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 rates of steel embedded in concrete [13–18]. However,
Corrosion of steel reinforcement in concrete, as in most corro- a number of uncertainties arise with the use of these techniques
sion processes, is of electrochemical nature. The corrosion process due to the several experimental precautions which should be taken
necessitates an anodic area where oxidation reaction occurs, a in account. Page [19] pointed out that the electrodes are made to
cathodic area where reduction reaction occurs and a conducting function as net anodes or net cathodes in cells in which the deriv-
medium for the transportation of ions between anode and cathode. ing force is supplied by an external power source. In practice, how-
In the case of steel reinforcement, the highly alkaline concrete pore ever, separate anodic and cathodic reactions occur simultaneously
solution serves as the ion conducting medium. This alkalinity is on the same electrode surface under the deriving force of the po-
largely due to the presence of sodium and potassium oxides in tential difference between the anodic and cathodic sites [20].
the cement, as well as, Ca(OH)2 produced in the hydration reaction Alternate current impedance is another technique used to esti-
of the cement minerals [1–6]. mate the corrosion process of reinforcement steel [21–23]. How-
In this connection, several electrochemical techniques have ever, the determination of A.C. impedance, although it gives very
been developed to asses the corrosion of reinforcing steel. The useful information related to the electrochemical process, is more
most well known of these techniques is the half-cell potential time-consuming and the impedance values measured in the range
mapping. The potentials of the steel are measured relative to a sta- of very low frequencies do not always give accurate information
ble reference half-cell on the outer surface of the concrete. These for calculating corrosion rate [24].
potentials can be related to the probability of corrosion occurring In the present investigation, a simple experimental arrange-
and provide little quantitative information regarding the corrosion ment is applied for the direct measurement and evaluation of the
rate [7–11]. corrosion current (corrosion rate) operating under natural condi-
Measurement of the resistivity of the concrete in conjunction tions. This is successfully accomplished by using a simple, divided
with potential mapping is another technique supposed to asses H-cell accommodating two similar steel electrodes immersed in a
the corrosion of steel in concrete [9,12–14]. A large potential gra- passivating Ca(OH)2 solution which represents the main constitu-
dient associated with a low concrete resistivity will normally result ent of concrete pore solution [1–6,25,26]. Chloride and sulfate
in high rate of corrosion. are used as aggressive anions. Chloride ions are being present as
original constituents of concrete mixture or as a result of penetra-
* Corresponding author. Tel.: +20 10 5280422; fax: +20 55 234 5452. tion from the environment. Sulfate ions, on the other hand, are
E-mail address: emad_abdelaal@hotmail.com (E.E. Abd El Aal). 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 few experiments, however, small currents were observed to flow,
electrodes are short circuited over a low resistance nanoamperom- apparently resulting from slight uncontrollable differences in envi-
eter. When equilibrium is established, SO42 or Cl, as corrosion ronmental conditions. These currents are decayed in a period of
anions is added to one side of the cell. After a short induction per- about 20 min. When this condition was established, a weighed
iod, an electric current starts to flow as a result of the propagation amount of Na2SO4 or NaCl, as aggressive anions, was added to
of pitting corrosion. As far as the authors are aware, it is the first the solution of the main compartment and the current flowing
time to measure the corrosion current and consequently the corro- was recorded as a function of time until steady values were estab-
sion rate of reinforcement steel under natural corrosion conditions lished. Since the two electrodes were initially in the passive state,
using no external power sources. the conditions are suitable for the initiation and propagation of pit-
ting corrosion after the addition of the aggressive anions. The mea-
2. Experimental sured current did not flow immediately upon the addition of the
corrosive agent, but a certain period (induction period) in which
The simple electrolytic cell that was used is shown diagram- no current flows was first recorded. The pitting corrosion current
matically in Fig. 1. It consists of a 250 ml borosilicate glass beaker density is defined here as: (total current flowing in the circuit)/(to-
containing 100 ml of the Ca(OH)2 solution as a passivating agent, tal surface area of the electrode undergoing attack).
one of the steel electrode (A) and a magnetic stirrer. The second Two sets of experiments were conducted. In one set, the effect
steel electrode (B) was enclosed in a borosilicate glass tube ended of different concentration of SO42 or Cl anions, as aggressive an-
with a fine porosity, fritted centered glass disc G4 (C). The two steel ions, on the magnitude of the pitting corrosion current was exam-
electrodes (A and B) were short-circuited through a nanoamper- ined in solutions of constant Ca(OH)2 concentration. In the second
ometer (Siemens type N 5536). set of experiments, the effect of the concentration of the Ca(OH)2
The steel electrodes were made from steel samples produced by on the corrosion current, at constant concentration of the aggres-
the Egyptian Mill Steel Company, always used as reinforcement, sive anions, was also studied. For each solution concentration,
and having the following chemical composition, in accordance duplicate measurements of the flowing current were carried out
with the Egyptian ASTM A615 standard [31]: and the mean value of the two readings was taken in consideration.
