Corrosion Science 53 (2011) 946–954

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

Microscopic investigation of mill scale and its proposed effect on the variability
of chloride-induced depassivation of carbon steel rebar
P. Ghods a, O.B. Isgor a,⇑, G.A. McRae a, J. Li b, G.P. Gu b
a
Carleton University, Ottawa, Ontario, Canada
b
CANMET Materials Technology Laboratory, Ottawa, Ontario, Canada

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

Article history: Electrochemical experiments have shown that mill scale on carbon steel rebar affects corrosion initiation
Received 12 May 2010 and variability associated with chloride-induced depassivation thresholds. In this study, scanning elec-
Accepted 17 November 2010 tron microscopy and focused ion beam microscopy were used to investigate the properties of mill scale
Available online 21 November 2010
and its effect on chloride thresholds of the underlying steel. The variability found in the literature for
chloride thresholds is suggested to result, in part, from the variability in the physical and chemical prop-
Keywords: erties of mill scale. A crevice corrosion mechanism is proposed to explain why as-received rebar is more
A. Steel reinforced concrete
susceptible to depassivation than rebar without mill scale.
B. SEM
C. Crevice corrosion
Ó 2010 Elsevier Ltd. All rights reserved.
C. Pitting corrosion
C. Alkaline corrosion

1. Introduction were exposed to chloride concentrations in excess of that typically

Carbon steel rebar in concrete is well protected against corrosion
by a passive oxide film that forms in the alkaline pore solution
(pH > 12.5). Chlorides are known to cause partial or complete loss
of the passive film (i.e., depassivation) if their concentrations exceed
threshold values, which are generally reported relative to hydroxide
concentrations, i.e., as chloride-to-hydroxide concentration ratios
(Cl/OH), however, these values cover a wide range and have a
large degree of uncertainty [1–3]. The following factors have been
reported to contribute to the variability in chloride thresholds: the
variability of the composition of the pore solutions in different types
of concrete [4–11]; the variability of the rebar-concrete interface
[12,13]; the chloride binding of the hydration products of concrete
[14–16]; the variability in oxygen availability around the rebar in
concrete [12,17,18]; the variability of environmental factors such
as relative humidity and temperature [14,18]; the mechanical integ-
rity of the steel–concrete interface [19] and; the surface characteris-
tics of rebar [10,17–22]. This paper focuses on the contribution of the
rebar surface, in particular the properties of mill scale, to the chlo-
ride-induced depassivation of carbon steel rebar.
Previous studies have shown that removing mill scale from the
surface of rebar by sandblasting, polishing or pickling increases
chloride thresholds by as much as one order of magnitude [17–
22]. In a rare case, Mammoliti [23] reported that corrosion did
not initiate on highly-polished rebar, even after the specimens
found in sea water. In a recent study, Ghods et al. [24] compared
the chloride thresholds of as-received (with mill scale) and
turned-and-polished rebar specimens (which were turned on a
lathe to remove the deformities and the mill scale and then pol-
ished to 600 Grit) in simulated service conditions. They reported
that surface modification, by turning and polishing, led to higher
chloride thresholds. More important, modifying the rebar surface
led to reduced variability in polarization resistance and reduced
fluctuations in free corrosion potential above the depassivation
threshold. The inference was that the turned-and-polished sur-
faces were uniformly the same everywhere, whereas the as-re-
ceived surfaces were locally much more diverse and complex.
This paper tests the hypothesis that the variability in chloride
thresholds may be, at least in part, attributed to the variability in
the mill scale that originates during the manufacturing process
[11,24]. The main objective of the present study was to investigate
whether mill scale makes rebar more susceptible to corrosion ini-
tiation. The study was carried out in two stages: In the first part,
the properties of mill scale on rebars from different manufacturers
were investigated. The second part focused on the role of mill scale
on chloride-induced depassivation of carbon steel rebar.
2. Experimental program
2.1. Investigation of mill scale properties

⇑ Corresponding author. Tel.: +1 613 5202600x2984; fax: +1 613 520 3951. Mill scales on as-received rebars from three different manufac-
E-mail address: burkan_isgor@carleton.ca (O.B. Isgor). tures were studied using a scanning electron microscope (SEM)

