Electrochimica Acta 54 (2009) 4067–4072

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Corrosion behavior of reinforcing steel in simulated concrete pore solutions:

A scanning micro-reference electrode study
Hui Xu, Yu Liu, Wen Chen, Rong-Gui Du ∗ , Chang-Jian Lin
State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University,
Xiamen, Fujian 361005, PR China

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

Article history: The scanning micro-reference electrode (SMRE) technique was used to study the corrosion behavior of
Received 25 August 2008 reinforcing steel in simulated concrete pore (SCP) solutions with different pH values. The early stage as
Received in revised form 2 February 2009 well as the propagation of the localized corrosion of reinforcing steel in different solutions was explored.
Accepted 17 February 2009
The results indicated that the potential distribution on the reinforcing steel surface changed in home-
Available online 25 February 2009
ostasis and the steel remained passive in the pure simulated concrete pore solution. The solution pH had
a significant effect on the localized corrosion of reinforcing steel, and the critical pH value for localized
Keywords:
corrosion of reinforcing steel in SCP solutions was between 11.46 and 11.31.
Reinforcing steel
Localized corrosion © 2009 Elsevier Ltd. All rights reserved.
Simulated concrete pore solution
Potential distribution
Scanning micro-reference electrode
technique

1. Introduction studies focusing on the depassivation of the steel caused by decreas-

Reinforced concrete is widely used for building materials and
plays a significant role in economic development. However, the
premature degradation of reinforced concrete structures due to the
reinforcing steel corrosion has become a serious problem in modern
society, which results in a huge economic loss [1–3].
Under normal conditions, reinforcing steel in concrete can be
protected from corrosion by forming a compact passive film on
its surface in concrete pore solution with high alkalinity (pH
12.5–13.5). However, the passive film can be locally damaged and
the localized corrosion of reinforcing steel takes place when pH
and/or the chloride concentration at the steel/concrete interface
reach the critical values for corrosion [4–9]. The pH of concrete
pore solution decreases during concrete carbonation due to the
neutralization of Ca(OH)2 in the interstitial solution with the acidic
gases (CO2 , SO2 , etc.) which diffuse into the steel/concrete inter-
face from the air [8]. The pH value of concrete pore solution is one
of the most important parameters affecting the corrosion behavior
of reinforcing steel in concrete.
In spite of the extensive studies of corrosion behaviors of rein-
forcing steel [4,6,9,10], the exact mechanism of its depassivation is
still unclear. Even though the effect of pH on the corrosion of rein-
forcing steel was discovered decades ago, there were only a few
ing pH of concrete pore solution during the carbonation process
[8,11–13]. In the urban and industrial areas, the acidic gases (CO2 ,
SO2 , NO2 , etc.) can make the local atmosphere acidic, and attack
the hydrated concrete. The reactions of neutralization in concrete
may decrease the pH value of concrete pore solution, induce the
steel surface depassivation, and consequently cause the steel cor-
rosion. Thus, further study of the pH influence on the stability of the
passive film is needed to understand the corrosion mechanisms of
reinforcing steel.
The scanning micro-reference electrode (SMRE) technique is a
powerful in situ monitoring method, which can identify the active
sites and monitor their development by measuring the potential
distribution on the metal surface [14–17]. The main purpose of this
work is to study the reinforcing steel corrosion behavior in sim-
ulated concrete pore solutions with different pH values using the
SMRE technique, and find the critical pH value for the occurrence of
localized corrosion of reinforcing steel. In addition, scanning elec-
tron microscopy (SEM) was used to examine the changes in surface
morphology of reinforcing steel after immersion in the test solu-
tions.
2. Experimental
2.1. Reinforcing steel specimens and solutions

∗ Corresponding author. Tel.: +86 592 2184655; fax: +86 592 2189354. The steel specimens (Ø 1.10 cm × 0.4 cm) used for all experi-
E-mail address: rgdu@xmu.edu.cn (R.-G. Du). ments were cut from a reinforcing steel rod (R235). The chemical

