aseptically transferred
in peptone water. The mixture was shaken for 5 min so that all
organisms were dispersed uniformly into the medium. After
30 min, the samples were serially diluted with sterile water to
get 104 dilution. Sample (0.1 ml) from the 104 dilution were separated on to the Zobell Marine Agar plates. Incubation of the plates
was carried out for 24 h at 37 C.
Colony forming units (CFU) were enumerated and original
counts were calculated from the dilution factor

Microbial counts Number of CFU  dilution factor:


S.M.A. Shibli et al. / Corrosion Science 50 (2008) 22322238

3. Results and discussion

3.1. Synthesis and morphology of nano cerium oxide
The probable precipitation reaction for the synthesis of nano
cerium oxide is as follows [13]. Cerium nitrate was hydrolyzed
with NH4OH. The hydrated Ce4+ ions can form complexes with
H2O molecules or OH ions. Polymers of this hydroxide,
, can then serve as the precursors of the oxide.
CeH2 Ox OH 4y
In aqueous solution, H2O as a polar molecule tends to take protons
away from coordinated hydroxide and the reaction can be expressed by equation [13,15]

CeH2 Ox OH 4y

H2 O ! CeO2  nH2 O H3 O
The calcination temperature was xed at 350 C since there
were reports showing that calcinations at higher temperature results in the micro size cerium oxide formation [16].
The powder X-ray diffraction patterns for cerium oxide calcined
at 350 C and 720 C are shown in Fig. 1. In the 2h range of 2080,
the ve typical peaks (1,1,1), (2,0,0), (2,2,0), (3,1,1) and (1,1,2) can
be indexed as F.C.C phase of cerium oxide [16]. The XRD pattern of
cerium oxide with uorite structure depends on annealing temperature since the phase transformation would take place when the
temperature increases above 300 C [13]. The d-spacing matched
closely with those of cubic cerium oxide phase at 720 C also
(JCPDS 81-0792). The crystalline size of cerium oxide at 350 C, calculated from the Scherrer formula using the (1,1,1) diffraction peak
was 15 nm. The width of the peaks gradually decreases with
increasing calcination temperature [16]. The XRD analysis was also
required to study about the stability of cerium oxide at 720 C
since the anode was to be cast at that temperature. However the
crystalline size of cerium oxide was found to be below 20 nm even
up to 720 C. The TEM image in Fig. 2, showed that the product was

Fig. 2. TEM images of nano cerium oxide used for the present study.

composed of homogeneous tiny cerium oxide nano particles,

revealing the particle size of <20 nm, which was consistent with
the result from XRD.
3.2. Metallurgical characteristics of the anode

Fig. 1. XRD patterns of nano cerium oxide heated at (A) 320 C and (B) 720 C.

The substrate chosen for the present work was Al+5%Zn alloy,
which has been proved to be the most suitable and efcient substrate through literature survey [8]. Considering the Al-Zn binary
system, Zn is concentrated in interdentritic or grain boundaries.
Numerous theories have been proposed in order to explain the
activating inuence of zinc on the dissolution of Al in chloride
aqueous media [17]. Extensive studies on the surface modication
of Al alloys by cerium oxide have been reported [11]. Cerium oxide
is used in sacricial anode to get a synergistic effect of both cerium
oxide and Zn alloy. Hence, the uniform and homogeneous distribution of cerium oxide effectively suppresses the formation of passive
Al2O3 on the Al alloy sacricial anode surface which in turn activates the anode i.e., oxidizes metal aluminium.
The SEM micrograph of Al+5%Zn alloy anode (Fig. 3) showed no
clear precipitation or segregation in the case of Al+5%Zn alloy matrix. This revealed the homogeneity of the alloy as seen at higher
magnications. Fig. 4 shows the SEM micrograph of nano cerium
oxide incorporated in Al+5%Zn alloy matrix. Diffused boundaries
are observed; parts of the boundaries contain some regions of
bright precipitate. It is expected that practically all the nano cerium oxide must be in the interdendritic boundaries, since cerium
oxide is practically insoluble in Al.
By means of incorporation of inert metal oxide, the hardness of
the alloy was improved. The hardness values of Al+5% Zn anodes
with 0%, 0.05%, 0.1%, 0.2%, 0.5% and 1% nano cerium oxide were
34 2.7, 31 2.2, 35 2.4, 36 2.2, 42 2.3 and 62 2.3 HVN,
respectively. This showed that the hardness increases with nano
cerium oxide incorporation and it also improved the metallurgical
properties of the anodes.

S.M.A. Shibli et al. / Corrosion Science 50 (2008) 22322238


Fig. 3. SEM micrograph of Al+5%Zn anodes at different magnications [(A) 500 and (B) 1.5 k].