0010-938X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.11.025
 P. Ghods et al. / Corrosion Science 53 (2011) 946–954 947

and a focused ion beam (FIB) microscope. Rebars were cut to 10- steel rebar [24]. Both electrochemical and SEM investigations were
mm lengths from as-received carbon steel rebars of 10 mm nomi- carried out on one type of as-received carbon steel rebar (Type (i))
nal diameter. The chemical composition of the steel is given in Ta- with 10 mm nominal diameter. The chemical composition of the
ble 1. One specimen from each producer was mounted in low steel is given in Table 1.
shrinkage epoxy under vacuum so that each cross section could Twenty-four 30-mm long rebar specimens were prepared and
be ground and finished with 1200 grit SiC paper. After grinding, kept in a beaker containing simulated concrete pore (CP) solution
all specimens were rinsed with distilled water and kept in a desic- (pH 13.3) for 8 days following the procedure in Ref. [24] to allow
cator to avoid surface oxidation prior to microscopy studies. Mill the formation of stable passive films on the steel surfaces. The CP
scale around the cross section of each specimen was studied using solution was prepared by dissolving calcium hydroxide [Ca(OH)2],
a Philips XL30 SEM and a Micrion 2500 FIB microscope. sodium hydroxide [NaOH], potassium hydroxide [KOH] and cal-
cium sulfate [Ca(SO4)] in distilled water, in the amounts shown
in Table 2. The measured concentrations presented in Table 2 were
2.2. Investigation of the effect of mill scale on chloride-induced
determined using Inductively Coupled Plasma – Atomic Emission
depassivation
Spectroscopy (ICP-AES) (Model: Varian Vista RL); pH of the solu-
tion was measured using VWR Symphony SP90M5
The second part of the investigation was carried out in parallel
Multiparameter.
with an electrochemical study of chloride thresholds of carbon
Following the initial 8-day passivation period, the chloride con-
centration in each beaker was increased at 7-day intervals for two
Table 1
months by adding reagent-grade sodium chloride. Before each
Elemental composition of the rebar used in the
investigation studying the effect of mill scale
chloride addition, three replicate specimens were removed for
on the chloride-induced depassivation. electrochemical measurements to determine if depassivation had
taken place. The electrochemical techniques included free corro-
Element Weight (%)
sion potential (FCP) measurements, electrochemical impedance
C 0.26 spectroscopy (EIS), linear polarization resistance (LPR) and anodic
Si 0.27
Mn 1.10
polarization (AP) as a function of added chloride. Negligible
Cr 0.05 changes were observed in the electrochemical responses (e.g. FCP
Ni 0.07 and polarization resistance) up to a threshold chloride concentra-
Mo <0.01 tion, after which further addition of chloride produced large
Cu 0.21
changes, which was interpreted as depassivation. Further chloride
Al <0.005
Nb <0.01 addition was followed by visible pits on the rebar surfaces. Once
V <0.005 the surface was depassivated, the specimen was cold-mounted
Ti <0.005 using low shrinkage epoxy to retain the integrity of the interface
B <0.0005 between the steel and mill scale. Further details about specimen
P 0.01
S 0.03
preparation for electrochemical experiments can be obtained from
W <0.01 Ghods et al. [24].
Sn 0.021 The cold-mounted rebar specimens were cut in half to 15-mm
Co 0.01 long specimens and ground with 1200 grit SiC paper. Three as-
Zr <0.01
received and three turned-and-polished rebar specimens that were
Fe Balance
not exposed to the pore solution were also cold-mounted to

Table 2
Concentrations of species in the simulated concrete pore solution (CP).

