Materials and Structures

DOI 10.1617/s11527-014-0343-2

ORIGINAL ARTICLE

The influence of reinforcement steel surface condition

on initiation of chloride induced corrosion
Dimitrios Boubitsas Luping Tang

Received: 11 March 2013 / Accepted: 29 May 2014

RILEM 2014

Abstract This paper describes a part of the work in

the development of a standard test method for
determining chloride threshold values required to
initiate corrosion on reinforcement in concrete. The
prerequisites of the test set-up are that the test
conditions should be reasonably comparable to those
in service and the test method should be fairly
reproducible and as rapid as possible concerning the
slow diffusion nature of the investigated phenomenon.
This paper presents the results from a study on the
influence of steel bar surface condition on chloride
induced corrosion. Various electrochemical techniques were employed in the study to monitor the
corrosion behaviour of the embedded bars with three
different surface conditions. It is shown that the steel
surface condition has a strong effect on the corrosion
initiation of reinforcement in concrete, and can likely
be the most decisive parameter attributing to the
variability in the reported chloride threshold values.

D. Boubitsas (&)  L. Tang

CBI Swedish Cement and Concrete Research Institute,
c/o SP, Box 857, SE-501 15 Boras, Sweden
e-mail: dimitrios.boubitsas@cbi.se
D. Boubitsas
Division of Building Materials, Lund Institute of
Technology, Lund, Sweden
L. Tang
Department of Civil and Environmental Engineering,
Chalmers University of Technology, Goteborg, Sweden

Keywords Chloride-induced corrosion  Chloride

threshold values  Reinforcement steel surface
condition  Concrete

1 Introduction
Chloride initiated reinforcement corrosion is one of
the major causes of deterioration of concrete structures
[17]. Steel in concrete is normally protected by the
high alkaline nature of the pore solution in concrete [7,
15, 28, 38]. Iron oxides will form a thin protective film
on the surface of the reinforcing steel (a passive layer),
and in this passive state the corrosion rate is insignificant [7, 15]. However, in practice reinforcement
corrosion due to the ingress of chloride ions from deicing salts or sea water may occur resulting in damage
which may lead to early failure of reinforced concrete
structures [17, 38].
When chloride ions ingress into concrete and reach
a certain critical concentration at the depth of the
reinforcement the passive film is broken down and the
steel becomes depassivated. In other words, the
corrosion rate becomes significant at the critical
chloride concentration. However the exact mechanism
is not well understood [9, 10, 15]. A lot of research has
been devoted to try to determine the critical chloride
concentration, or the chloride threshold value as it is
often referred to. In the recent years comprehensive
literature reviews on the subject have been published

Materials and Structures

[2, 5]. Angst et al. [5] found a large scatter in the

reported values and pointed out that the large scatter is
mainly related to different experimental procedures.
Also Alonso and Sanchez [2] concluded that the
testing methods used contribute largely to the variability found in the reported data. Obviously, there is a
need for a practice-related test method under conditions as realistic as possible to evaluate the chloride
threshold values for embedded reinforcement steel, as
identified by Page [27]. Recently, the RILEM TC
235-CTC Corrosion Initiating Chloride Threshold
Concentrations in Concrete is working for the
development of a practice-related test method.
Numerous parameters affect the initiation of chloride induced corrosion of steel in concrete. One of the
parameters believed to be of importance is the surface
condition of the reinforcement steel [2, 5, 27]. To
achieve reproducible specimens the reinforcing steel
is often prepared prior to laboratory testing in different
ways, e.g. by sandblasting, chemically cleaning and
polishing. A condition referred to as-received is also
common. The term as-received is vague, implying a
metal surface that might be more or less rusty and
covered completely or partially with mill scale.
In the literature the surface condition of the steel is
often not adequately reported which could account for
apparent inconsistencies in results of different investigators. Some of the reported data in the literature [16,
18, 19, 22, 37] indicate that the surface condition of the
steel has a major influence on the chloride threshold
value for corrosion, but the reported data are not
always in agreement.
Mammoliti et al. [19] showed that for steel exposed
in an alkaline solution pitting initiation took place at a
chloride concentration that was three times higher for
polished than for ground steel, with the chloride
concentration for pitting initiation of the as-received
(not further specified) steel specimens lying in
between. In [18] it was shown that for sandblasted
steel in an alkaline solution the chloride concentration
required to initiate active corrosion was about twice as
high as for as-received and pre-rusted steel. The asreceived condition was described as a surface with
black mill scale and some red rust on the surface, while
the pre-rusted condition was obtained by immersing
specimens with mill scale in a 3.5 % sodium chloride
solution for 3 days.
Hansson and Srensen [16] found that the presence
of rust increased the resistance against corrosion

initiation from chlorides on steel bars embedded in

mortars. The steel conditions used in their investigation were as-received (described as slightly rusted),
cleaned by sandblasting, and further rusted. Further
rusted implies that the as-received bars (AR) were
further exposed outdoors for 2 weeks under a condition not further specified. In contrast to these results,
Treadaway et al. [37] found by comparing grit-blast
cleaned and pre-rusted reinforcement steels embedded
in concrete that the corrosion resistance can be
reduced by the presence of a rust layer. In this
investigation the pre-rusted steels were weathered in
open exposure to remove mill-scale and produce
uniform rusty condition. Mohammed and Hamada
[22] tested steel bars cast in concrete specimens that
were cyclically exposed to natural seawater. The
different surface conditions of the steels in this
investigation were, polished (P), mill-scaled (M),
brown-rusted (BR) by wetting and drying (in tap
water) for 4 weeks, black-rusted (BL) without
describing how this was achieved, and pre-passivated
(PP) by applying a cement paste coat before cast in
concrete. The authors concluded that the chloride
threshold levels for the steel bars with different surface
conditions were sequenced as PP [ BL [ P [
BR [ M.
Clearly from the literature review, without a
standard method it is difficult to quantitatively investigate the parameters affecting corrosion initiation. In
the effort to develop a standard test method for
determining chloride threshold values (CT-values),
under conditions reasonably comparable to those in
service, with satisfactory reproducibility and as rapid
as possible concerning the slow diffusion nature of the
investigated phenomenon, a series of studies intending
to isolate parameters which can have a major influence
on variability of the reported CT-values were undertaken by the authors of this paper, as a pilot work of the
RILEM TC 235-CTC. This paper presents the results
from a study on the influence of reinforcement steel
surface condition on chloride induced corrosion.
Various electrochemical techniques are used to study
the corrosion behaviour of rebar with three different
surface conditions cast in concrete specimens. The
electrochemical techniques include free corrosion
potential (Ecorr) measurements, polarising current
under potentiostatic controlled conditions (Ip) and
corrosion rate (icorr) measurements with a galvanostatic pulse method.