0013-4686/$ – see front matter © 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2009.02.046
4068 H. Xu et al. / Electrochimica Acta 54 (2009) 4067–4072
composition of the steel was (in wt.%): 0.390% C; 0.083% Si; 0.254%
Mn; 0.101% Cu; 0.012% S; 0.015% P; 0.027% Ni; 98.944% Fe. The side
surface of a steel sample was sealed with epoxy resin in a poly-
methyl methacrylate holder for SMRE measurements [16]. The steel
surface for tests was polished down to 1500 (for SMRE experiments)
or 1200 (for SEM experiments) grade SiC paper and rinsed with
double-distilled water. Before measurements, all the steel speci-
mens were ultrasonically rinsed with ethanol and dried in air.
Simple alkaline solutions simulating concrete pore solutions
were usually used for reinforcing steel corrosion testing [4,18,19].
In this work, concrete pore solution was simulated by a satu-
rated Ca(OH)2 solution (pH 12.56) [8], which was prepared with
analytical grade reagents and double-distilled water. The artificial
interfusion of electrolyte was considered and carried out. The SCP
solutions with different pHs between 12.56 and 9.78 were pre-
pared and used as the electrolytes for SMRE measurements. The
pH value was adjusted by adding double-distilled water into the
saturated Ca(OH)2 solution and the solution was transferred to the
electrochemical cell with a pipette before measurements. Most of
the test solution in the electrochemical cell was renewed every 0.5 h
by the fresh one with the same pH as the test solution between
measurements to keep the pH of the solution constant and avoid
the influence of the very little Cl− diffusing from the micro-luggin
bridge.
2.2. Scanning micro-reference electrode measurements
The measurements of the potential distribution on the reinforc-
ing steel surface were carried out using a home-designed SMRE
system, which is shown schematically in Fig. 1 [15,16]. The detail
information of the system could be found in literature [16]. The
microposition device was computer-aided with ␮m displacements
by two stepper motors for the SMRE measurements. One of them
controlled a probe scanning over the sample surface, the other con-
trolled another probe which tip was resting in the electrolyte as a
micro-reference electrode. Both probes were uniform. A high-input
impedance operational amplifier, as a voltage follower, was used to
minimize current leakage. A computer program was designed to
control the SMRE system, collect and analyze data [15,16].
Ag/AgCl electrodes were used for the probes, which could serve
not only as a scanning microprobe but also as a micro-reference
electrode for the SMRE experiments [15,16]. To obtain a high qual-
ity electrode, a glass capillary was hot-drawn to a tip of about 5 ␮m
inner diameter and filled with 1 M KCl solution containing agar
gel as a micro-luggin bridge of the Ag/AgCl electrode. Both micro-
luggin bridge and Ag/AgCl electrode were inserted into a larger glass
Fig. 1. Schematic diagram of SMRE measuring system.
tube. 1 M KCl solution was injected into the tube, and the top of the
glass tube was sealed with molten wax.
A steel specimen in electrochemical cell was installed face
upward onto the scanning stage of the SMRE system. The scan-
ning probe tip was close to the specimen surface (about 20 ␮m)
adjusted by a manual micrometer and an optical microscopy. Then
the electrolyte was added into the cell. Only 2 min were needed
for scanning an area of 5 mm × 5 mm with a scan step of 0.1 mm.
The electrolyte near the electrode might be stirred during probing
the electrode via Luggin capillary, but the electrolyte convection
caused by the stir was not severe since the outer diameter of a Lug-
gin capillary tip was very small (about 20 ␮m), which did not affect
the net current caused by the localized corrosion of the reinforcing
steel. Therefore, stirring the electrolyte near the electrode did not
differ from those that were set by natural convection during the
measurement of corrosion without the capillary motion. However,
the measurement conditions must be kept consistent in order to
obtain comparative results.
The measurements were carried out in air at open circuit poten-
tial at the room temperature (25 ± 2 ◦ C). The potential of the
steel electrode was not measured, and the difference in poten-
tial was measured between the two Ag/AgCl electrodes based on
our research objectives. The electrochemical signals monitored and
collected by a computer represented the potential distributions as
3D maps and their variations over the scanning area of the rein-
forcing steel surface during different immersion periods. On the
potential maps, a parameter on the vertical axis represented the
potential relative to the ground plane, and the difference between
a potential and the minimum potential value on the axis repre-
sented the difference between the scanning microprobe and the
micro-reference electrode. Positive potential values were selected
by the computer program automatically, which could clearly show
comparative results in the potential maps.
2.3. Scanning electron microscopy (SEM)
The morphology changes of reinforcing steel immersed in the
simulated concrete pore solutions with different pH values for
about 5 h were observed by Phillips-FEI XL30 ESEM-TMP and LEO
1530 SEM instrument.
2.4. X-ray energy dispersive spectroscopy (EDS)
The chemical composition of the corrosion products on reinforc-
ing steel surface was measured by the EDS instrument attached to
the above LEO 1530 SEM instrument.
3. Results and discussion
3.1. Potential distribution on the reinforcing steel surface in the
SCP solution
When localized corrosion of reinforcing steel takes place in a
solution, the potential fields will occur in the solution because the
direct current caused by the electrochemical reactions moves from
the anodes to the cathodes through the solution by an ionic path.
The potential distribution map on the steel surface can be obtained
by measuring the potential difference between a scanning micro-
probe and a micro-reference electrode. On the potential map, the
anodic areas and the cathodic areas can be identified, each poten-
tial peak represents single current flow or more, and the height of
a potential peak represents the magnitude of the current, as well
as a tendency toward localized corrosion. The SMRE technique can
detect and monitor potential changes during the various stages of
localized corrosion with good time and spatial resolutions.
 H. Xu et al. / Electrochimica Acta 54 (2009) 4067–4072 4069