The error in corrosion current measurements was evaluated at less
C Si Mn P S Fe than 10%.
Naturally aerated calcium hydroxide was used as passivating
0.32 0.24 0.89 0.024 0.019 bal. ‘‘98.507” 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
Each electrode was fixed to a borosilicate glass tube with epoxy re- out with freshly prepared electrodes and with new portion of the
sin so that only the bottom surface area (1.33 cm2) was exposed to solutions. The cell has a double wall jacket through which water,
the solution. The steel electrodes were abraded into uniform sur- at the adjusted temperature, was circulated. Measurements were
faces by a grinding machine (model Jean Wirtz TG 200, Germany) carried out at a constant temperature 25 ± 0.1 °C, except those re-
with successive 0-, 00- and 000-grades emery papers. The elec- lated to the effect of temperature. The cell temperature was con-
trodes were then degreased with acetone and finally washed with trolled using an ultra thermostat type polyscience (USA).
triply-distilled water. Scanning electron micrographs of the tested electrodes were taken
Since the surface treatment of the two electrodes was the same, using a Jeol Scanning Microscope JSM-T100 (Japan).
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 3. Results and discussion
on connecting the electrodes through the nanoamperometer. In a
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-
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, sive anion and the initiation of pitting corrosion. These currents at-
G4, and nA is a nanoamperometer. 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 repassivation is slightly inferior to that of film breakdown, meta-
anions. stable pits are assumed to be formed and current flows. The meta-
The curves of Fig. 2(A and B) show the variation of the current stable pits generated had a very limited lifetime which depends on
flowing in the circuit with time, in solutions of 5  103 M the aggressive anion concentration after which they have been
Ca(OH)2, slightly lower than saturation, to which increasing repassivated again and the current ceases to flow. During the pro-
amounts of Na2SO4 and NaCl as aggressive anions were, respec- cess of repassivation, the aggressive anions at the pit surface
tively, added to give known aggressive anion concentrations. On should be replaced by passivating anions [44].
the other hand, Fig. 3(A and B) show the behavior of the steel elec- On further increasing of the concentration of the aggressive an-
trode when the Na2SO4 or NaCl content of the solution was kept ions, above threshold concentrations which depend on the concen-
constant (5  102 M) while that of Ca(OH)2 was varied. tration of the passivating solution [45–47], current starts to flow
When the aggressive anions present in very small concentra- after the elapses of an induction period, s, to reach steady-values
tions that can be tolerated by the Ca(OH)2, no current flows in which depend on both Ca(OH)2 and aggressive anion concentra-
the cell, curves 1 in Fig. 2(A and B). These concentrations of the tions, [(curves 3–12 in Fig. 2(A and B)]. In one and the same passi-
aggressive anions are not sufficient to undermine the passive oxide vator solution, the induction period, fore pitting corrosion to occur,
film and initiation of pitting of the steel. When the concentration of becomes shorter the higher the concentration of the attacking
the aggressive anions is slightly increased, an electric current starts agent. This period is usually associated with the initiation of pitting
to flow in the circuit. This current does not flow immediately after corrosion [48,49] and could be attributed to the time taken by the
the addition of the aggressive anion, but after a period of a nil-cur- aggressive anions either to penetrate through the passivating film
rent was recorded, curves 2 in Fig. 2 (A and B). The existence of [50] or to compete with the passivating anions for adsorption sites
such current is an indication of the occurrence of an electrochem- on the metal surface [51]. Visible pits are observed by examination
ical reaction at the surface of the electrode [36–40]. Since the elec- of the electrode surface, under scanning electron microscope, after
trode is initially in the passive state, the conditions are suitable for immersion for a period of 2 hours in solutions of 5  103 M
the destruction of passivity and initiation of pitting corrosion after Ca(OH)2 containing 5  102 M each of Na2SO4 and NaCl, Fig. 4(A
addition of the aggressive anions [36–40]. However, after the and B), respectively. It is clear that this concentration of the aggres-
elapses of a certain time, the current starts to decrease and finally sive anions causes the formation of clear pits, some of which con-
attains a zero value. This behavior could be attributed to the tain inside traces of the corrosion products. Few fine pits are also
repassivation of the preformed pits [41–43]. When the rate of 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 log s ¼ a þ b log C CaðOHÞ2 ð2Þ
different concentrations of Ca(OH)2 in the presence of (A) 5  102 M Na2SO4 and
(B) 5  102 M NaCl at 25 °C. 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-
the large corroded areas might probably have resulted from smal- siveness towards the initiation of pitting corrosion on the steel
ler pits expanded equally laterally as well as inwardly so that they surface.