Materials and Structures

Table 1 Concrete mix design used in the experimental study (w/c 0.50)
Cement)
(kg/m3)

Water
(kg/m3)

Aggregate
(kg/m3)

Superplasticizer
(% by cement weight)

Slump (mm)

Air (%)

Compressive strength
at 28 days (MPa)

380

190

1,817

0.5

180

58

Table 2 Properties of the binder (according to supplier)

Swedish structural cement (CEM I 42.5N MH/SR/LA)
Blain fineness (m2/kg)

310

C3A (%)

Na2O-equivalent (%)

0.57

Chloride content (%)

\0.01

2 Materials and methods

2.1 Materials
The mix design of the concrete used in this study is
given in Table 1 (w/c 0.50).
Swedish Portland cement for civil engineering
(CEM I 42.5N MH/SR/LA according to the European
standard EN 206) was used, with the properties given
in Table 2. The maximum aggregate size was limited
to 10 mm due to the shallow cover thickness.
Three concrete specimens each with 2 sets of 4
embedded steel bars (i.e. a total of 8 bars for each
surface condition) were cast with the dimensions
given in Fig. 1.
The eight reinforcement bars of cold-drawn smooth
carbon steel (SS260s) of diameter 10 mm were cast
with four different cover depths of 10, 15, 20 and
25 mm. The composition of the steel is given in
Table 3.
Three different steel surface conditions are shown
in Fig. 2, where (a, c, f) on the left hand side present
photographic images and (b, d, e) on the right hand
side present corresponding light microscopy optical
images. In Fig. 2b, d, e the light areas are the steel base
material and the dark areas are the molded plastic used
to mount the specimens.
The three different conditions of steel surface were
achieved by: (a) special delivery with protection
against corrosion (wrapped in plastic) during the
transportation from the production plant to the laboratory, (b) as-received from the local steel supplier,
and (c) chemically cleaned (CC) by pickling the AR in

sulphuric acid in accordance with ASTM G109. The

specially delivered steel bars (SD) had bright metallic
luster surface covered partially with strongly adherent
mill-scale (Fig. 2a). Further, the microscopy image
(Fig. 2b) shows localized cracks in the mill-scale and
crevices between the steel surface and the mill-scale.
In Fig. 2b it can also be observed that in some
locations in those crevices darker spots can be
distinguished, probably some type of corrosion products. Figure 2c, d show that the AR, in general
exhibited a fairly uniform, thin continuous rust layer.
From light microscopy optical image Fig. 2d the
thickness of this rust layer can be estimated to
approximately 10 lm. The CC bars had a greyish
matt surface finish, as shown in Fig. 2e. In the
microscope the effect of the acid-pickling could be
observed as tiny cavities (less than 5 lm) on an
otherwise oxide-free surface (Fig. 2f).
The three reinforced concrete specimens, with
additional three cubes for testing compressive
strength, were cast from the same concrete batch.
Compaction was performed on a vibrating table. The
moulds were first filled to half followed by 5 s of
vibration and then the moulds were fully filled
followed with additional vibration of approximately
5 s until air bubbles no longer appeared on the surface.
In the following the reinforced concrete specimens are
noted as CSD (concrete specimen with SD bars), CAR
(concrete specimen with AR bars) and CCC (concrete
specimen with CC bars).
The reinforced concrete specimens were demoulded 1 day after casting and cured in sealed plastic
sheets until the age of 14 days. The specimens were
then cut by sawing to the T-shape form as shown in
Fig. 1. After cutting, the concrete cover thickness of
the steel bars, on each side, amounted to 10, 15, 20 and
25 mm. Different concrete cover thicknesses were
chosen for studying the effect of cover thickness and
also eliminating the risk of chlorides penetration due
to the accelerated preconditioning (to be mentioned
later) to an extent beyond the CT-values initiating
corrosion at all levels of the bars. The shape of the

Materials and Structures

Fig. 1 Concrete specimen
with embedded steel bars.
Dimensions given in mm

Table 3 Composition of the steel (according to supplier)

Residual elements (% by weight)
C

Si

Mn

Cr

Mo

Ni

Cu

0.11

0.29

1.26

0.008

0.014

0.039

0.001

0.04

0.007

0.035

0.0038

specimen is similar to that proposed by Nygaard and

Geiker [26]. The major benefit with this kind of
T-shape is to hinder sodium chloride crystals developing at the surface of the specimen. These salt
crystals often climb upto the top of the specimen and
contaminate the protruding part of the steel bars
causing crevice corrosion. Another advantage is that it
is easier to detect defects such as air voids on a sawn
surface, some air voids were observed in all specimens
despite the compaction. After sawing, all the surfaces
except the two sawn surfaces of the specimens were
coated with epoxy resin for preventing the protruding
bars from crevice corrosion, and also for accomplishing a one dimensional chloride penetration. The
coating was allowed to harden for 1 day and the
specimens were then stored in tap water for 6 days.
At the age of 21 days the specimens were preconditioned for 2 weeks at a temperature of 20 C and a

relative humidity of 50 %. This was for achieving

some drying out and consequently an accelerated
chloride penetration (resulting from a combination of
capillary suction and diffusion) as it would have been
very time consuming if saturated specimens had been
exposed to the chloride solution for ingress simply by
diffusion. After 2 weeks of preconditioning the specimens were exposed to sodium chloride solution of
6 % by weight (about 1 mol/l). The exposure solution
reached to a height of 130 mm from the bottom of the
specimens (see Fig. 1).
2.2 Methods
2.2.1 Electrochemical measurements
As it has been pointed out by [5], the method for
detecting active corrosion can influence the measured

Materials and Structures

Fig. 2 Photos and light microscopy images (cross section in the longitudinal direction) of the three different steel surface conditions
tested, a, b special delivery, c, d as received, and e, f chemically cleaned