Fig. 2. Potential maps of the reinforcing steel surface in the saturated Ca(OH)2 solu-
tion with pH 12.56 after immersion for (a) 5 min and (b) 305 min.
active anodic sites of the steel surface and the reference electrode
was evidently greater than the other cathodic sites, corresponding
to the sharp peaks on a potential distribution map. Thus, it is easy to
find whether localized corrosion occurs on the steel surface. The ini-
tiation and propagation of the sites can be monitored by measuring
the potential distribution maps at different time.
It is known that localized corrosion takes place when the pH
value of interstitial solution decreases to or below 10 resulting
from the concrete carbonation [8]. In order to study the reinforcing
steel corrosion behavior in solutions below pH 10, we measured
the potential distribution changes of the reinforcing steel surface
in a SCP solution with a pH of 9.78. The results indicated that the
large potential peaks appeared after only 1 min exposure to the
electrolyte (Fig. 3a). The height and the size of the potential peak
on the right-up corner increased with time indicating the contin-
uous growth of the active pits in that area (Fig. 3b). After 7 min
immersion, the yellow-brown corrosion products were observed
on the certain parts of the steel surface, where the large potential
peaks were observed. The SEM image (Fig. 4) showed that the steel
surface was rough and corrosion products appeared. To explore the
surface at pH below the critical value for reinforcing steel localized
corrosion, the yellow-brown corrosion products on the steel surface
immersed for 6 h in a SCP solution with pH 9.78 were analyzed by
EDS, and the results are shown in Fig. 5 Based on the EDS data, the
corrosion products mainly contained iron (about 78 wt.%) and oxy-
gen (about 14 wt.%), and might be hydroxides Fe(OH)2 and Fe(OH)3
or hydrated oxides depending on pH, etc., reference to Pourbaix
diagram for iron. Based on these results, it is obvious that the steel
localized corrosion occurred on steel in the SCP solution with such
a low pH value.

