608 DOI: 10.1002/maco.200905276 Materials and Corrosion 2009, 60, No.

Depassivation of steel reinforcement in case of pitting

corrosion: detection techniques for laboratory studies
L. Bertolini* and E. Redaelli

Methods for service life prediction of reinforced concrete structures exposed to

chloride-bearing environments require, amongst other parameters, the
knowledge of the chloride threshold for pitting corrosion initiation (Clth).
Nowadays, although the main factors influencing the chloride threshold are well
known, it is often difficult to quantify a value of the chloride threshold, partly
because of its intrinsic high variability, and partly because of the different test
methods that have been used to measure it. All the experimental tests rely on
the detection of steel depassivation and simultaneous measurement of chloride
content or steel potential. This paper deals with the methods that can be used to
detect steel depassivation in relation with the determination of the chloride
threshold. Tests in concrete-pore-simulating solutions as well as tests in
concrete will be considered, and advantages and limitations will be discussed.

1 Introduction experimental details, such as the way chlorides are introduced in

According to Tuutti’s model, methods for the design of durability
of reinforced concrete structures exposed to marine environ-
ments or the action of de-icing salts, divide the service life into an
initiation period, during which chloride ions penetrate the
concrete cover and initiate pitting corrosion, and a subsequent
propagation period during which corrosion leads to a limit state
affecting the serviceability or safety of the structure [1]. In order to
calculate the initiation period, the chloride threshold (Clth), i.e.
the minimum amount of chloride ions required to break the
passive film and initiate pitting corrosion (i.e. to cause
depassivation), should be defined. If the penetration of chloride
as a function of depth (x) and time (t) is known (Cl(x,t)), the
chloride threshold may be measured as the chloride content
detected at the depth of the bars when corrosion initiates, i.e.
Clth ¼ Clðx ¼ c; t ¼ ti Þ (1)
where c is the thickness of the concrete cover and ti is the
initiation time, as depicted in Fig. 1.
The definition of Clth is quite complex for several reasons.
First of all, pitting corrosion initiation is a stochastic phenom-
enon that is influenced by a great number of parameters. Clth, in
principle, should be defined through probability distributions
that take into account the effects of those parameters. However,
such an approach would require a huge amount of experimental
data which, in practice, is impossible to collect. Furthermore,
L. Bertolini, E. Redaelli
Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria
Chimica ‘‘G. Natta’’, via Mancinelli 7, 20131 Milan (Italy)
E-mail: luca.bertolini@polimi.it
the concrete (e.g. added to the mixing water or penetrated by
diffusion or migration), the means of measuring the chloride
content (e.g. total acid soluble chlorides expressed by mass of
cement or free chlorides from pore solution expressed as
concentration in solution) or the surface preparation of the rebar
sample, may have a considerable influence on the resulting value
of the chloride threshold. The technique used to detect the
depassivation of steel may also have a remarkable effect on the
chloride threshold.
Since there are no standardised methods for the evaluation of
the chloride threshold as well as for the detection of depassiva-
tion, a large variety of techniques has been used by different
researchers. Indeed, even the definition of the initiation of pitting
corrosion is not simple. In fact, an initial phase, where breakdown
of the passive film alternates to repassivation at incipient anodic
sites, is followed by a permanent active corrosion stage, where
sustained pit propagation takes place [2]. From a practical point of
view, it is often assumed that corrosion initiates when an anodic
current density above a certain threshold (i.e. 1 mA/m2,
corresponding to roughly 1 mm/year of average corrosion rate)
is reached, although this may be inappropriate in the case of
strong localisation of corrosion.
This paper describes some of the main approaches used to
detect corrosion initiation of steel in relation to the definition of
Clth. Firstly, an overview of the main features of the electro-
chemical behaviour of steel in chloride contaminated concrete
will be given. Then, electrochemical tests in alkaline solutions
that simulate the concrete pore liquid will be described. Finally,
tests on steel bars embedded in concrete (or mortar) specimens
will be discussed. Examples of different methodologies utilised
for the detection of depassivation, based on the above-mentioned
techniques, will be presented and the advantages and limitations

