Corrosion Science 51 (2009) 1611–1618

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Environmental factors affecting the corrosion behavior of reinforcing steel III.

Measurement of pitting corrosion currents of steel in Ca(OH)2 solutions under
natural corrosion conditions
E.E. Abd El Aal *, S. Abd El Wanees, A. Diab, S.M. Abd El Haleem
Chemistry Department, Faculty of Science, Zagazig University, Zagazig 44519, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: Using a simple electrolytic cell, the pitting corrosion current of reinforcing steel is measured in Ca(OH)2
Received 4 October 2008 solutions in presence of chloride and sulfate as aggressive ions. Pitting corrosion current starts to flow
Accepted 14 April 2009 after an induction period which depends on the concentration of both the aggressive and the passivating
Available online 22 April 2009
anions. The pitting corrosion current densities reach steady-state values which depend also on the type
and concentration of the corrosive and passivating anions. The corrosive action of the aggressive species
Keywords: decreased in the order: SO42 > Cl. Corrosion of the steel is found to be governed by a single electron
A. Steel
transfer reaction. Raising the temperature decreases the induction period associated with pit initiation
A. Steel reinforced concrete
C. Passive films
and increases the corrosion current associated with pit propagation. From Arrhenius plots, the activation
C. Passivity energies for both pit initiation and pit propagation in presence of chloride and sulfate ions are calculated.
C. Pitting corrosion Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction Dynamic polarization techniques are also used to estimate the

Corrosion of steel reinforcement in concrete, as in most corro-
sion processes, is of electrochemical nature. The corrosion process
necessitates an anodic area where oxidation reaction occurs, a
cathodic area where reduction reaction occurs and a conducting
medium for the transportation of ions between anode and cathode.
In the case of steel reinforcement, the highly alkaline concrete pore
solution serves as the ion conducting medium. This alkalinity is
largely due to the presence of sodium and potassium oxides in
the cement, as well as, Ca(OH)2 produced in the hydration reaction
of the cement minerals [1–6].
In this connection, several electrochemical techniques have
been developed to asses the corrosion of reinforcing steel. The
most well known of these techniques is the half-cell potential
mapping. The potentials of the steel are measured relative to a sta-
ble reference half-cell on the outer surface of the concrete. These
potentials can be related to the probability of corrosion occurring
and provide little quantitative information regarding the corrosion
rate [7–11].
Measurement of the resistivity of the concrete in conjunction
with potential mapping is another technique supposed to asses
the corrosion of steel in concrete [9,12–14]. A large potential gra-
dient associated with a low concrete resistivity will normally result
in high rate of corrosion.
* Corresponding author. Tel.: +20 10 5280422; fax: +20 55 234 5452.
E-mail address: emad_abdelaal@hotmail.com (E.E. Abd El Aal).
corrosion rates of steel embedded in concrete [13–18]. However,
a number of uncertainties arise with the use of these techniques
due to the several experimental precautions which should be taken
in account. Page [19] pointed out that the electrodes are made to
function as net anodes or net cathodes in cells in which the deriv-
ing force is supplied by an external power source. In practice, how-
ever, separate anodic and cathodic reactions occur simultaneously
on the same electrode surface under the deriving force of the po-
tential difference between the anodic and cathodic sites [20].
Alternate current impedance is another technique used to esti-
mate the corrosion process of reinforcement steel [21–23]. How-
ever, the determination of A.C. impedance, although it gives very
useful information related to the electrochemical process, is more
time-consuming and the impedance values measured in the range
of very low frequencies do not always give accurate information
for calculating corrosion rate [24].
In the present investigation, a simple experimental arrange-
ment is applied for the direct measurement and evaluation of the
corrosion current (corrosion rate) operating under natural condi-
tions. This is successfully accomplished by using a simple, divided
H-cell accommodating two similar steel electrodes immersed in a
passivating Ca(OH)2 solution which represents the main constitu-
ent of concrete pore solution [1–6,25,26]. Chloride and sulfate
are used as aggressive anions. Chloride ions are being present as
original constituents of concrete mixture or as a result of penetra-
tion from the environment. Sulfate ions, on the other hand, are
found to be actively participated in the corrosion of reinforcing