CT-values. In this pilot work three different electrochemical techniques for monitoring the corrosion
process were used: free corrosion potential (Ecorr),
polarising current under a potentiostatic controlled
condition (Ip) and corrosion rate (icorr) with a galvanostatic pulse method. The galvanostatic pulse method
allowed also recording the Ecorr simultaneously with
the icorr measurements. Due to the limitation of
resources, only a small number of steel bars were
monitored by each method.
The concrete specimen with the specially delivered
bars SD1-4, were monitored by the free corrosion
potential Ecorr, and bars SD5-8 were monitored by the
Ip under the potentiostatic controlled condition. In
both cases a potentiostat developed by Arup and
Srensen [8] was used. The measurement principle is
illustrated in Fig. 3. The Ecorr for bars 14 (W2 in

Fig. 3) was measured against the reference electrode

(R). For bar 58 (W1 in Fig. 3) the Ip was measured
against the counter electrode (C) as the voltage drop
through a 100 X build-in resistor in the potentiostat.
More about this technique can be found in references
[25, 30].
A commercial available manganese oxide reference
electrode (ERE 20, made by FORCE Technology in
Denmark) placed in the saline solution and a datalogger was employed for data acquisition. Typical
potential values measured with the manganese oxide
reference electrode in saturated calcium hydroxide
solution at 23 C are around ?200 mV versus saturated calomel electrode (SCE) according to the
producer. This type of reference electrode possesses
individual but relatively constant potential even after
long time immersion (over 1 year in our study) in the

Materials and Structures

Potentiost
R
W1
C

0 mV SCE
100

E corr

W2
Solution surface

Fig. 3 Measurement principle for Ecorr and Ip for the SD bars

saline solution. All the measured Ecorr values in this

study were converted to mV versus SCE for conformity. The conversion factor for the specific MnO2
reference electrode used in this study was ?178 mV
versus SCE. The conversion factor was determined by
measuring at certain occasions the steel bars also
manually with a calibrated silver silver chloride
electrode (?36 mV vs. SCE). For the potentiostatic
control a mixed metal oxide titanium mesh placed in
the exposure solution as shown in Fig. 3 was used as a
counter electrode and the potentiostat was employed
for maintaining the potential at a predefined level
(0 mV vs. SCE).
The Ecorr for passive steel in concrete depends on
properties like the pH of the pore solution and oxygen
availability (moisture content), and can vary over a
wide range of potentials [11]. The Ecorr was recorded
every 2 h; a sudden drop of the Ecorr (the absolute
value normally [100 mV in a few hours) indicates
depassivation. Corroding steel in chloride contaminated concrete typically shows potentials ranging
from around -525 to -325 mV versus SCE [11].
For potentiostatically controlled monitoring the
level of the applied potential has previously been
found to influence the chloride threshold values.
Alonso et al. [1] found that the measured chloride
threshold values were independent of the potential if
the level was more positive than -200 50 mV
versus SCE and upto ?250 mV versus. SCE. In this
study the controlled potential was set at 0 mV versus
SCE, which is in the middle of the above range, as
suggested by Nygaard and Geiker [26]. The currents

applied to maintain the steel bars at the fixed potential

were recorded every 2 h. This polarisation current was
normally in a range of 05 lA for the passive steel bar
in this study. An abrupt increase of the applied current
([15 lA) to maintain the controlled potential indicates the initiation of corrosion [8, 16, 26].
The commercially available handheld instrument
RapiCor based on the galvanostatic pulse technique
was used to monitor the corrosion process in the
specimens containing the embedded AR and CC steel
bars. The instrument imposes a 5-s galvanostatic pulse
of 10 lA to the steel for measurement of polarisation
potential. If the potential response is less than 10 mV
(implying very low polarisation resistance due to
depassivation) another 5-s galvanostatic pulse of
165 lA is imposed for a better potential response.
As the result the instrument gives the corrosion rate in
lm/year assuming uniform corrosion. In this paper the
corrosion rate is converted back to corrosion current
density (icorr) by using Faradays law. Further the
instrument gives the Ecorr versus the copper/copper
sulphate reference electrode, which correspond to
approximately -74 mV versus the SCE. As previous
mentioned for consistency Ecorr is converted to mV
versus SCE. A more detailed description of this
technique can be found in Tang [33] and Tang and Fu
[35].
After the test period all of the steel bars were
removed from the specimens for visual examination of
the corrosion status. The test period extended to
329 day for the SD bars and 403 days for the AR and
CC bars. Some of the steel bars were removed earlier,
at the time when corrosion initiation was indicated.
2.2.2 Chloride exposure and chloride threshold value
measurements
All concrete specimens were continually submerged
in the saline solution during the first 75 days. Gradually decreasing potential was noted for some of the
steel bars that were under free corrosion potential,
which can be an indication of oxygen depletion [10].
Oxygen availability is one of the key factors for the
electrochemical mechanism of corrosion of steel in
concrete [10], therefore after 75 days all the concrete
specimens were cyclically exposed to air (T = 20 C
and RH = 50 %) for 3 days and submerged for
10 days. The aim of this procedure was firstly to try
to make oxygen available, and secondly, this

Materials and Structures

100

Ecorr (mV vs. SCE)

Bar SD1

Bar SD2

Bar SD3

Bar SD4

-100
-200
-300
-400
-500
0

50

100

150

200

250

300

350

Time (days)

Fig. 4 Free corrosion potential as function of time for the bars

SD1SD4

procedure can have an accelerating effect on the

chloride ingress. After about 2 months cyclic exposure it was found that this cyclic exposure did not seem
to have any acceleration effect on the corrosion
initiation. Hence this procedure was terminated and
the specimens were continually submerged from then
on. It must be pointed out that no potential control (for
bars SD5SD8) could be achieved during the periods
the specimens were out of the saline solution. As can
be seen in Fig. 4 after the cyclic exposure was started
the trend of decreasing potentials stopped for the
freely corroding bars and quite stable corrosion
potentials (in the passive state) were maintained
throughout the whole test period.
Parallel to the visual examination at the end of the
test periods, two concrete prisms from the bottom end
of each concrete specimen (see Fig. 1), with the
dimensions of approximately 50 9 50 9 80 mm
were cut out for measuring chloride penetration
profiles. This allowed for determining two chloride
profiles for each concrete specimen. Chloride profiles
were also determined in conjunction with visual
inspection made during the test periods. In these
occasions only one profile could be measured due to
limited accessibility of concrete sample. For the
chloride profile measurements the concrete prisms
were cut into small slices of 45 mm thickness, and
these small slices were then ground to powder. Four to
six slices were cut for each profile. The acid-soluble
chloride content in the powder (here assumed as total
chloride content) was determined principally in
accordance with AASHTO T260 (American