Fig. 4. SEM micrograph of nano cerium oxide incorporated Al+5%Zn anodes at different magnications [(C) 500 and (D) 1.5 k].

3.3. Evaluation of galvanic performance

The trend of anode potential (OCP) against time when the anodes were immersed in a 3% NaCl solution is reported in Fig. 5.
The initial OCP of the nano cerium oxide incorporated anode
showed more negative value than the bare anode. The initial OCP
value of the Al+5%Zn anode was found to be 0.944 V. After 1
month of immersion the potential changes to 0.986 V. The OCP
values of different concentration of nano cerium oxide incorporated anodes were found to lie in the range from 0.953 V to
0.967 V and after 1 month of immersion it shifted in the range
from 0.986 V to 0.989 V. As time goes on the OCP values slowly
shifted to more cathodic region. There was no marked difference in
potential among the anodes after 1 month. OCP cannot be considered as a sole factor determining the anodic performance, further

analysis were conducted to asses the performance of anodes in

The closed circuit potential (CCP) of the Al+5%Zn alloy anodes
incorporated with different amounts of nano cerium oxide were
also compared (Table 1). An active CCP is desirable because a relatively noble potential could indicate the presence of passivation.
The Al+5%Zn alloy anodes with 0.2% nano cerium oxide incorporation shows a more cathodic CCP value of 0.987 V and is least
polarized (Fig. 6). Anodes must also possess high galvanic efciency in order to avoid frequent anode replacement. Duplicate
experiments were conducted and the average values of the efciency of 0.05%, 0.1%, 0.2%, 0.5% and 1% nano cerium oxide incorporated anodes were 38.4%, 63.9%, 78.6%, 62.6% and 48.5%,
respectively and the efciency of Al+5%Zn anode was 44.4%. There
were variations of below or around 1% of the efciency values.
Thus the galvanic performance of anodes was much improved by
the incorporation of nano cerium oxide. The overall galvanic performances of the nano cerium oxide incorporated anodes are compared in Table 1. From the data it is clear that lower self-corrosion
values were observed for higher amount of cerium oxide incorporation. The reduction in self-corrosion values of the anodes could
be attributed to the reduction in grain boundary corrosion. The
0.2% nano cerium oxide incorporated anodes showed least self-corrosion value. The cerium oxide addition offered better reinforcement to the Al+5%Zn alloy matrix caused very low metal
dissolution during long-term exposure.
3.4. Potentiodynamic polarization

Fig. 5. Variation of OCP with time of nano cerium oxide incorporated Al+5% Zn alloy
anode. [() 0%, (h) 0.05%, (N) 0.1%, (e) 0.2%, (j) 0.5%, (4)  1% nano
cerium oxide].

The effect of nano cerium oxide on the polarization behaviour of

aluminium alloy sacricial anode is shown in Fig. 7. Addition of
nano cerium oxide to the anode alloy shifts the corrosion potential
to more negative values, which is desirable for the cathodic protec-


S.M.A. Shibli et al. / Corrosion Science 50 (2008) 22322238

Table 1
The galvanic performance of Al+5 wt% Zn incorporated with nano cerium oxide (Electrolyte: 3% NaCl, temp: 30 2 C, stagnant condition)
Sl no.

Amount of nano cerium oxide (%)





CCP V vs. SCE at different current densities (mA cm2)







Self-corrosion  106 g cm2 h1

Efciency (%)



was revealed. Duplicates also showed similar results. The above results revealed that compared to other concentrations of cerium
oxide, 0.2% nano cerium oxide imparted better performance to
the anode.
3.5. Electrochemical impedance spectroscopy (EIS) measurements

Fig. 6. Variation of CCP with time of nano cerium oxide incorporated Al+5% Zn alloy
anode. [() 0%, (h) 0.05%, (N) 0.1%, (e) 0.2%, (j) 0.5%, (4) 1% nano
cerium oxide].

Fig. 7. Polarization behaviour of Al+5%Zn anodes incorporated with nano cerium

oxide. [(A) 0%, (B) 0.05%, (C) 0.1%, (D) 0.2%, (E) 0.5% nano cerium oxide].

tion systems. The presence of nano cerium oxide decreased the

polarization resistance (Rp) and increased the corrosion potential
Ecorr in the negative direction (Table 2). The corrosion rate and Icorr
were maximum and Rp value was minimum for 0.2% nano cerium
oxide incorporated Al alloy sacricial anode. Though the potential
variations are not more than few mV, they were comparable and
from those results, the optimum concentration of cerium oxide