Added compounds (mol/L) Measured ions (mg/L) pH

Ca(OH)2 Na(OH) K(OH) CaSO4 Ca2+ Na+ K+ SO42
0.1 0.1 0.2 0.003 3 2232 8059 277 13.3

Fig. 1. Optical images of rebar specimens with two different surface conditions: (a) as-received with mill scale; (b) turned-and-polished. Banding in Fig. 2 (b) is an artifact of
the light reflected from the polished surface.
948 P. Ghods et al. / Corrosion Science 53 (2011) 946–954

compare with the depassivated specimens. SEM images of the

cold-mounted specimens were obtained with a Phillips XL30
microscope equipped with an energy dispersive X-ray spectrome-
ter (EDS) for chemical composition analyses.

3. Results

3.1. Investigation of mill scale properties

Optical images of as-received and turned-and-polished rebar

Fig. 2. FIB secondary electron image showing the crystal grains of the mill scale and
the underlying steel.
surfaces are shown in Fig. 1(a) and (b), respectively. Fig. 2 shows
a FIB secondary electron image obtained from the cross section
of an as-received rebar before exposure to the simulated concrete
pore solution. The micrographs show the difference between the
larger columnar grains of the mill scale and the smaller equiaxed
grains of the underlying steel. Note also that, unlike most corrosion
products which show amorphous structure, mill scale has a crys-
talline structure.
In Fig. 3, cross-sectional SEM micrographs of as-received rebar
specimens from three manufacturers are presented. As shown in
Fig. 3(i-b–d), the surface of rebar (i) is covered with a thick
(30 lm) and relatively uniform layer of mill scale; however,
localized cracks can be seen that connect the steel surface to the
rebar free surface, and crevices between the steel surface and mill
scale, and voids within the mill scale are visible. Fig. 3(ii-b–d)