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.04.006
1612 E.E. Abd El Aal et al. / Corrosion Science 51 (2009) 1611–1618
steel especially in the area of the Middle East [27–30]. The two
electrodes are short circuited over a low resistance nanoamperom-
eter. When equilibrium is established, SO42 or Cl, as corrosion
anions is added to one side of the cell. After a short induction per-
iod, an electric current starts to flow as a result of the propagation
of pitting corrosion. As far as the authors are aware, it is the first
time to measure the corrosion current and consequently the corro-
sion rate of reinforcement steel under natural corrosion conditions
using no external power sources.
2. Experimental
The simple electrolytic cell that was used is shown diagram-
matically in Fig. 1. It consists of a 250 ml borosilicate glass beaker
containing 100 ml of the Ca(OH)2 solution as a passivating agent,
one of the steel electrode (A) and a magnetic stirrer. The second
steel electrode (B) was enclosed in a borosilicate glass tube ended
with a fine porosity, fritted centered glass disc G4 (C). The two steel
electrodes (A and B) were short-circuited through a nanoamper-
ometer (Siemens type N 5536).
The steel electrodes were made from steel samples produced by
the Egyptian Mill Steel Company, always used as reinforcement,
and having the following chemical composition, in accordance
with the Egyptian ASTM A615 standard [31]:
C Si Mn P S Fe
0.32 0.24 0.89 0.024 0.019 bal. ‘‘98.507”
Each electrode was fixed to a borosilicate glass tube with epoxy re-
sin so that only the bottom surface area (1.33 cm2) was exposed to
the solution. The steel electrodes were abraded into uniform sur-
faces by a grinding machine (model Jean Wirtz TG 200, Germany)
with successive 0-, 00- and 000-grades emery papers. The elec-
trodes were then degreased with acetone and finally washed with
triply-distilled water.
Since the surface treatment of the two electrodes was the same,
and the composition of the electrolyte in the cell compartments
was identical (the two sides of the cell were filled with the same
solution of the passivating agent), no current could be detected
on connecting the electrodes through the nanoamperometer. In a
Fig. 1. Electrical circuit and electrolytic cell used for measuring pitting corrosion
currents. A and B are two identical electrodes while C is a fritted centered glass disk,
G4, and nA is a nanoamperometer.
few experiments, however, small currents were observed to flow,
apparently resulting from slight uncontrollable differences in envi-
ronmental conditions. These currents are decayed in a period of
about 20 min. When this condition was established, a weighed
amount of Na2SO4 or NaCl, as aggressive anions, was added to
the solution of the main compartment and the current flowing
was recorded as a function of time until steady values were estab-
lished. Since the two electrodes were initially in the passive state,
the conditions are suitable for the initiation and propagation of pit-
ting corrosion after the addition of the aggressive anions. The mea-
sured current did not flow immediately upon the addition of the
corrosive agent, but a certain period (induction period) in which
no current flows was first recorded. The pitting corrosion current
density is defined here as: (total current flowing in the circuit)/(to-
tal surface area of the electrode undergoing attack).
Two sets of experiments were conducted. In one set, the effect
of different concentration of SO42 or Cl anions, as aggressive an-
ions, on the magnitude of the pitting corrosion current was exam-
ined in solutions of constant Ca(OH)2 concentration. In the second
set of experiments, the effect of the concentration of the Ca(OH)2
on the corrosion current, at constant concentration of the aggres-
sive anions, was also studied. For each solution concentration,
duplicate measurements of the flowing current were carried out
and the mean value of the two readings was taken in consideration.
The error in corrosion current measurements was evaluated at less
than 10%.
Naturally aerated calcium hydroxide was used as passivating
agent, while Na2SO4 and NaCl were used as attacking agents. All
chemicals were of analytical-grade qualities. Solutions were pre-
pared using triply-distilled water. Each experiment was carried
out with freshly prepared electrodes and with new portion of the
solutions. The cell has a double wall jacket through which water,
at the adjusted temperature, was circulated. Measurements were
carried out at a constant temperature 25 ± 0.1 °C, except those re-
lated to the effect of temperature. The cell temperature was con-
trolled using an ultra thermostat type polyscience (USA).
Scanning electron micrographs of the tested electrodes were taken
using a Jeol Scanning Microscope JSM-T100 (Japan).
3. Results and discussion
When the steel electrodes are immersed in a naturally aerated
solutions of Ca(OH)2 of sufficient concentrations, a state of perma-
nent passivity occurs and practically no current could be detected.
Hausman [32] attributed this passivity to the formation of a hy-
drated iron oxidation films on the metal surface. The composition
of the oxide layer has been suggested to be spinal a-Fe3O4-c-Fe2O3
solid solution [33,34]. Lattice discontinuities occurring in the oxide
layer in the form of dislocations or, on large scale, as pores which
were viewed as channels through which mass transfer can occur.
Cao et al. [20], on the other hand, are of the opinion that the pas-
sive layer is formed through electrochemical reactions in which a
dense 3-D non-porous iron (III) layer is formed intimately adherent
to the steel surface. The initial rate of oxide film thickening is evi-
dently slow, as demonstrated by the STEM image [35]. The slow
growth and maturation of the initial oxide film constitute the pas-
sive state [35]. The electrochemical mechanisms of protection dur-
ing this stage are identical to those operative during the early
stages of film formation and are conventionally described by the
anodic half-cell reaction.
On addition of the aggressive anions to the main compartment
of the cell, currents start to flow, after an induction period, due to
the destruction of the passivating oxide film by the added aggres-
sive anion and the initiation of pitting corrosion. These currents at-
tain steady-state values, icorr, which depend on the concentration
 E.E. Abd El Aal et al. / Corrosion Science 51 (2009) 1611–1618 1613