Association of State Highway and Transportation

Officials [3]. An automatic potentiometric titrator
(Metrohm 716 DMS Titrino) with chloride selective
electrode and a 0.01 N silver nitrate solution was
employed for the chloride analysis. After the chloride
titration, the calcium content in the same solution was
determined also using potentiometric titration with
calcium selective electrode and a 0.1 N EDTA
solution [34]. The cement content in each concrete
sample could then be estimated from the calcium
content since the aggregates used did not contain any
soluble calcium.
Ideally, the chloride content at the steel depth
should be measured when the corrosion is detected. In
this study with multi-bars in a concrete specimen, the
destructive sampling of individual corroding bar may
interrupt the test of the remaining passive bars.
Therefore, instead of destructive sampling immediately after the depassivation, chloride penetration
profiles were measured at four different occasions;
after 75, 138, 329, and 403 days of exposure in the salt
solution. The first two occasions were determined after
detection of corrosion initiation of steel bars while the
last two occasions were at the end of the test periods.
These chloride penetration profiles were used to
evaluate the chloride threshold values as described in
the following.
A simple empirical model that considers the time
dependence both of the surface chloride content and of
the chloride diffusion coefficient, similar with that
proposed by Nilsson [23] was used for predicting the
chloride ingress. The principle of the model is to
obtain the apparent diffusion coefficient Da(t) and
the apparent surface chloride content Csa(t) by curve
fitting using the error function solution to Ficks
second law (Eq. 1), after different exposure times t1
and t2.



x
Cx; t  Cini Csa  Cini  1  erf p
2 Da t
1
Cini is the initial chloride content in concrete, C(x, t)
is the total chloride content (mass% of cement) at
depth x at time t. The time-depended diffusivity Da(t)
is given by Eq. (2), from which the age factor n can be
calculated based on two measured chloride profiles.
 n
t1
Da2 Da1
2
t2

Materials and Structures

400

300

Ip (A)

The apparent diffusion coefficient Da(tcorr) at the

time of corrosion initiation (tcorr) can then be estimated
from the above equation. The time-dependency of Csa
is assumed to be linear between the two curve-fitting
occasions. The chloride content, i.e. the chloride
threshold value, at the time of corrosion initiation
(tcorr) is calculated using again Eq. (1), with constant
parameters Da(tcorr) and Csa(tcorr). It must be emphasized that Eq. (1) is not the correct solution of Ficks
second law with concern to the boundary conditions
(i.e. the time-dependency of Csa), so the model must be
considered as purely empirical for interpolation
between the exposure periods or slightly extrapolation
out of the curve-fitted occasions.

Bar SD6

Bar SD7

Bar SD8

200

100

0
0

50

100

150

200

250

300

350

Time (days)
Fig. 5 Current as function of time for the bars SD5SD8, under
the potentiostatic controlled condition

3 Results

10

icorr (A/cm2)

3.1 Corrosion monitoring measurements

Bar AR1

Bar AR2

Bar AR3

Bar AR4

0.1

0.01
0

50

100

150

200

250

300

350

400

450

Time (days)

Fig. 6 Corrosion rate as function of time for the bars AR1

AR4, monitored with the RapiCor instrument

10

icorr (A/cm2)

In Fig. 4 the development of the potential over time

for the set of bars freely corroding in concrete
specimen CSD is shown. A sudden drop to a more
negative potential indicates initiation of corrosion, in
this case bar SD1 (cover depth 10 mm) after
*110 days, bar SD2 (cover depth 15 mm) after
*241 days, and bar SD3 (cover depth 20 mm) after
approximately 279 days. Bar SD1 showed signs of
corrosion initiation even earlier, after about 75 day,
but this was followed by a repassivation period, i.e. a
period where the potential returns to the initial less
negative value, which means that corrosion ceased and
then restarted after *110 days.
In Fig. 5 the development of the polarising current
over time for the set of bars under potentostatic control
in concrete specimen CSD is shown. An abrupt
increase of the applied current to maintain the
controlled potential indicates the initiation of corrosion. Rapidly increasing currents for bar SD6 (cover
depth 15 mm) after 140 days, and for bar SD7 (cover
depth 20 mm) after 298 days, can be noticed. A few
measurement points for bar SD5 (cover depth 10 mm)
are also presented in Fig. 5, but because of a failure in
the acquisition system during the first 12 days of
exposure the uncertainty in the initiation time for this
bar is considered to be large.
The measurements with the RapiCor-instrument for
the AR bars are shown in Figs. 6 and 7 where the
development of the corrosion rate over time are

Bar SD5

Bar AR5

Bar AR6

Bar AR7

Bar AR8

0.1

0.01
0

50

100

150

200

250

300

350

400

450

Time (days)

Fig. 7 Corrosion rate as function of time for the bars AR5

AR8, monitored with the RapiCor instrument

Materials and Structures

100

10

i corr (A/cm 2 )

Ecorr (mV vs SCE)

0
-100
-200
-300

Bar CC2

Bar CC3

Bar CC4

Bar CC5

Bar CC6

Bar CC7

Bar CC8

0.1

0.01
-400

Bar AR1

Bar AR2

Bar AR3

Bar AR 4

0.001

-500
0

50

100

150

200

250

300

350

400

450

Fig. 8 Free corrosion potential as function of time for the bars

AR1AR4, monitored with the RapiCor instrument

100
0
-100
-200
-300
-400

Bar AR5

Bar AR6

Bar AR7

Bar AR8

-500
0

50

100

150

200

250

50

100

150

200

250

300

350

400

450

Time (days)

Time (days)

Ecorr (mV vs SCE)

Bar CC1

300

350

400

450

Time (days)