3.3. The critical pH value for reinforcing steel localized corrosion

The potential distribution images over the surface of reinforc-
ing steel in a pure SCP solution (saturated Ca(OH)2 solution) after
To determine the critical pH value for localized corrosion on the
immersion for different time are shown in Fig. 2. There was no large
reinforcing steel surface, the try and error method was used know-
or stable peak on the potential map during the exposure (about
ing the pH values for the steel passivation and severe corrosion as
5 h immersion). Only several small peaks (less than 3 mV) were
discussed above.
observed indicating that no localized corrosion occurred on the
steel surface. In the pure SCP solution with high pH, the steel surface
was quite stable with a dynamic balance between breakdown and
repassivation of the passive film. Under this condition, the localized
corrosion did not occur.
From Fig. 2 one may notice that the potential distribution on the
steel surface is inhomogeneous, which is due to the inhomogene-
ity of the surface structure. Some structural defects and impurities
always exist on the steel surface and may serve as micro-active sites,
which are indicated as the small potential peaks on the potential
maps. However, micropits do not develop to macro ones because
the critical conditions are not satisfied, and the reinforcing steel
remains passive state. There are many factors affecting the rein-
forcing steel corrosion behaviors. Under normal conditions, the pH
value of the medium that the steel exposed to is one of the most
important factors that affect the resistance of passive film break-
down. If pH of the concrete pore solutions is lower than the critical
value, the severe localized corrosion will occur on the steel surface.
Thus, it is possible to determine the critical pH for localized corro-
sion of reinforcing steel in SCP solutions by monitoring the potential
distribution changes of the steel surface in the different solutions
with various pH values.

3.2. Potential distribution on the reinforcing steel surface with

localized corrosion

The active anodic sites have higher current density than other
parts of the bulk reinforcing steel surface (as the cathodic area with- Fig. 3. Potential maps of the reinforcing steel surface in the simulated pore solution
out corrosion). The potential difference in the solution between the with pH 9.78 after immersion for (a) 1 min and (b) 5 min.
4070 H. Xu et al. / Electrochimica Acta 54 (2009) 4067–4072

Fig. 4. SEM image of reinforcing steel surface in the simulated pore solution with
pH 9.78 after immersion for 6 h.

Various SCP solutions were prepared with pH values between

12.56 and 9.78. It was found that no big or stable potential peak
occurred on the potential maps if the pH was 11.46 or higher, even
though the potential differences were greater than that observed
in Fig. 2, which meant the passive film of the steel was balanced by
the competition between the passivation and depassivation. Fig. 6
shows the varieties of potential images measured at different time
when the reinforcing steel was immersed in the SCP solution with
pH 11.46. During the measurement (about 5 h), there was no stable
potential peak on the potential maps. The biggest potential differ-
ence was about 8 mV, corresponding to the two small active pits
after 10 min exposure (Fig. 6a). They disappeared successively after
48 min immersion (Fig. 6b). The potential difference on the reinforc-
ing steel surface decreased below 2 mV after 81 min of immersion
and maintained this value for 5 h until the measurement was com-
pleted. After testing, there was no corrosion product on the steel
surface. In addition, the other immersion test for reinforcing steel
in the SCP solution with pH 11.46 for 5 d showed that the corro-
sion potential (vs. SCE) of the steel shifted positively from −0.365
to −0.280 V during 60 min immersion, and kept in a narrow range
of −0.260 to −0.240 V after 10 h immersion without sharply nega-
tive shift, which is a characteristic of the occurrence of passivity of
a metal. Therefore, we concluded that reinforcing steel was passive
in the SCP solution with pH 11.46. The critical pH value for localized
corrosion of steel should be lower than 11.46. Fig. 6. Potential maps of the reinforcing steel surface in the simulated pore solution
In the SCP solution with a pH of 11.31, no stable or large peak with pH 11.46 after immersion for (a) 10 min, (b) 48 min and (c) 81 min.