Fig. 3. Images of rebar from three different manufacturers (i, ii and iii). The optical images at the top (a) are supplemented with SEM micrographs in figures (b)–(d) of
increasing magnification for each rebar type. The mill scale thickness varies depending on the manufacturer: for rebar (i) 30 lm uniformly over the surface; for rebar (ii)
2 lm and non-uniform, and for rebar (iii) 40 lm and non-uniform. (M: Mill scale, S: Steel).
 P. Ghods et al. / Corrosion Science 53 (2011) 946–954
shows that the mill scale on the surface of rebar from the second
manufacturer (ii) is mostly in the form of non-uniform patches
with a maximum thickness of 2 lm, and there are some areas
on the steel surface where there is no mill scale. SEM images of re-
bar specimens from the third manufacturer are shown in Fig. 3(iii-
b–d). The mill scale is thick (40 lm), and contains cracks, crevices
and voids as seen in the images of rebar (i), but unlike rebar (ii), the
mill scale for rebar (iii) does not cover the surface of the steel
completely.
Higher magnification SEM micrographs shown in Fig. 3(i-d) and
Fig. 3(iii-d) indicate that mill scale consists of two regions, which
can be clearly seen in the backscattered electron images as a darker
outer layer and a lighter inner layer. The EDS analyses shown in
Fig. 4(a) and (b) indicate that mill scale consists of iron and oxygen,
with different intensity ratios of iron to oxygen (Fe/O) that can be
related to the chemical composition of the two layers. EDS analyses
indicate that Fe/O in the light region is consistently larger than that
in the dark region.
Fig. 4. EDS analysis of mill scale of rebar (i): (a) dark layer; (b) light layer. For the case shown in the figure, Fe/O was 2.18 for the light layer and 1.64 for the dark layer.
949
3.2. Investigation of the effect of mill scale on chloride-induced
depassivation
The SEM micrographs of the cross sections of turned-and-pol-
ished and as-received rebar specimens before immersion in the
simulated concrete pore solution are shown in Fig. 5. The surface
of steel for the turned-and-polished specimen is smooth and free
of any visible oxide (Fig. 5(a)). In contrast, the surface of the as-re-
ceived specimen is covered with a thick layer of mill scale (Fig. 5(b)
and (c)): the thickness was found to vary between 20 lm and
40 lm (Fig. 5(b)). An SEM micrograph of the mill scale with higher
magnification (Fig. 5(c)) revealed that the interface of steel and
mill scale was filled with crevices with lengths as long as
500 lm, and the mill scale contained cracks with widths as wide
as 1 lm. In some locations around the steel surface, these cracks
linked the crevices to the free surface (Fig. 5(c)), hence, providing
pathways for the concrete pore solution to penetrate into the voids
and the crevices. An SEM image of an as-received rebar surface be-
950 P. Ghods et al. / Corrosion Science 53 (2011) 946–954
Fig. 5. SEM cross-section images of rebar specimens before exposure to the simulated concrete pore solution: (a) micrograph of turned-and-polished specimen; (b) low
magnification micrograph of as-received specimen and (c) high magnification micrograph of as-received specimen.
Fig. 6. SEM surface images of as-received rebar samples before exposure. The large
dark features (marked by arrows) have similar dimensions (1–2 lm) as crack
openings in mill scale.
fore exposure to solution is shown in Fig. 6. The large dark surface
features in Fig. 6 are approximately micrometers in dimension, and
have similar dimensions as crack openings in mill scale observed in
Fig. 5(c).
Fig. 7(a) shows an SEM image of an as-received rebar specimen
that was exposed to 0.15 mol/L NaCl, which was sufficient salt con-
centration to cause depassivation of the steel surface as deter-
mined by the electrochemical experiments [24]. In this figure,
there are two cracks connecting the free surface to the crevice be-
tween the steel and the mill scale. An enlarged section of Fig. 7(a) is
shown in Fig. 7(b). The results of EDS analysis at sites A, B and C
show the existence of iron and oxygen, which suggests the pres-
ence of iron oxides at these sites. In addition, the presence of cal-
cium, sodium, potassium and chloride indicates that concrete
pore solution was present in the crevices. The crevice has a width
that varies between 5 and 10 lm, and some parts of the crevice are
narrower because they are filled with iron oxide corrosion prod-
ucts. The corrosion of the metal cannot be described as ‘general
corrosion’; corrosion in the crevice is local in extent, with small
protrusions into the underlying metal that we shall characterize
as pit-initiation sites. Corrosion pits at different stages are visible
in Fig. 7(a). Although these pits are hidden under the mill scale,
their existence is inferred using FCP and polarization resistance
as described in Section 2.2 and Ref. [24]. It was also observed that
at locations without mill scale, there were no obvious signs of cor-
rosion. This suggests that for as-received rebar, crevices between
the underlying steel and the mill scale provide a local environment
for corrosion.
Fig. 8 illustrates an advanced-stage of local pitting corrosion.
These pits can be observed on the rebar surface, well after the elec-
trochemical observation of depassivation. In Fig. 8(a) it appears
that some of the mill scale has been destroyed by expanding me-
tal-corrosion products, which occupy a larger volume than steel.
The EDS analysis of area E confirmed the presence of corrosion
products (i.e., iron oxides). Fig. 8(b) shows the propagation of a
pit penetrating the steel; the EDS analysis of area F confirmed cor-
rosion products and the presence of chloride in this area. Finally
Fig. 8(c) shows an advanced stage of rebar corrosion where the mill
scale had spalled, apparently because of pressure from below.
4. Discussion
Mill scale is an iron oxide layer that forms on the steel surface
during the hot rolling process of steel production; therefore, it is
 P. Ghods et al. / Corrosion Science 53 (2011) 946–954 951

Fig. 7. SEM images of representative mill-scale cross sections taken from as-received rebar with mill scale after immersion in the simulated concrete pore solution plus
0.15 mol/L NaCl: (a) lower magnification image showing the location of corrosion initiation; (b) higher magnification image of area ‘‘D’’ marked in (a). EDS analysis of spots A,
B and C suggest the presence of iron oxide and pore solution species in the crevice.