Fig. 9 Free corrosion potential as function of time for the bars

AR5AR8, monitored with the RapiCor instrument

presented. Figures 8 and 9 show the corresponding

potentials with time.
According to the RapiCors measurement principle,
a 5-s galvanostatic pulse of 10 lA was applied to the
reinforcement. If the measured corrosion rate was
[0.7 lA/cm2 (with the polarisation area of 40 cm2 in
this study), a 5-s galvanostatic pulse of 165 lA was
applied for increasing the polarisation response so as to
increase measurement precision. The measured corrosion rates in Figs. 6 and 7 show some fluctuation with
time, ranging from 0.02 to 1.1 lA/cm2 with some
exceptions. Bar AR1 was an exception with a mean
value around 0.3 lA/cm2, this bar was removed after
4 months of exposure for visual examination. From the
results obtained for the corrosion rate measurements as
shown in Figs. 6 and 7 it is difficult to distinguish a

Fig. 10 Corrosion rate as function of time for the bars CC1

CC8, monitored with the RapiCor instrument

clear corrosion initiation event for any of the bars, but

for bar AR2 (cover depth 15 mm) an increase of the
corrosion rate from about 0.05 upto 0.4 lA/cm2 after
*260 days can be noticed, also for bar AR5 (cover
depth 10 mm) a change in corrosion rate from around
0.06 upto 0.5 lA/cm2 after approximately 190 days
can be observed. In both cases the corrosion rate
decreases from the peak values, and for rebar AR2 the
corrosion process seems to cease and go back to the
same values as before the corrosion initiation.
In Figs. 8 and 9 a quite stable potential with time can
be observed for almost all AR bars, nevertheless a
slight tendency to shift to a less negative potential can
be observed. In two cases the development of the
potential with time deviates from the rest, for bar AR2
after *260 days (Fig. 8) and for bar AR5 after about
190 days (Fig. 9). In both cases a sudden drop of the
Ecorr can be noticed, which is in accordance with the
increase in corrosion rate as shown in Figs. 6 and 7, an
indication of corrosion initiation. In both cases the Ecorr
shifted later on from the lowest dip to a less negative
potential, this is more pronounced for bar AR2.
The measured corrosion rates for the CC bars were
0 lA/cm2 or close to zero, see Fig. 10. At some
isolated measurement occasions corrosion rates upto
0.03 lA/cm2 were recorded, which are still very low.
Due to the logarithmic scale in Fig. 10 the measured
corrosion rates that were 0 lA/cm2 are not plotted.
The results for the Ecorr measurements for the CC bars
are showed in Fig. 11.
In Fig. 11 a fairly steady Ecorr potential can be
observed for all bars with a tendency to shift to a less
negative potential with time. Bar CC2 shows more

Materials and Structures

100

Ecorr (mV vs SCE)

0
-100
-200
-300
-400

Bar CC1

Bar CC2

Bar CC3

Bar CC4

Bar CC5

Bar CC6

Bar CC7

Bar CC8

-500
0

50

100

150

200

250

300

350

400

450

Time (days)
Fig. 11 Free corrosion potential as function of time for the bars
CC1CC8, monitored with the RapiCor instrument

variation between measuring occasions when compared

with the other bars, but still the same development
tendency with time can be observed. No signs of
corrosion initiation (neither a significant increase in
corrosion rate nor a significant potential drop) were
observed for the CC bars.
3.2 Visual examination
The splitting of the specimens for visual examination
of corrosion condition was done several days
(28 days) to a couple of months (192 days) after the
indication of corrosion initiation by the electrochemical monitoring.
Figures 12 and 13 show pictures from the visual
examination of the SD bars. From the visual examinations corrosion could be confirmed on the steel bars
where corrosion initiation was observed from the
electrochemical monitoring. Further, no sign of corrosion was found on the steel bars where corrosion
initiation was not observed by the electrochemical
monitoring. The general appearance of the corrosion
immediately after removing the concrete cover was
one or a couple of dark blue-greenish localized
corrosion attacks with a size of 510 mm surrounded
with reddish-coloured rust. The corroded locations
coincide with air voids of size of 110 mm which were
present (in the concrete) at the steelconcrete interface.
Figure 14 shows picture from the visual examination of the bar AR5. According to the electrochemical
monitoring only bars AR2 and AR5 showed clear
signs of corrosion initiation for the as received bars,
this was confirmed by the visual examination.

Fig. 12 Picture showing corrosion attack at a steel/concrete

interface defect (bar SD1)

The corrosion spots in these cases did not coincide

with air voids or other visible defects on the steel/
concrete interface. Bars AR2 and AR5 showed corrosion initiation at the bottom side of the bar, at the end
that was cast in concrete. In both cases corrosion attack
was identified on the cut bright surface just at the edge
to the as received surface, Fig. 14. A somewhat
enhanced corrosion rate was recorded from the start for
bar AR1 (Fig. 7), the visual examination showed
corrosion attack on the top side where the bar protrudes
from the concrete, otherwise no corrosion could be
observed under the concrete covered part.
Figure 15 shows a picture from the visual examination of bar CC5 with concrete cover 10 mm. Despite
the presence of defects such as air voids at the steel/
concrete interface no visual sign of corrosion occurred
in any of the CC bars, which is in agreement with the
electrochemical monitoring.
Regardless of the initial steel surface condition, the
visually observed corrosion attack was always initiated on the side facing the direction of chloride
ingress. In no case did the initiated corrosion cause
visible cracks or any other break down of the concrete
cover. For all types of initial surface condition the bars
after splitting looked almost identical (except for the
parts that corroded) to the condition at the time of
casting except for a more whitish surface.
3.3 Threshold values
Chloride profiles measured at different times during
the exposure to sodium chloride solution are presented

Materials and Structures

Fig. 13 Picture showing corrosion location after removing the (steel bar) at a steel/concrete interface defect (bar SD7)