AC impedance spectroscopic studies were carried out to get

information about the electrochemical and physico-chemical phenomena associated with the electrode reactions during galvanic
dissolution process. The EIS plots of Al alloy sacricial anodes
incorporated with nano cerium oxide are shown in Fig. 8. The
impedance spectra of all the anodes, studied in the present work
have centre lies under the real axis, which is the characteristic
behaviour of AlZn alloys undergoing uniform galvanic dissolution
[18]. The high frequency plot has been associated with the charge
transfer process and the low frequency plot with mass transfer
process. The semicircle at the high frequency was found to have
similar behaviour in spite of the variation in the cerium oxide content. The second semicircle can be attributed to the formation of a
Zn(OH)2 and Al(OH)2 layers on the anode surface due to the oxidation of Zn and Al [19]. The depression and pseudo inductive behaviour of the second semicircles can be attributed to active
dissolution [19]. Depressed semicircular shape of the complex
impedance plane is due to the inhomogenities of the anode surface
The experimental data can be described using a simple equivalent circuit. In this equivalent circuit, Rs is the solution resistance,
Rp is the polarization resistance, A constant phase element
(CPE) is introduced for better data tting instead of an ideal capacitance parameter. The impedance expression of CPE is dened as

Z CPE Ajwn 1 ;

where A and n are frequency independent t parameter, j = (1)1/2
and w = 2kf, the frequency. Depending on the values of n, the CPE
can represent resistance (n = 0 and A = R), capacitance (n = 1,
A = C), inductance (n = 1, A = L) and Warburg impedance (n = 0.5
and A = W). CPE is related to some inhomogenities on the surface
of the anodes. The objective of impedance analysis was to measure
the total polarization resistance (Rp) that constitutes the main practical parameter useful for the understanding of the anode dissolution rate. The double layer capacitor in real cells often behaves
like a CPE instead of like a capacitor. Several theories have been pro-

Table 2
The LSV parameters of nano cerium oxide incorporated Al alloy sacricial anode in 3.5% NaCl at 30 2 C
Percentage of cerium oxide

Ecorr (V)

Icorr (A cm2)  105

Rp (X cm2)

bc V dec1

ba V dec1

Corrosion rate mm/year









S.M.A. Shibli et al. / Corrosion Science 50 (2008) 22322238

Fig. 8. Impedance plots of nano cerium oxide incorporated Al+5% Zn alloy anodes.
[(A) 0%, (B) 0.05%, (C) 0.1%, (D) 0.2%, (E) 0.5% nano cerium oxide].

posed to account for the non-ideal behavior of the double layer but
none has been universally accepted. In most cases n is treated as an
empirical constant and not have much physical basis.
It is possible by EIS to study the behaviour of the oxide lm on
the anode surface when it is exposed to an electrolyte. Rp value is
an indication of the effective interaction between the oxide lm
and the substrate, which lowers the surface resistance, a requisite
to sacricial anodes [5]. Duplicate experiments were conducted
and the average values were compared. The Rp value of nano cerium oxide incorporated alloys are in the order 0.2% < 0.5% <
0% < 0.1% < 1% (Table 3). Rp value is minimum for 0.2% nano cerium
oxide incorporated anodes. From the experimental data it is clear
that higher and lower concentration of cerium oxide addition to
the Al alloy resulted in less improvement, but particle incorporation in between 0.2% and 0.5% resulted in improvement in the performance of the sacricial anode.
3.6. Bio analysis
Microorganisms inuence the corrosion by changing the electrochemical condition of the metal surface. Microbial adhesion
process leads to modications of metal solution interface accounting for serious failure and loss of energy due to biolm accumulation and bio corrosion [21].
Cerium oxide is a semiconductor with a band gap of 3.2 eV. It is
also a highly efcient UV absorber. The absorption at high wavelength probably enhances the photo induced biocidal activity under day light exposure. The mechanism of photo induced biocidal
action is similar to that of the photo catalyst TiO2. The electron
trapped in Ce4+/Ce3+ site was subsequently transferred to the surrounding absorbed oxygen. The conduction band electrons reduced
O2 to O
2 radical and it becomes H2O2 on further reduction. The
presence of Ce4+ in the matrix might promote the formation of

radicals. Cerium oxide has high
2 and then with H form OH
oxygen transport and storage capacity [22]. The combination of

Table 3
The impedance data of cerium oxide incorporated Al alloy sacricial anode
Percentage of cerium oxide


Impedance parameters
Rp (X cm2)

CPE (F cm2)  108

80. 103



Fig. 9. Pour plate culture of microbes grown on nutrient agar developed from the
surface of nano cerium oxide incorporated Al alloy sacricial anode. [(A) 0%, (B)
0.05%, (C) 0.1%, (D) 0.2% (E), 0.5% (F) 1% nano cerium oxide].