expected that the properties of mill scale will vary because of the
vagaries of production, and variables such as rolling temperature,
for example. The present investigation is in accord with this expec-
tation because three rebars produced by three different manufac-
turers had different physical properties in terms of thickness,
uniformity and microstructure. Even for the same rebar specimen,
mill scale was not uniform and was full of cracks, voids and
crevices.
In this study, the chemical composition of mill scale was seen in
SEM images to be typically composed of two layers. Schweitzer
[25] reported that mill scale is generally composed of magnetite
(Fe3O4), and smaller quantities of other oxides. Raman spectros-
copy studies by Marcotte [26] found that mill scale is largely com-
posed of magnetite (Fe3O4) with a surface layer of hematite (a-
Fe2O3) and goethite (a-FeOOH). From the Fe/O ratios observed in
the backscattered SEM images of this study, we cannot make con-
clusions regarding the chemical stoichiometry of the iron oxides in
the mill scale, however, the light layer, which was adjacent to the
steel surface, consistently had the higher Fe/O ratio when com-
pared with the dark layer closer to the free surface. This observa-

Fig. 8. SEM–EDS analyses showing corrosion of as-received rebar (i.e., with mill scale) after immersion in simulated concrete pore solution containing chloride (0.15 mol/L).
(a) SEM image of corrosion at the interface between the steel and mill scale; (b) an image of a pit and (c) an image showing where the mill scale had spalled. EDS analysis of
spots E and F showed the presence of iron oxide and pore solution species and chloride.
952 P. Ghods et al. / Corrosion Science 53 (2011) 946–954

tion is consistent with previous results suggesting mill scale has an
inner layer of magnetite and an outer layer of hematite [25,26], and
agrees with the reported composition of other carbon steel oxides
[27]. The relative volume fractions of the light and dark regions are
highly variable between different manufacturers, and even for the
same rebar at different locations.
The second part of the current investigation focusing on the ef-
fect of mill scale on chloride-induced depassivation of as-received
rebar specimens has shown that corrosion initiates in the crevices
between the mill scale and the steel surface. This suggests that
without the mill scale and crevices, corrosion would be more diffi-
cult to initiate, which is in accord with previous electrochemical
studies that reported when mill scale was removed, chloride
thresholds increased [17–20]. In addition, modifying the rebar by
removing the mill scale and deformities, and then polishing the
surface, has been reported to reduce variability and fluctuations
in electrochemical measurements (e.g. FCP and polarization resis-
tance) [24]; these results were attributed to the modified surfaces
being uniformly the same everywhere, whereas the as-received
surfaces are locally much more diverse and complex due to the
presence of mill scale. These results underscore the importance
of mill scale to chloride-induced depassivation of rebar, and pro-
vide more credence to the contention that the variability associ-
ated with reported chloride thresholds may be attributed to the
variability in mill scale properties resulting from the variability
in manufacturing. A practical implication of this work is that rebar
without mill scale could provide a longer service life in high chlo-
ride environments. More work is required to find the optimum
cost-benefit conditions.
The current study provides clues about why as-received rebar is
more susceptible to corrosion initiation than rebar without mill
scale. Cross-sectional SEM images of rebar specimens showed that
voids and crevices exist at the interface between steel and mill
scale. Some of these voids and crevices were connected to the pore
solution by cracks, which serve as pathways for concrete pore solu-
tion to reach the steel surface, hence allowing ion movement be-
tween the pore solution and the crevices through electrical
migration and diffusion. We speculate that over time, the chemical
composition of the pore solution within the crevices begins to dif-
fer from that of the bulk solution through a process similar to the
suggested mechanisms of typical crevice corrosion [27,28]. Here a
brief description of the mechanism is discussed.
Fig. 9 shows a schematic of a crevice at the interface of the steel
and mill scale that is connected to the free surface by a crack. In
this figure, the mechanism is divided into two stages to facilitate
the explanation. The initial stage refers to the condition when oxy-