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Materials and Corrosion 2009, 60, No. 8
Figure 1. (a) Tuutti’s diagram defining the service life as the sum of the
initiation time (ti) and the propagation time (tp) [1] and (b) schematic
representation of chloride profile in concrete at the time of pitting
corrosion initiation
of tests will be addressed. The authors do not intend to be
exhaustive and thus, only those techniques used to detect
depassivation that have found a general diffusion for the
determination of the chloride threshold would be considered.
Moreover, a comparison of chloride threshold values obtained
from different techniques and available in the literature is outside
the scope of this paper, and will be addressed in another
contribution in this special issue of Materials and Corrosion [3].
2 Electrochemical behaviour of steel in
concrete
The electrochemical behaviour of steel in chloride contaminated
concrete can be described through the anodic polarisation curve
depicted in Fig. 2a (proposed by Pourbaix [4]), that plots the anodic
current density (that measures the rate of steel dissolution) as a
function of the steel potential in concrete with a given content of
chloride ions. This figure shows, at low potential values, the
passive range where the corrosion rate is negligible. Pitting
corrosion may take place when the potential of the steel is above
the pitting potential Ep (or breakdown potential), which is a
function of the chloride content, but also of several other
parameters (pH of the pore solution, temperature, microstructure
and composition of the steel-concrete interface, composition and
Figure 2. (a) Polarisation curve of steel in chloride contaminated concrete and definition of the pitting potential Ep (or breakdown potential). (b)
Definition of the chloride threshold. (c) Definition of the protection potential Er (or repassivation potential) and of the regions of stability of the
passive layer [4]
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Detection of steel reinforcement depassivation 609
Figure 3. Pitting potential (Ep) and repassivation potential (Er) as a
function of the chloride content in the concrete [6]
surface finishing of the steel bar, etc.). In particular, the pitting
potential decreases as the chloride content increases [5]. If Ecor is
the corrosion potential of the passive steel in chloride
contaminated concrete, corrosion will initiate if the amount of
chlorides is high enough to decrease Ep below Ecor. Therefore, the
chloride threshold Clth can be defined as the amount of chloride
that brings about a value of Ep equal to Ecor. This condition is
shown in Fig. 2b.
The anodic polarisation curve of steel can also be used to
define the regions of stability of the passive film, as shown in
Fig. 2c that plots the curve obtained from a cyclical polarisation
test in which the potential of the steel, after exceeding Ep, is
decreased until conditions of passivity are established again [4].
To stop the pitting attack, it is necessary to reach a potential value
Er (named repassivation potential or protection potential) which is
more negative than Ep. Therefore, in the range of potential
between Ep and Er, the attack cannot initiate but if it has already
initiated, it can propagate. Er varies with the same parameters that
affect Er and is usually about 200–300 mV below Er.
Depending on the potential of steel and the chloride content
in the concrete, it is possible to define different domains where
pitting corrosion can initiate and propagate. Figure 3 depicts the
trends of pitting potential and repassivation potential of carbon
steel as a function of the chloride content in concrete [6]: though
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610 Bertolini and Redaelli
in a qualitative way, the line Ep shows the dependence of the
pitting potential on the chloride content. In the mean time, the
same curve can also be considered as the line that describes the
dependence of the chloride threshold on the potential of the steel.
In fact, the line describes the highest content of chlorides
compatible with the condition of passivity (i.e. the chloride
threshold) for a given potential of the steel. For instance, for a
corrosion potential value of around
100/þ100 mV/SCE, typical
of steel in concrete exposed to atmosphere, the chloride threshold
is around 0.4% with respect to cement mass, while for a steel
potential below
250/
300 mV/SCE, as in a situation of reduced
oxygen availability or small external cathodic polarisation, the
chloride threshold may be higher than 1%.
Amongst factors that have an influence on the chloride
threshold, there are the pH values of the concrete pore solution
(i.e. the concentration of hydroxyl ions [7]) and the presence of
voids at the steel/concrete interface [8]. The concentration of
hydroxyl ions in the pore solution depends on the type of cement
and additions: most blended cement concretes obtained with
pozzolanic additions have a lower alkalinity compared to portland
cement concretes. The presence of voids near the steel surface is
determined by the workability of the fresh concrete and also by
the effectiveness of the compaction methods that contribute to
determine the volume of entrapped air. To this regard, it should
be noted that chloride thresholds found in real structures are
usually lower than those found in well-compacted laboratory
specimens with similar materials [9]. Another contribution in this
special issue will address the role of the interfacial zone on the
initiation of chloride-induced corrosion in concrete [10].