Fig. 14 Picture showing corrosion at the cut bottom end of steel

bar AR 5

in Fig. 16. In concrete specimen CSD one chloride

profile was measured after 75 days and two profiles at
the end of the test period which was after 329 days of
exposure, see Fig. 16a.
In concrete specimen CAR one chloride profile was
measured after 138 days of exposure and two profiles
at the end of the test period which was after 403 days
of exposure, see Fig. 16b. In concrete specimen CCC
one chloride profile was measured after 138 days, and
one at the end of the test period which was also after
403 days of exposure (Fig. 16b). The chloride threshold values were evaluated by following the calculation
procedure described in Sect. 2.2.2, and are presented
in Tables 4 and 5. When two profiles were determined
in the same occasion, a mean value of the regression

parameters from the curve fitting procedure described

in Sect. 2.2.2 was used in the calculation of the
chloride threshold values.
Table 4 presents the initiation time for corrosion
and the chloride threshold values for the SD bars. For
bar SD5 no chloride threshold value was calculated
because as earlier mentioned the corrosion initiation
time could not be accurately confirmed.
Table 5 presents the corrosion initiation times
and the chloride threshold values for the AR bars.
Because a data logger was not used in this case for
monitoring the corrosion state the actual initiation
time could not be exactly determined, corrosion
initiation could have occurred at whatever time
between two measuring occasions. Therefore the
values in Table 5 can be taken as lower and higher
values. In the case of bar AR1 no chloride threshold
value was calculated because the indication for
corrosion initiation, i.e. an enhanced corrosion rate
(Fig. 6), was recorded immediately at the first
measuring occasion (7 days after exposed to the
solution).
No chloride threshold value was calculated for the
CC bars, because the CC bars neither show any sign of
corrosion initiation in the electrochemical monitoring,
nor at the visual examination.

Fig. 15 Picture showing the steel/concrete interface after removing bar CC5

Materials and Structures

Fig. 16 Chloride profiles measured at different times. a Chloride profiles measured on concrete specimen CSD. b Chloride
profiles measured on concrete specimens CAS and CCC

4 Discussion
4.1 Corrosion initiation
In the passive state, the Ecorr was around -100 mV
versus SCE for the free corroding SD bars. At various
times all the free corroding SD bars except the one
with the thickest concrete cover (25 mm) showed a
sudden drop, more than 250 mV to a more negative
potential, indicating corrosion initiation (Fig. 4). Bar
SD1 showed corrosion initiation at an early stage but
this indication was followed by a period where the
potential returns to less negative values. This suggests
that corrosion has ceased, and then restarted after
about 1 month. This phenomenon is called repassivation, although the reason why and the mechanism how
actively corroding steel repassivates is not completely
known with certainty. It has been suggested that in
pitting corrosion a cap of porous corrosion products
acts as a barrier and seals off the active local
corrosion by limiting the exchange of local and bulk

electrolytes [21]. Also the SD bars with the pre-set

potential 0 mV versus SCE showed corrosion initiation at various times, with exception for the bar (SD8)
with the thickest concrete cover (Fig. 5). The detection of depassivation for the corroding bars in this case
is straightforward by a rapid increase of the current
required to keep the pre-set potential. No repassivation
was possible due to the imposed potential. The
increase of the polarising current stopped only when
the corroding bar was disconnected, which was done
14 days after corrosion initiation. These bars were
then allowed to corrode freely (upto a month) and the
Ecorr was recorded by the data logger, no repassivation
was recorded with in this time period.
Despite the observed scattering in initiation time,
the results reveals that the time to corrosion initiation
for all SD bars was determined by the thickness of the
concrete cover. Further, the visual examination
showed that the corroded locations coincide with air
voids of size of 110 mm which were present (in the
concrete) at the steelconcrete interface in the chloride
penetration direction. This means that the actual
concrete cover thickness at the corrosion locations
scattered due to these defects, and can be one of the
reasons for the observed scattering in corrosion
initiation time when comparing the bars with similar
concrete covers. One must still keep in mind that
studies of corrosion initiation time always reveal a
wide scatter of data, even for metals tested in solutions
due to its stochastic nature [32]. The presence of
entrapped air voids (or other defects) at the steel
concrete interface has been postulated to have a
detrimental effect on the chloride threshold values
[39]. In their literature review Glass and Buenfeld [13]
stated that it appears that the most important parameter
affecting the threshold levels is actually the condition
of the steelconcrete interface.
For the AR bars the results showed that in the
passive state the potentials of the bars were about
-50 mV versus SCE at the start of the exposure to the
sodium chloride solution. Furthermore, a tendency to
attain more noble potential values (upto 0 mV vs.
SCE) with time can be observed in Figs. 8 and 9. The
same trend of the potential development with time was
also observed for the CC bars, with the exception that
the measured bar potentials were more negative
starting from about -150 mV versus SCE and being
around -100 mV versus SCE at the end of the test
(Fig. 11). This observed continuous increase of Ecorr

Materials and Structures

Table 4 Corrosion initiation time and threshold values for the SD bars
Bar

Monitoring method
Open circuit potential
SD1

SD2

Potentiostatically controlled
SD3

SD4
25

SD5

SD6

SD7

SD8
25

Cover depth (mm)

10

15

20

10

15

20

Corr. init. time (days)

77a/110

241

279

\12

137

298

Ccr (mass% of cem)

1.4a/1.5

1.4

1.1

1.3

1.1

The first sudden drop of potential as shown in Fig. 5

Table 5 Corrosion initiation time and threshold values for the AR bars (corrosion monitoring with RapiCor)
Bar

AR1

AR2

AR3

AR4

AR5

AR6

AR7

AR8

Cover depth (mm)

10

15

20

25

10

15

20

25

Corr. init. time (days)a

264299

187264

Ccr (mass% of cem.)