Fig. 9. Illustration of a mechanism for the chloride-induced depassivation of rebar with mill scale. (a) The cathodic reactions on the steel surface in the crevice, the mill-scale
free surface and, possibly on the mill-scale, all consume electrons obtained from the anodic reaction on the steel surface in the crevice. (b) The cathodic reaction in the crevice
is absent because oxygen from the concrete pore solution cannot be replenished quickly enough, and chlorides are driven into the crevice to offset the positive charges of the
iron ions, which continue to be produced by the remaining cathodic reactions on the steel and mill-scale.
 P. Ghods et al. / Corrosion Science 53 (2011) 946–954
gen is readily available on the surface of the steel beneath the mill
scale (Fig. 9(a)); in the second ‘depassivating’ stage, oxygen is de-
pleted because of the cathodic reaction in the crevice (Fig. 9(b)).
In Fig. 9, iron ionizes and moves into the concrete pore solution
in the crevice by the anodic reaction at the steel surface:
Fe ! Fe2þ þ 2e ð1Þ
The rate of metal loss is proportional to the passive current den-
sity because initially the steel is in the passive state. At the same
time, in the presence of oxygen, the following cathodic reaction
also takes place on the steel surface via:
1
O2 þ H2 O þ 2e ! 2OH ð2Þ
2 (RIEM) Program. Both contributions are gratefully acknowledged.
The solubility of Fe(OH)2 is low [29] and iron hydroxide precip-
itates under these conditions. During this initial stage, the concen-
trations of anions and cations in the crevice are the same as those
in the bulk concrete pore solution. In particular, Cl/OH, which is
a measure of chloride threshold, is the same for the bulk solution
and for the solution inside the crevice. As the anodic and cathodic
reactions proceed, depending on the geometry of the crevice, and
the size of the cracks, etc., oxygen consumed in the cathodic reac-
tion inside the crevice cannot be replenished by the diffusion-dri-
ven transport of oxygen from the bulk solution; therefore, after
some time, oxygen is depleted in some crevices. In these crevices,
the cathodic reaction (Eq. (2)) and the local production of hydrox-
ide slows. However, the cathodic reaction can still take place on
other parts of the steel surface that are not covered with mill scale,
or even on the mill scale surface if the mill scale is sufficiently con-
ductive; this continues to drive iron corrosion via Eq. (1) on the in-
side of the crevice. Chlorides and hydroxides move into the crevice
to maintain electroneutrality, but chlorides move faster, and
hydroxides precipitate as Fe(OH)2. The result is that Cl/OH in-
creases within the crevice relative to the bulk value. Hence,
depending on the shapes and sizes of cracks, voids and crevices
in the mill scale, which depends on manufacturing particularities,
different rebar steel surfaces could see much different ratios of
Cl/OH for the same operational/experimental conditions and,
hence, we should expect large variability in reported chloride
depassivation thresholds (Cl/OH ratios), as is observed. A finite
element model of the mechanism proposed in this paper is pre-
sented in a separate publication [30].
5. Conclusions
The main conclusions of the study are as follows:
1. The interface of steel and mill scale is filled with voids and cre-
vices, and the mill scale contains cracks. In some locations
around the steel surface, these cracks link the voids and crevices
to the free surface, hence, providing pathways for the concrete
pore solution to penetrate into the voids and the crevices.
2. Crevices between mill scale and steel provide sites for pit initi-
ation. Although these pits are hidden under the mill scale, their
existence can be determined electrochemically.
3. Mill scale has large variability in its physical and chemical prop-
erties. The results of this study suggest that the variability asso-
ciated with reported chloride thresholds may be partly
attributed to the variability in mill scale properties resulting
from the variability originating in the manufacturing process.
4. The present study provides clues that can be used to explain
why as-received rebar is more susceptible to chloride-induced
depassivation than rebar without mill scale. We suggest a
mechanism that is similar to that of typical crevice corrosion:
oxygen depletion in the crevice results in reduced hydroxide
953
concentrations, chlorides migrate into the crevice to maintain
electroneutrality and, hence, the ratio Cl/OH within the mill
scale crevices of as-received rebar is higher than in the bulk
concrete pore solution, and the steel depassivates more readily.
Acknowledgments
This research was supported by a grant from the Natural Sci-
ences and Engineering Research Council (NSERC) of Canada along
with technical and financial support of CANMET-MTL Laboratories,
through the Resource for Innovation of Engineered Materials
We also would like to thank Renata Zavadil and Pei Liu for their
help with sample preparation and SEM analysis. In addition, we
acknowledge thankfully the help provided by Sahar Soleimani dur-
ing the preparation of the figures.
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