of Ca(OH)2 and the type and concentration of the aggressive
anions.
The curves of Fig. 2(A and B) show the variation of the current
flowing in the circuit with time, in solutions of 5  103 M
Ca(OH)2, slightly lower than saturation, to which increasing
amounts of Na2SO4 and NaCl as aggressive anions were, respec-
tively, added to give known aggressive anion concentrations. On
the other hand, Fig. 3(A and B) show the behavior of the steel elec-
trode when the Na2SO4 or NaCl content of the solution was kept
constant (5  102 M) while that of Ca(OH)2 was varied.
When the aggressive anions present in very small concentra-
tions that can be tolerated by the Ca(OH)2, no current flows in
the cell, curves 1 in Fig. 2(A and B). These concentrations of the
aggressive anions are not sufficient to undermine the passive oxide
film and initiation of pitting of the steel. When the concentration of
the aggressive anions is slightly increased, an electric current starts
to flow in the circuit. This current does not flow immediately after
the addition of the aggressive anion, but after a period of a nil-cur-
rent was recorded, curves 2 in Fig. 2 (A and B). The existence of
such current is an indication of the occurrence of an electrochem-
ical reaction at the surface of the electrode [36–40]. Since the elec-
trode is initially in the passive state, the conditions are suitable for
the destruction of passivity and initiation of pitting corrosion after
addition of the aggressive anions [36–40]. However, after the
elapses of a certain time, the current starts to decrease and finally
attains a zero value. This behavior could be attributed to the
repassivation of the preformed pits [41–43]. When the rate of
repassivation is slightly inferior to that of film breakdown, meta-
stable pits are assumed to be formed and current flows. The meta-
stable pits generated had a very limited lifetime which depends on
the aggressive anion concentration after which they have been
repassivated again and the current ceases to flow. During the pro-
cess of repassivation, the aggressive anions at the pit surface
should be replaced by passivating anions [44].
On further increasing of the concentration of the aggressive an-
ions, above threshold concentrations which depend on the concen-
tration of the passivating solution [45–47], current starts to flow
after the elapses of an induction period, s, to reach steady-values
which depend on both Ca(OH)2 and aggressive anion concentra-
tions, [(curves 3–12 in Fig. 2(A and B)]. In one and the same passi-
vator solution, the induction period, fore pitting corrosion to occur,
becomes shorter the higher the concentration of the attacking
agent. This period is usually associated with the initiation of pitting
corrosion [48,49] and could be attributed to the time taken by the
aggressive anions either to penetrate through the passivating film
[50] or to compete with the passivating anions for adsorption sites
on the metal surface [51]. Visible pits are observed by examination
of the electrode surface, under scanning electron microscope, after
immersion for a period of 2 hours in solutions of 5  103 M
Ca(OH)2 containing 5  102 M each of Na2SO4 and NaCl, Fig. 4(A
and B), respectively. It is clear that this concentration of the aggres-
sive anions causes the formation of clear pits, some of which con-
tain inside traces of the corrosion products. Few fine pits are also
noted in the micrographs. However, in sulfate solutions, Fig. 4(A),