was observed on the potential distribution over the surface of rein-

forcing steel until at the 138 min immersion (Fig. 7b). The height
and size of the potential peak increased with exposure time and
the potential difference reached to 80.00 mV after 4 min immersion
Fig. 5. EDS spectra for the products on the reinforcing steel surface shown in Fig. 4.
since it appeared. This potential peak corresponded to a grow-
ing anodic area on the steel surface. Compared with the results
measured in pH 9.78 solution (Fig. 3), the large potential peak did
not appear until a longer exposure period (more than 2 h) due to
the enhanced stability of the passive film in the higher pH solu-
tion.
The peak values of micropits on the potential maps in different
corrosion systems can not be directly compared due to the dif-
ference of the corrosion systems and test conditions, e.g., solution
conductivity. Whether the micropits develop into corrosion macro-
pits significantly depends on whether the peak position is immobile
and its potential value increases with time. In the present work, the
potential of 7.2 mV in Fig. 7b was stable on the potential map with
its value increasing, which indicated pitting corrosion occurred on
the metal surface in this system. This conclusion was also verified
by observing the visible yellow-brown corrosion products on the
same location after the SMRE measurements.
 H. Xu et al. / Electrochimica Acta 54 (2009) 4067–4072 4071

Fig. 6a measured under a different pH value has shown a distinct

potential trend compared with that in Fig. 7b. In Fig. 6, the peak
value (about 8 mV) of two micropits did not increase with time and
disappeared after 48 min of immersion (Fig. 6b). After 67 min, the
potential difference on the whole map maintained below 2 mV and
the potential distribution kept in a dynamic balance (Fig. 6c), and
no further stable sharp peak appeared on the potential map. Thus,
the potential peaks (about 8 mV) observed in early time could be
associated with micropits.
Metastable pits on metal surface are initiated as functions of
both time and position [20]. As shown in Fig. 6, there were some
metastable pits on the steel surface associated with the potential
peaks. Some might initiate and then cease, some might continue to
grow for a longer time. Pitting initiation was caused by the break-
down of the passive film and the active dissolution of structural
defects and impurities, which were the random fluctuations on
the map. The metastable pits may repassivate quickly or grow and
then repassivate, and possibly develop to depassivation, severely
depending on the surrounding condition [21,22]. The peak values
of the micropits on the potential map are not the same in the differ-
ent corrosion conditions, such as the different kinds of electrodes
and the different values of solution conductivity. It is well known
that the pitting corrosion has a stochastic characteristic [21,22]. The
surrounding condition plays an important role on the pitting devel-
opment. In our work, the pH value of the SCP solution is the most
important factor affecting the passivity of reinforcing steel.

Fig. 8. SEM images of the reinforcing steel surface in the simulated pore solutions
with different pH values after 5 h immersion. pH values: (a) 11.46 and (b) 11.31.

Based on the results presented above, we conclude that the criti-

cal pH value for localized corrosion of reinforcing steel in simulated
concrete pore solutions should be between 11.46 and 11.31. When
the pH of the solution decreases to or below 11.31, localized corro-
sion will occur on the steel surface.
To confirm this conclusion, SEM images of the reinforcing steel
specimens after about 5 h exposure to the SCP solutions with dif-
ferent pH values are shown in Fig. 8. In the pH 11.46 solution,
the steel surface was smooth and had no obvious corrosion site
on it due to the protection of a compact oxide layer (Fig. 8a).
When the pH of the solution decreased to 11.31, the surface became
rough and large pits appeared because of the occurrence of local-
ized corrosion (Fig. 8b, in the circle). In general, the critical value
of the size for micropits developing to corrosion macropits is
20–30 ␮m [23]. Thus, the small black points in Fig. 8a might not
be corrosion pits. They might be some impurities from the SiC
paper that was used to polish the steel specimens before mea-
surements. This was confirmed by the EDS data, which showed
Si and Al in those sites. The size of the biggest pit area in Fig. 8b
reached about 20 ␮m and suggested the pitting corrosion of the
steel.