1.41.5

1.92.1

Interval between the two measuring occasions when corrosion initiation was detected

with time have often been reported for steel bars in

alkaline environments, such as in simulated concrete
pore solution and for bars embedded in cement-based
materials [6, 18, 39] This trend towards a less negative
potential has been suggested to be due to growing of
thickness and transformation of composition of the
passive film [29].
The Ecorr measurements showed only for two of
eight AR bars indication of corrosion initiation, by
sudden drop of the potential to significantly more
negative potentials. These findings were supported by
the corrosion rate measurements and also confirmed in
the visual examination. In contrast to the SD bars the
corrosion locations for the AR bars did not coincided
with defects on the steelconcrete interface. In both
cases the local corrosion attack occurred just at the
edge between the as-received surface and the cut
surface. This is likely due to the heterogeneous nature
of the metal surface at that area, owing to a combination of a strained metal lattice because of the cut and
shaping of the end, and the presence of different site
energies due to various surface conditions [21]. As for
one of the SD bars also one of the corroding AR bars
showed a tendency of repassivasion, where Ecorr
returns to less negative values (Fig. 8) and icorr drops
(Fig. 6) to insignificant levels from a corrosion point
of view.
No sign of corrosion initiation could be observed
for any of the CC bars neither from the

electrochemical monitoring after exposure through

the whole test period (Figs. 10 and 11), nor from the
visual examinations. During the whole test period the
measured corrosion rates for the CC bars were at levels
barely detectible (Fig. 10). One interesting observation is the markedly difference in the measured
corrosion rates between the AR bars and the CC bars
in the passive state, see Figs. 6, 7 and 10. It is generally
accepted that corrosion rates less than 0.1 lA/cm2
represent the passive state of steel in concrete [4]. The
measured corrosion rates for some of the AR bars were
around or even exceeded this value even in the early
stage of exposure to the saline solution. This would
imply that the bars were in an active corrosion state,
but neither the potential monitoring, nor the visual
examination supported this. Our explanation is that the
AR bars has low polarization resistance due to some
superficial corrosion spots, leading to measurable
corrosion rate but not necessarily very negative halfcell potential which is an indication of pitting corrosion. Similar results for pre-rusted reinforcement bars
that would have been expected to be in the passive
state were reported by Novak et al. [24]. In another
investigation Gonzalez et al. [14] found a direct
relation between an enhanced measured corrosion rate
and the amount of rust initially present on the steel
surface of their specimens. In both these investigations
the corrosion rate was estimated with traditional linear
polarization resistance measurements. The authors in

Materials and Structures

[24] and [14] made additional gravimetrical measurements and came to two different conclusions. Novak
et al. [24] concluded that the pre-rusted bars exhibited
unacceptable high corrosion rates even when the
chloride content was practically zero in the concrete.
The major cause was pointed out to be that the porous
rust acting as barrier for alkaline solution from
concrete to passivate the metal. Gonzales et al. [14]
found that the electrochemical measurement overestimated corrosion and thought that polarization resistance is not suitable for measuring corrosion rate of
pre-rusted specimens. In our investigation the corrosion rate measurements were used only as an indication for corrosion initiation, by following a sudden
increase of the corrosion rate, this could quit clearly be
identified even though the scattering in the measured
data for the AR bars (Figs. 6, 7). However, it must be
pointed out that the identification of corrosion initiation only through corrosion rate measurements could
have been more difficult if the measurements were not
made continuously and if the support of the Ecorr
measurements (Figs. 8 and 9) were lacking. The
scattering in measured corrosion rates between the
different AR bars in the passive state is likely due to
the heterogeneous state of the surface conditions.
4.2 Threshold values
Concrete is an inhomogeneous material entailing to a
non-uniform chloride ingress, thus the chloride content is not constant at a certain depth in a concrete
specimen. The sampling procedure for chloride analysis used in this study provides average values of the
chloride content, which under practical point of view
can be seen as adequate. Keeping in mind that the
sampling for measuring the chloride profiles was made
in different location from each concrete specimen the
results in Fig. 16 are quite consistent.
The mean value of chloride threshold values
evaluated from the chloride penetration profiles for
the SD bars was 1.2 % by weight of cement with a
standard deviation of 0.2 %. Despite the imprecise
time for corrosion initiation of the AR bars, the results
in Table 5 suggest that the chloride threshold values
for the corroded AR bars are higher than those for the
SD bars. None of the CC bars started to corrode even
after more than 1 year of exposure, even with chloride
contents between 1.5 and 2.1 % by weight of cement

at the depth where some of the CC bars were located.

The chloride threshold values reported in the literature
scatter over a wide range and it is difficult to make a
direct comparison between studies with different
experimental set-ups [2, 5]. However, the mean
chloride threshold value for the SD bars in this study
is in line with the mean values reported in the
statistical analysis of published chloride threshold
values made by Alonso and Sanchez [2], for similar
experimental procedures.
One question often arising from chloride threshold
values obtained in laboratory tests is the relation with
data obtained in the field. A mean value of 0.64 % by
weight of cement with a standard deviation of
0.61 % for chloride threshold values from reported
data obtained from specimens under outdoor exposure
or field structures is given by Alonzo and Sanchez [2].
As in our results, higher chloride threshold values are
generally reported in laboratory set-ups than in field
structures, although a wide range of variability is
detected in both cases [2, 5]. Because several variables
affect chloride level for depassivation, it is difficult to
clearly point out the cause of the differences in
chloride threshold values between laboratory set-ups
and field structures. However, some decisive parameters have been suggested: Page [27] emphasized that
the exclusion of macroscopic defects from the steel
concrete interfacial zone in laboratory conditions lead
to observation of higher chloride values, Page [27]
also mentioned that the cleaning of the steel before
embedding also can be of importance. Alonzo and
Sanchez [2] found that the presence of cracks
([0.4 mm) in concrete situated in a splash zone where
the cracks were exposed to air significantly reduce the
chloride threshold values. While Angst et al. [6]
suggested that a possible explanation for the unrealistically high chloride threshold values measured in
their laboratory study is the effect of specimen size,
viz. an increasing susceptibility to pitting corrosion
with increasing exposed steel area. On the other hand,
Tang and Utgenannt [36] found from the investigation
of over 10 years field exposure that the chloride level
of 1 % by mass of binder is critical for significant ongoing corrosion observed by destructive visual examination. The laboratory threshold values in Tables 4
and 5 obtained in this study are, in fact, not far away
from the field investigation in Tang and Utgenannt
[36].

