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Corrosion Science
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a r t i c l e
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Article history:
Received 17 December 2007
Accepted 9 June 2008
Available online 21 June 2008
Keywords:
A. Aluminium
A. Alloy
B. EIS
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: smashibli@yahoo.com (S.M.A. Shibli).
0010-938X/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2008.06.017
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
air.
2233
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].
DXRD
0:9k
;
b cos h
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
Corrosion rate
2234
Fig. 2. TEM images of nano cerium oxide used for the present study.
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.
2235
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].
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].
2236
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.
1
2
3
4
5
6
0
0.05
0.1
0.2
0.5
1
0.944
0.953
0.957
0.961
0.955
0.967
10
15
0.965
0.983
0.972
0.987
0.982
0.974
9.922
0.935
0.943
0.954
0.964
0.956
0.910
0.932
0.940
0.941
0.942
0.950
Efciency (%)
19.01
20.83
22.14
14.14
16.21
18.34
44.4
38.4
63.9
78.6
62.6
48.5
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].
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)
Rp (X cm2)
bc V dec1
ba V dec1
0
0.05
0.1
0.2
0.5
1
0.924
0.935
0.910
0.931
0.924
0.930
0.644
2.839
1.795
15.86
1.527
1.209
799.1
791.4
371.2
168.6
414.9
892.1
0.385
0.142
0.059
0.056
0.216
0.289
0.011
0.012
0.012
0.029
0.014
0.023
0.062
0.276
0.174
1.538
0.148
0.117
2237
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
O
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
0
0.05
0.1
0.2
0.5
1
Impedance parameters
Rp (X cm2)
80. 103
80.389
80.463
79.330
79.607
87.215
1.074
1.103
1.094
1.152
1.161
1.055
1.293
1.292
1.292
1.309
1.305
1.289
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 (%)
0
0.05
0.1
0.2
0.5
1
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
environments.
2238
Acknowledgements
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.
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