Table 4
The bacterial count of sacricial anodes incorporated with different percentage of
nano cerium oxide
Sample (%)

Bacterial count (CFU cm2)


3.8  104
3.2  104
2.2  103
8.1  103
9.9  102
2.8  103

the hydroxyl radicals themselves also could produce H2O2. The hydroxyl radical and hydrogen peroxide are responsible for the biocidal effect. Fig. 9 shows the photos of the microorganisms
grown on nutrient agar developed from the biolm. Table 4 indicates the bacterial count in different samples. From these data it
is clear that as the amount of composite in the anode increases
the microbial count decrease from 3.8  104 to 9.9  102. Thus by
the incorporation of nano cerium oxide, a biocide, in Al alloy sacricial anode the growth of microorganisms on the anode surface is
signicantly reduced.
4. Conclusions
The metallurgical characteristics of the anodes were signicantly improved by the incorporation of cerium oxide in the anode
matrix. The hardness increased with respect to increase in nano
cerium oxide content. The reinforcement of the Al+5%Zn alloy anode with 0.2% nano cerium oxide increased the efciency from
44.43% to 78.62%. The 0.2% nano cerium oxide incorporated anode
also exhibited excellent electrochemical characteristics and this
concentration was selected as optimized amount. The presence of
nano cerium oxide in the anode matrix caused effective destruction of the passive alumina lm. The destruction of alumina lm
facilitated enhancement of galvanic performance of the anode.
The nano particles in the anode matrix effectively reduced biofouling on the anode surface. The anodes also have merits of low cost,
easy development, moderate galvanic performance and bio-resistance. Still better performance of the anodes could have been
achieved if other metal activators or other nano material based
activators were also added along with the nano cerium oxide.
The improved biocidal activity of the anodes can be made use for
formation of modied anodes suitable for use in aggressive marine


S.M.A. Shibli et al. / Corrosion Science 50 (2008) 22322238

The authors are grateful to the Head of the Department of
Chemistry, University of Kerala for his kind encouragement and
for extending facilities to complete this work.
[1] A.R. Despic, D.M. Drazic, M.M. Purenovic, N. Cikovic, J. Appl. Electrochem. 6
(1976) 527.
[2] I. Gurappa, J.S. Karnic, Corros. Prev. Control 43 (1996) 77.
[3] H. Sina, M. Emamy, M. Sareni, A. Keyvani, M. Mahta, J. Campbell, Mater. Sci.
Eng. A 431 (2006) 263.
[4] A. Barbucci, G. Cerissola, G. Bruzzone, A. Saccone, Electrochim. Acta. 42 (1997)
[5] M.A. Talavera, S. Valdez, J.A. Jurez Islas, B. Mena, J. Genesca, J. Appl.
Electrochem. 32 (2002) 897.
[6] E.Y. Lyublinskii, Electrochemiya 9 (1973) 461.
[7] B. Li, B.E. Logan, Colloids Surf. B: Biointerf. 41 (2005) 153.


S.M.A. Shibli, B. Jabeera, R. Manu, Mater. Lett. 252 (2006) 3520.

W. Xiao, Q. Guo, E.G. Wang, Chem. Phys. Lett. 368 (2003) 527.
L. Martineau, P.N. Shek, Burns 32 (2006) 172.
P. Muhamed Ashraf, S.M.A. Shibli, Electrochem. Commun. 9 (2007) 443.
Y. Yanping, W. Chen, W. Kefeng, Faming Zhuante Shenqing Gongkai
Shuomingshu, CN 1566 403 (2005) [C.A. vol. 143, No: 428738r].
Y.P. Fu, C.H. Lin, C.S. Shang, J. Alloys Compds. 391 (2005) 110.
B.D. Cullity, Elements of X-ray Diffraction, second ed., Wiley, New York, 1978.
X.H. Liao, J.M. Zhu, J.J. Zhu, J.Z. Xu, H.Y. Chen, Chem. Commun. 10 (2001) 937.
P. Nachimuttu, W.C. Shih, R.S. Liu, L.Y. Jang, J.M. Chen, J. Solid State Chem. 149
(2000) 408.
A.G. Manoz, S.B. Saidman, J.B. Bessone, Corros. Sci. 43 (2001) 1245.
T. Noguchi, P. Sawanyama, A.F. Shima, K. Hashimoto, Environ. Sci. Technol. 32
(1998) 3831.
A. Barbucci, G. Cerisola, P.L. Cabot, G. Bruzzone, Mater. Sci. Forum 529 (1998)
V. Ramlet, G. Reinhard, Electrochim. Acta 35 (1990) 1045.
W.G. Characklis, K.C. Marshall, Biolms, John Wiley and Sons Inc., New York,
Y.B. Xie, C.N. Yuan, Appl. Catal. B Environ. 46 (2003) 251.