A 0.6
1
-5
1.0x10 M Na2SO4
12 -5
2 2.5x10 M
0.5 11 -4
3 1.0x10 M
10 -4
4 5.0x10 M
-3
0.4 5 5.0x10 M
2

-2
Current density, μA/cm

6 1.0x10 M
9 -2
7 2.5x10 M
0.3 -2
8 5.0x10 M
8 -1
9 1.0x10 M
-1
10 3.0x10 M
0.2 7 -1
6 11 5.0x10 M
-1
12 7.5x10 M
5
0.1
4
3
0.0 2
1
0 20 40 60 80 100 120 140 160 180
Time, min.

B 0.6

0.5
2

-5
1
Current density, μA/cm

12 5.0x10 M NaCl
0.4 -5
11 2 7.5x10
-4
10 3 1.0x10
0.3 -4
4 5.0x10
9 -3
5 5.0x10
-2
0.2 6 1.0x10
8 -2
7 7 2.5x10
6 -2
8 5.0x10
0.1 -1
5 9 1.0x10
4 -1
10 3.0x10
3 -1
0.0 2 11 5.0x10
1 12 7.5x10
-1
0 20 40 60 80 100 120 140 160 180
Time, min.

Fig. 2. Variation of the pitting corrosion current density with time in solutions of 5  103 M Ca(OH)2 at 25 °C in presence of different: (A) Na2SO4 and (B) NaCl additives.
1614 E.E. Abd El Aal et al. / Corrosion Science 51 (2009) 1611–1618

A 1 1x10-5 M Ca(OH)2
2 1x10-4 M
0.7
3 1x10-3 M 1
4 2.5x10-3M
0.6 5 5x10-3 M
6 1x10-2 M
2
0.5
2
Current density, μA./cm

0.4
3
4
0.3
5
6
0.2

0.1

0.0

0 20 40 60 80 100 120 140 160

Time, min.

B 0.7 1 1.0x10-5 M Ca(OH)2

2 1.0x10-4 M
0.6 3 1.0x10-3 M
4 2.5x10-3 M 1
0.5
5 5.0x10-3 M
6 1.0x10-2 M
2
Current density, μ A/cm

0.4 2

0.3 3
4
5
0.2 6

0.1

Fig. 4. (A) and (B). Scanning electron micrographs of the pitted steel surface in
0.0
5  103 M Ca(OH)2 in presence of: (A) 5  102 M Na2SO4 and (B) 5  102 M NaCl,
after immersion for 2 h.
0 20 40 60 80 100 120 140 160
Time, min.