appear as large attacked areas. Following the induction period, the current density rises stea-
The dependence of the induction period, s in min., on the con- dily, due to the propagation and the increase in the number of ac-
centration of the aggressive anions (Cagg in mol l1), in tive pits on the electrode surface and the corresponding increase in
5  103 M Ca(OH)2, can be seen from the curves of Fig. 5(A). These the total anodic area. The current density ultimately reaches steady
curves represent the relation between the two variables on a dou- values, which depend on the concentration of both the passivating
ble logarithmic scale. Straight-line relationships are obtained satis- and corroding agents. The steady value of current denotes that the
fying the following equation [36–40]: corrosion of the metal occurs at the bottom of the pits formed
while their number remains constant [36–40]. However, the de-
log s ¼ a  b log C agg ð1Þ
tected increase of the steady-state currents upon increasing the
where a and b are constants. The value of the constant, b, of the aggressive anion concentration denotes an increase in the number
nearly parallel lines of Fig. 5(A) was approximately 0.35 min/dec- of the initiated pits, i.e. an increase in the total anodic area [36].
ade. The constancy of this value could be explained on the basis that Since the area of the anodic pits is not known, and the study is
the mechanism of the breakdown of passive film on steel in the of a comparative nature, the pitting corrosion current density is
presence of SO42 and Cl anions is the same. The values of the con- here defined as: (total current flowing in the circuit)/(total area
stant, a, decreases in the order: SO42 > Cl. This reflects the order of the electrode undergoing attack).
of aggressiveness of these anions toward the initiation of pitting As is seen from the curves of Fig. 2(A and B), the corrosion cur-
corrosion on the steel surface. rent density, i in lA/cm2, measured in one and the same Ca(OH)2
However, in solutions of constant aggressive anions concentra- solution, increases with the increase in concentration of SO42
tion, the induction time for pitting corrosion to take place, s, in- and Cl anions, Fig. 2(A and B). On the other hand, when keeping
creases with increasing the Ca(OH)2 concentration, C CaðOHÞ2 in the concentration of the aggressive anions constant, the corrosion
mol l1, Fig. 5(B), according to the following equation: 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 Z2 = 2 and for n1 equals 1 for reaction (5), b2 should have a value
3 as for the reaction: (Fe ? Fe3+ + 3e) and Z1 is 1 or 2 for Cl and of 0.15 as a lower limit and 0.35 as an upper limit. Inspection of
SO42 anions, the term a1n1/Z1 assumes the values of 0.9–2.1 for the values of b2 in Table 1 reveals that it is within the predicted
Cl  and 0.45–1.05 for SO42 anions. The third alternative sets in range of the theoretical derivation. The values of a2 listed in Table
when, n1 equal 1 as for the reaction (Fe2+ ? Fe3+ + e). In this case 1 show that at equimolar concentrations of SO42 and Cl anions
the values of the slope b1 should equal 0.3 as a lower limit and and in solutions of comparable concentrations of Ca(OH)2, the rate
0.7 as an upper limit for Cl anions and 0.15–0.35 for the SO42 an- of attack decreases in the order: SO42 > Cl [see Fig. 6 (A) and (B)].
ions. Examination of the b1 values listed in Table 1 reveals that The variation of the corrosion current of steel electrode, in
these values are, to a large extent, within the predicted range of 1  103 M Ca(OH)2 solutions in presence of 5  102 M of SO42
the oxidation reaction: 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,
Fe2þ ! Fe3þ þ e ð5Þ when the temperature is increased, the induction time, s, required
for the initiation of pitting corrosion decreases while the steady-
The term, a1, i.e. the value of log icorr at Cagg = 1 M, is a measure of the state corrosion current density associated with pit propagation in-
corrosivity of the particular aggressive anion. The value depends pri- creases. This behavior could be attributed to the increased corro-
marily on the type and secondly on the concentration of the passiva- sion rate of steel as the temperature increases, due to the
tor anions used. In the case of Ca(OH)2 solution, the magnitude of a1 increased reactivity of the aggressive anion at high temperature.
decreases in the order SO42 > Cl. This is the expected order as re- This behavior could be also attributed to either larger desorption
vealed by other authors [52]. The decrease in the value of a1 with the of the passivator anions compared to the aggressive anion, or to
increase in the concentration of the passivating Ca(OH)2 solution is a faster rate of penetration of the latter into the passivating film
independent of the nature of the aggressive anions due to the corre- [53]. In general, on raising the temperature, the increased rate of
sponding increase in the surface coverage by the passivators. pit initiation as reflected by the decrease of the induction period,
The assessment of the b2 values from the theoretical derivation s, and the increased rate of pit propagation as shown by the in-
of Eq. (4) is also of interest (b2 = a2n2/Z2). In the case of Ca(OH)2, 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 1617

DH a [8] A.K. Suryavanshi, S. Syam Sunder, B.U. Nayak, A comparison of surface

log rate ¼ log A  ð6Þ potentials of r. c. structures using reference electrodes, Corrosion Prevention
2:303RT
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