4. Conclusions

The SMRE technique was demonstrated to be a powerful tool

to in situ measure the potential distribution on reinforcing steel
surfaces in the interested electrolytes.
Fig. 7. Potential maps of the reinforcing steel surface in the simulated pore solution Mechanism of the initiation and propagation process of pit-
with pH 11.31 after immersion for (a) 128 min, (b) 138 min and (c) 142 min. ting corrosion is complicated, and is affected by many factors.
4072 H. Xu et al. / Electrochimica Acta 54 (2009) 4067–4072

Strictly speaking, the critical pH values for steel localized corro- References
sion measured by SMRE technique in this work are approximation,
but it is anticipated that the research method and results will [1] S. Ahmad, Cement Concrete Comp. 25 (2003) 459.
[2] M.V. Biezma, J.R. San Cristobal, Corros. Eng. Sci. Techn. 40 (2005) 344.
provide a useful help to the study on metal corrosion and protec- [3] K. Thangavel, Corros. Rev. 22 (2004) 55.
tion. [4] M. Moreno, W. Morris, M.G. Alvarez, G.S. Duffo, Corros. Sci. 46 (2004) 2681.
There were some unstable micropits which did not develop to [5] V. Kumar, Corros. Rev. 16 (1998) 317.
[6] M. Maslehuddin, M.M. Al-Zahrani, M. Ibrahim, M.H. Al-Mehthel, S.H. Al-Idi,
macro-corrosion pits on the reinforcing steel surface in the pure Constr. Build. Mater. 21 (2007) 1825.
simulated concrete pore solution (pH 12.56), and the steel surface [7] R.G. Du, R.G. Hu, R.S. Huang, C.J. Lin, Anal. Chem. 78 (2006) 3179.
was passive without corrosion. [8] B. Huet, V. L’Hostis, F. Miserque, H. Idrissi, Electrochim. Acta 51 (2005) 172.
[9] C. Alonso, M. Castellote, C. Andrade, Electrochim. Acta 47 (2002) 3469.
The lower the pH value of solutions, the more unstable the pas- [10] O. Poupard, A. Ait-Mokhtar, P. Dumargue, Cement Concrete Res. 34 (2004) 991.
sive film of reinforcing steel. The large and stable peak would occur [11] G.S. Duffo, W. Morris, I. Raspini, C. Saragovi, Corros. Sci. 46 (2004) 2143.
on the potential maps of the reinforcing steel surface when the [12] W.C. Yeih, J.J. Chang, Constr. Build. Mater. 19 (2005) 516.
[13] P. Garces, M.C. Andrade, A. Saez, M.C. Alonso, Corros. Sci. 47 (2005) 289.
localized corrosion took place in the test solutions. We found the
[14] N. Cui, H.Y. Ma, J.L. Luo, S. Chiovelli, Electrochem. Commun. 3 (2001) 716.
critical pH value for the localized corrosion of the reinforcing steel [15] M.H. Shao, Y. Fu, R.G. Du, C.J. Lin, Mater. Sci. Eng. A Struct. 344 (2003) 323.
in SCP solutions was between 11.46 and 11.31 based on the potential [16] C.J. Lin, J.L. Lou, X.D. Zhou, Z.W. Tian, Corrosion 54 (1998) 265.
distribution changes measured by SMRE. [17] A.M. Lafront, W. Zhang, S. Jin, R. Tremblay, D. Dube, E. Ghali, Electrochim. Acta
51 (2005) 489.
[18] A. Poursaee, C.M. Hansson, Cement Concrete Res. 37 (2007) 1127.
Acknowledgements [19] J.Z. Zhang, JianYun Li, N.R. Buenfeld, Cement Concrete Comp. 24 (2002) 451.
[20] L. Organ, J.R. Scully, A.S. Mikhailov, J.L. Hudson, Electrochim. Acta 51 (2005) 225.
[21] J. Lopez, De La Cruz, R.H.A. Lindelauf, L. Koene, M.A. Gutierrez, Electrochem.
We thank Drs. M.H. Shao, R.S. Huang, and Z.D. Feng for helpful Commun. 9 (2007) 325.
conversations. This work was supported by the National Natural Sci- [22] A. Valor, F. Caleyo, L. Alfonso, D. Rivas, J.M. Hallen, Corros. Sci. 49 (2007) 559.
ence Foundation of China (Nos. 20473066, 50731004) and National [23] H. Kaesche, Corrosion of Metals: Physicochemical Principles and Current Prob-
lems, Springer, Heidelberg, Berlin, 2003.
Key Technology R&D Program (No. 2007BAB27B04).