Fig. 3. Variation of the pitting corrosion current density with time in solutions of
different concentrations of Ca(OH)2 in the presence of (A) 5  102 M Na2SO4 and
(B) 5  102 M NaCl at 25 °C.
the large corroded areas might probably have resulted from smal-
ler pits expanded equally laterally as well as inwardly so that they
appear as large attacked areas.
The dependence of the induction period, s in min., on the con-
centration of the aggressive anions (Cagg in mol l1), in
5  103 M Ca(OH)2, can be seen from the curves of Fig. 5(A). These
curves represent the relation between the two variables on a dou-
ble logarithmic scale. Straight-line relationships are obtained satis-
fying the following equation [36–40]:
log s ¼ a  b log C agg
where a and b are constants. The value of the constant, b, of the
nearly parallel lines of Fig. 5(A) was approximately 0.35 min/dec-
ade. The constancy of this value could be explained on the basis that
the mechanism of the breakdown of passive film on steel in the
presence of SO42 and Cl anions is the same. The values of the con-
stant, a, decreases in the order: SO42 > Cl. This reflects the order
of aggressiveness of these anions toward the initiation of pitting
corrosion on the steel surface.
However, in solutions of constant aggressive anions concentra-
tion, the induction time for pitting corrosion to take place, s, in-
creases with increasing the Ca(OH)2 concentration, C CaðOHÞ2 in
mol l1, Fig. 5(B), according to the following equation:
log s ¼ a þ b log C CaðOHÞ2 ð2Þ
where a and b are constants, depend on the type of aggressive an-
ions in solution. The values of the constant a decrease in the order
SO42 > Cl which is also the same order of decrease in their aggres-
siveness towards the initiation of pitting corrosion on the steel
surface.
Following the induction period, the current density rises stea-
dily, due to the propagation and the increase in the number of ac-
tive pits on the electrode surface and the corresponding increase in
the total anodic area. The current density ultimately reaches steady
values, which depend on the concentration of both the passivating
and corroding agents. The steady value of current denotes that the
corrosion of the metal occurs at the bottom of the pits formed
while their number remains constant [36–40]. However, the de-
ð1Þ
tected increase of the steady-state currents upon increasing the
aggressive anion concentration denotes an increase in the number
of the initiated pits, i.e. an increase in the total anodic area [36].
Since the area of the anodic pits is not known, and the study is
of a comparative nature, the pitting corrosion current density is
here defined as: (total current flowing in the circuit)/(total area
of the electrode undergoing attack).
As is seen from the curves of Fig. 2(A and B), the corrosion cur-
rent density, i in lA/cm2, measured in one and the same Ca(OH)2
solution, increases with the increase in concentration of SO42
and Cl anions, Fig. 2(A and B). On the other hand, when keeping
the concentration of the aggressive anions constant, the corrosion
current density decreases as the concentrations of Ca(OH)2 in-
 E.E. Abd El Aal et al. / Corrosion Science 51 (2009) 1611–1618 1615

A 2.5 Eqs. (3) and (4) were derived theoretically by Shams El Din et al.
[36] on the basis of competitive adsorption of the two opposing
agents (inhibitor and aggressive anions) on the surface of the me-
2.0 tal, and its effect on structure of the double layer at the metal/solu-
tion interface. Comparison between the experimental values of a1
(a2) and b1 (b2) with the corresponding terms of the theoretical
log τ, min.

1.5 equations was confirmed in the case of pitting of Zn [36], Fe [37],

and steel [38]. According to the theoretical derivation of Eq. (3)
[36], the slope ‘‘b1” of the (log icorr  log Cagg) curves should amount
1.0 to the value, a1n1/Z1, where a1 is the transfer coefficient of the ano-
dic reaction, n1 is the number of electrons involved in the oxidation
reaction and Z1 is the valency of the aggressive ions. The magni-
0.5 tude of the transfer coefficient, a1, depends on the nature of the
electrode reaction as well as on the type and concentration of
Na2SO4
NaCl
the supporting electrolyte [36]. For electrode reactions governed
0.0 by transfer across a single energy barrier, values of the transfer
-5.5 -5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 coefficient varying between 0.3 and 0.7 are commonly given [36].
log Cagg., M Accordingly, the values of the constant b1 should depend on the
number of electrons, n1, and the valency of the aggressive anions,
Z1. Therefore, three alternatives are expected for the values of the
B 2.5
slope b1. Thus, when n1 sets equal to 2 for the reaction (Fe ? -
Fe2+ + 2e) and Z1 sets equal to 1 and 2 for Cl and SO42 anions,
2.0 the term a1n1/Z1 assumes the values of 0.6–1.4 for Cl anions

1.5 A 0.0
log τ, min.

-0.2

1.0 -0.4
2
log current density, μA/cm

-0.6

0.5
-0.8 Na2SO4
Na2SO4
NaCl NaCl
-1.0
0.0
-5.5 -5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5
-1.2
log CCa(OH) , M
2
-1.4

Fig. 5. Variation of the induction period, s, with the molar concentration of (A) the
-1.6
aggressive anions and (B) the passivator anions, on double logarithmic scales.