Materials and Structures

Fig. 17 Total chloride content profiles along the interface for

the three different steel surface conditions (Silva [31]). The
designations SD2-A1 stands for bar SD1, AR-A1 stand for bar
AR1 and CC-A1 stands for bar CC1

4.3 The influence of steel surface condition

In this study macroscopic defects, such as large air
voids on the steelconcrete interface were generally
observed in all specimens (see Figs. 12, 13 and 15),
and susceptibility of the rebar to pitting corrosion at
those locations was confirmed, at least for the SD bars.
However, defects on the steelconcrete interface did
not seem to have the same strong influence on the
susceptibility to pitting corrosion for the AR bars and
CC bars. This is clearly evident e.g. from bar CC1 and
CC5, at the times of the visual examination the
chloride concentration was about 1.7 and 2.1 %,
respectively, by weight of cement and despite macroscopic defects at the steelconcrete interface (see
Fig. 15 for bar CC5), no corrosion initiation was
observed. This emphasizes how important the surface
condition of the steel bar is for the susceptibility to
corrosion initiation. According to Silva [31] who
performed chloride content profiles on the specimens
from this investigation, the average chloride content
along the concrete-steel interface of the bars with these
three different surface conditions are at similar level at
the same cover depth after the same exposure period,
as shown in Fig. 17. At this level of chloride content
only the SD bar was found corroded, but not the other
bars in Fig. 17, especially the AR bar which even has
slightly higher average chloride content. It is evident
that the influence of the steel surface condition is
stronger than that of inhomogeneous chloride ingress.
Therefore, the steel surface condition can be one of the
most decisive parameters attributing to the variability
in the reported chloride threshold values.

Some of the basic phenomena associated with

passivity and depassivation of pure metals immersed
in aqueous solutions are still incompletely understood
[21]. The embedment of steel in concrete further
complicates the aspects of the electrochemical behaviour. Nevertheless, for corrosion initiation of steel in
aqueous solution, localized corrosion, typically pitting
occurs due to inhomogeneity of metal surface and/or
the environment to which the steel is exposed [20].
Analogically, this implies that for the SD bars
inhomogeneity of metal surface, in the form of
patched mill-scale, coinciding with inhomogeneity
of the environment, in the form of defects on the steel
concrete interface, resulted in a higher susceptibility to
corrosion initiation compared to the AR and CC bars
where the metal surfaces can be assumed to be more
homogenous. The susceptibility to corrosion initiation
due to defects on the steelconcrete interface in these
cases (AR and CC bars) seems to be overshadowed by
the homogenous metal surface.
Also from what is known about steel in aqueous
solutions corrosion product films protect the underlying steel from corrosion to some extent by acting as a
barrier layer against the corrosive environment. If this
barrier layer is damaged at a fixed area, the steel
surface exposed will be susceptible to corrosion [20].
This can explain why corrosion initiation appeared at
the cut surface of the AR bars.
A simple explanation to the different susceptibility
to corrosion initiation is that an inhomogeneous metal
surface such as that of the SD bars may produces a less
homogeneous passive film than the metal surface of
the CC bars. Especially at the phase boundaries
between mill scale and substrate steel, as the mill scale
was not uniform on the SD bars. Ghods et al. [12]
showed that even for steel bar with apparently
continues mill scale crevices exist between the mill
scale and substrate steel and also that cracks through
the mill scale are connecting the steel surface with the
surrounding environment (pore solution). The authors
in Ghods et al. [12] suggested a mechanism typical to
that of crevice corrosion for the susceptibility to
corrosion initiation of rebar with mill scale.
4.4 Methods for monitoring corrosion initiation
From the visual examinations it can be concluded that
all three corrosion monitoring methods seem to give
reliable results in identifying corrosion initiation,

Materials and Structures

although the number of steel bars monitored by each

method was limited.
The advantage with the RapiCor handheld instrument is that it simultaneously records corrosion rate
and Ecorr which makes it easier to decide if corrosion
has initiated or not. The drawbacks with the handheld
instrument is that it is relatively laborious and cannot
be used for continuous monitoring, implying the exact
corrosion initiation time can occur between two
measuring intervals. However, this does not lead to a
significant error in the calculated threshold values as
shown in Table 5, despite the long interval between
the measuring occasions.
The benefits with continuous monitoring of Ecorr
using a data acquisition system include a more precise
registration of the corrosion initiation time, less
laborious, and hence, more cost-efficient. The drawback with monitoring of Ecorr only is that the
electrochemical potential can change because of other
reasons than corrosion initiation, for instance oxygen
depletion [11]. A tendency of this decrease in potential
can be seen in Fig. 4 during the first 75 days of
immersion. If this tendency was kept longer, it might
be difficult to distinguish the corrosion initiation.
The potentiostatic controlled method can very
clearly and sharply detect the initiation of corrosion,
but is criticized for being an artificial state and not
related to reality. For example, a phenomenon like
repassivation as noted in Fig. 4 for bar SD1 would not
appear in the potentiostatic controlled method as once
corrosion has been initiated the current will continue
to increase until the bar in the specimen is disconnected. In their literature review Alonso and Sanchez
[2] showed that generally lower CT-values were
reported from potentiostatic tests than natural open
circuit potential tests, although this was not the case in
this study as can be seen in Table 4.
5 Conclusions
From this study, the following major conclusions can
be drawn:
1.

The steel surface condition has a strong effect on

the corrosion initiation of reinforcement in concrete, and can likely be one of the most decisive
parameters attributing to the variability in the
reported chloride threshold values obtained in
laboratory experiments.

2.

3.

Among the three different surface conditions

investigated in this study, the bars with CC
surface reveal the lowest susceptibility to corrosion initiation (highest CT-values) and M bars
reveal the highest susceptibility to corrosion
initiation (lowest CT-values), whilst the bars with
the as-received rusty surface had a corrosion
initiation susceptibility between the above two
conditions.
Concerning the development of a laboratory tests
under conditions that are as realistic as possible to
predict threshold chloride values for embedded
reinforcement steel, this study has identified the
necessity of agreement upon a standard metal
surface condition that can be considered as
general representative and reproducible.

As a pilot work, the results from this study

highlighted the importance of steel surface condition
in a test method for CT-values. As a speculation of the
significance for practice, the findings from this study, a
pre-conditioning procedure involving chemical cleaning and pre-rusting of steel bars before being embedded in concrete specimens has been proposed by the
RILEM TC 235-CTC for inter-laboratory comparison.
It is hoped that this preconditioning procedure can
provide relatively consistent steel surfaces for testing
chloride threshold values with an acceptable precision
for comparison of concrete materials with regard to
corrosion resistance.
Acknowledgments The authors are grateful for the financial
support from the Swedish Consortium for Financing Basic
Research in the Field of Concrete.

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Materials and Structures

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