-1.8
-5.5 -5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
creases, Fig. 3(A and B). The relation between the two parameters log Cagg., M
is not, however, linear within the concentration ranges examined
in the present investigation. The two variables are best represented
by double logarithmic relations, Fig. 6(A and B). B 0.0
-0.1
For solutions of constant Ca(OH)2 concentrations, the relation -0.2
becomes: -0.3
-0.4
2

log icorr ¼ a1 þ b1 log C agg ð3Þ

log current density , μA/cm

-0.5
-0.6
On the other hand, in solutions of constant SO42 
or Cl concentra-
-0.7
tions, the corresponding relation is: -0.8
-0.9
log icorr ¼ a2  b2 log C CaðOHÞ2 ð4Þ
-1.0
where a1 (a2) and b1 (b2) are constants. In Table 1, the values of -1.1
-1.2
these constants for the various systems are grouped together.
-1.3
-1.4
-1.5 Na2SO4
-1.6 NaCl
Table 1 -1.7
Values of the parameters, a1, b1, a2 and b2 for the various systems studied. -1.8
-5.5 -5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5
System Concentration a1 b1 a2 b2
log CCa(OH) , M
SO42 5  103 M Ca(OH)2 0.24 0.26 2
Cl 5  103 M Ca(OH)2 0.26 0.35
Ca(OH)2 5  102 M SO42 0.89 0.15 Fig. 6. Variation of the corrosion current density with the molar concentration of:
Ca(OH)2 5  103 M Cl 0.99 0.15 (A) the aggressive anions and (B) the passivating anions on double logarithmic
scales.
1616 E.E. Abd El Aal et al. / Corrosion Science 51 (2009) 1611–1618

and 0.3–0.7 for SO42 anions, respectively. When, n1, is set equal to
3 as for the reaction: (Fe ? Fe3+ + 3e) and Z1 is 1 or 2 for Cl and
SO42 anions, the term a1n1/Z1 assumes the values of 0.9–2.1 for
Cl  and 0.45–1.05 for SO42 anions. The third alternative sets in
when, n1 equal 1 as for the reaction (Fe2+ ? Fe3+ + e). In this case
the values of the slope b1 should equal 0.3 as a lower limit and
0.7 as an upper limit for Cl anions and 0.15–0.35 for the SO42 an-
ions. Examination of the b1 values listed in Table 1 reveals that
these values are, to a large extent, within the predicted range of
the oxidation reaction:
Fe2þ ! Fe3þ þ e
The term, a1, i.e. the value of log icorr at Cagg = 1 M, is a measure of the
corrosivity of the particular aggressive anion. The value depends pri-
marily on the type and secondly on the concentration of the passiva-
tor anions used. In the case of Ca(OH)2 solution, the magnitude of a1
decreases in the order SO42 > Cl. This is the expected order as re-
vealed by other authors [52]. The decrease in the value of a1 with the
increase in the concentration of the passivating Ca(OH)2 solution is
independent of the nature of the aggressive anions due to the corre-
sponding increase in the surface coverage by the passivators.
The assessment of the b2 values from the theoretical derivation
of Eq. (4) is also of interest (b2 = a2n2/Z2). In the case of Ca(OH)2,
Z2 = 2 and for n1 equals 1 for reaction (5), b2 should have a value
of 0.15 as a lower limit and 0.35 as an upper limit. Inspection of
the values of b2 in Table 1 reveals that it is within the predicted
range of the theoretical derivation. The values of a2 listed in Table
1 show that at equimolar concentrations of SO42 and Cl anions
and in solutions of comparable concentrations of Ca(OH)2, the rate
of attack decreases in the order: SO42 > Cl [see Fig. 6 (A) and (B)].
The variation of the corrosion current of steel electrode, in
1  103 M Ca(OH)2 solutions in presence of 5  102 M of SO42
and Cl anions, at different temperatures ranged from 25 °C to
65 °C, is shown in Fig. 7. As can be seen from the curves of Fig. 7,
ð5Þ when the temperature is increased, the induction time, s, required
for the initiation of pitting corrosion decreases while the steady-
state corrosion current density associated with pit propagation in-
creases. This behavior could be attributed to the increased corro-
sion rate of steel as the temperature increases, due to the
increased reactivity of the aggressive anion at high temperature.
This behavior could be also attributed to either larger desorption
of the passivator anions compared to the aggressive anion, or to
a faster rate of penetration of the latter into the passivating film
[53]. In general, on raising the temperature, the increased rate of
pit initiation as reflected by the decrease of the induction period,
s, and the increased rate of pit propagation as shown by the in-
crease in the steady corrosion current density, could be repre-
sented by the familiar Arrhenius equation:

A
o
3.5 1 25 C
o
2 35 C
3.0 3
o
45 C 5
A 1.4

o 1.2
4 55 C
o
5 65 C 1.0
2.5
4 0.8
2
Current density, μA/cm

2.0
log τ, min.

0.6

1.5 0.4
3
0.2
1.0
2 0.0

0.5 -0.2
1
-0.4 Na2SO4
0.0 NaCl
-0.6
0 20 40 60 80 100 120
-0.8
0.0029 0.0030 0.0031 0.0032 0.0033 0.0034
Time, min.
1/T, k
B 3.5
B 1.4

3.0 1.2

o 1.0
1 25 C
2

2.5
log current density, μA/cm

o
2

2 35 C 0.8
Current density, μA/cm

o
3 45 C
2.0 o 0.6
4 55 C
5
o
65 C 5 0.4
1.5
4 0.2

0.0
1.0
3 -0.2
0.5 2 -0.4
Na2SO4
1 NaCl
-0.6
0.0
0 20 40 60 80 100 120 -0.8
0.0029 0.0030 0.0031 0.0032 0.0033 0.0034
Time, min.
1/T, k
Fig. 7. Variation of the current density with time in solutions containing: (A)
1  103 M Ca(OH)2 + 5  102 M Na2SO4 and (B) 1  103 M Ca(OH)2 + 5  102 M Fig. 8. Arrhenius plots of: (A) the induction period and (B) the corrosion current
NaCl, at different temperatures. density of steel in solutions containing Na2SO4 and NaCl with 1/T.
 E.E. Abd El Aal et al. / Corrosion Science 51 (2009) 1611–1618
DH a
log rate ¼ log A  ð6Þ
2:303RT
where A is the pre-exponential factor, DHa the molar activation en-
ergy of the respective process and R the gas constant. From Arrhe-
nius plots of the induction period, Fig. 8(A), the activation energy
for the initiation of pitting corrosion on steel electrode in presence
of SO42 and Cl anions is computed to be 39.30 and 51.87 KJ mol1,
respectively. At the same time, from the Arrhenius plots of the cor-
rosion current (rate of corrosion), the activation energy, DHa,
Fig. 8(B), for the propagation of pitting corrosion of steel by SO42
and Cl anions is found to be 41.04 and 39.40 KJ mol1, respectively.
4. Conclusions
(1) A simple divided H-cell was used for measuring and evaluat-
ing the pitting corrosion currents on reinforcing steel elec-
trode in Ca(OH)2 solutions in presence of SO42 and Cl
anions.
(2) Pitting corrosion currents started to flow after an induction
period, s, which depended on the concentration of both
the passivating Ca(OH)2 and the aggressive anions.
(3) The pitting corrosion currents finally reached steady-state
values which varied with the concentration of counter acting
anions. In solutions of constant Ca(OH)2 concentration, the
corrosion current varied with the concentration of the
aggressive anions according to: log icorr = a1 + b1 log Cagg,
and in solutions of constant aggressive anions concentra-
tions, according to: log icorr = a2 + b2 log C CaðOHÞ2 , where a1
(a2) and b1 (b2) are constants. From the values of the con-
stant a2 the corrosivity of the aggressive anions decreases
in the order: SO42 > Cl.
(4) From the values of the constant, b1, the corrosion process
was found to be controlled by a single electron transfer
reaction.
(5) Raising the temperature decreased the induction period
associated with pit initiation and increased the corrosion
current associated with pit propagation. From Arrhenius
plots, the activation energies for both pit initiation and pit
propagation were calculated.
Acknowledgement
The authors appreciate the financial support and facilities pro-
vided by the University of Zagazig to finish this work.
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