Several other factors, such as the temperature, the
composition of the cement, the composition or surface roughness
of the steel reinforcement and the polarisation with anodic or
cathodic current may affect both the pitting potential and the
chloride threshold. Some of these factors, that can be used to
detect steel depassivation in relation with the determination of
chloride threshold, will be mentioned in the following sections
while discussing the main techniques.
3 Electrochemical tests in solution
Electrochemical tests in solutions that simulate the concrete pore
solution are usually performed according to the experimental
arrangement shown in Fig. 4. A steel specimen (a portion of a bar)
Figure 4. Experimental arrangement for electrochemical tests in
solution
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Materials and Corrosion 2009, 60, No. 8
is immersed in the test solution and connected to a potentiostat
that can impose a polarisation potential (Epol) by means of a
suitable polarisation current (Ipol).
Tests in solution are often used to evaluate the resistance of
steel to pitting corrosion, e.g. to compare different types of steel or
the effect of preventative techniques (such as corrosion
inhibitors). In order to obtain results that are representative of
the behaviour of steel in concrete, the testing solution has to
simulate the concrete pore solution; with this regard, the method
of pore solution extraction allowed a step forward in the
understanding of factors that determine pore solution composi-
tion [11]. Usually, alkaline solutions of saturated calcium
hydroxide are used, possibly with the addition of sodium
hydroxide and potassium hydroxide. Saturated calcium hydroxide
allows to reach a pH of about 12.6, and in the mean time, provides
a buffer effect owing to the presence of portlandite (i.e.
precipitated crystals of calcium hydroxide). Addition of appro-
priate concentrations of sodium hydroxide and potassium
hydroxide may increase the pH above 12.6 and thus
achieve pH values more similar to those measured in the
extracted pore solution. Chloride ions are added to simulate
chloride contamination, usually as sodium chloride or calcium
chloride.
Even when a test solution has the same chemical
composition of the concrete pore solution, other effects
connected to the role of the steel/concrete interface are neglected,
such as the porosity of the cement paste, the binding effect and
the buffering effect of the hydration products of cement [9]. In
particular, the pore solution can only simulate free chlorides and
does not take into account the equilibrium between bound and
free chlorides, while bound chlorides have also been shown to
have an effect on pitting corrosion initiation [8]. Moreover, the
chloride concentration in the solution, usually expressed as mass
percentage, cannot be converted to chloride content in concrete,
and this does not allow a direct comparison between results from
solution tests and results from concrete tests.
Tests are usually carried out without stirring the solution,
since mixing would force a redistribution of chlorides and
alkalinity which is far from occurring in the real concrete pore
solution.
3.1 Potentiodynamic polarisation tests
Potentiodynamic polarisation tests are aimed at plotting the
polarisation curve of steel so as to detect the pitting potential Ep.
The steel potential is forced to vary towards anodic values, starting
either from the free corrosion potential or from lower values up to
a potential value, where the measured current undergoes a
considerable increase after pitting corrosion initiates. The steel
potential is varied with a certain scan rate, usually around 0.6 V/h
(i.e. 10 mV/min), and the current Ipol is recorded continuously
(Fig. 5a) [12–14]. Tests can also be carried out in de-aerated
solutions (e.g. by means of nitrogen flow) in order to lower the
steel potential and prevent corrosion initiation before the
beginning of the test. Examples of polarisation curves obtained
on carbon steel in solutions with different chloride concentra-
tions are shown in Fig. 6. The recorded current Ipol is the total
current exchanged at the surface of the specimen, i.e. the
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Materials and Corrosion 2009, 60, No. 8
Figure 5. Interpretation of potentiodynamic polarisation curve
algebraic sum of the anodic (Ia) and cathodic (Ic) current
Ipol ¼ Ia þ Ic (2)
due to anodic and cathodic reactions occurring simultaneously at
the surface of the electrode. The anodic contribution, Ia, is
isolated in order to obtain the anodic polarisation curve shown in
Fig. 5b.
By repeating the test in solutions with varying concentrations
of chloride ions [Cl
], the relationship between Ep and [Cl
] can
be plotted. For instance, Fig. 7 shows that such a relationship was
obtained from potentiodynamic polarisation tests in solutions of
saturated calcium hydroxide with different chloride concentra-
tions, for a carbon steel and for two types of stainless steel [15].
These results clearly show that for carbon steel, the pitting
potential starts from a very high value (>600 mV/SCE) in
solutions with 0.2% chlorides and decreases rather rapidly with
chloride concentration; for stainless steels, pitting potential was
around 400 mV/SCE, regardless of the chloride concentration that
varied in the range 1–8% by mass in solution.
These types of graphs are mainly used to compare the
resistance to pitting corrosion of different materials. Potentio-
dynamic polarisation tests have the advantage of being rather easy
to be performed in a wide range of composition of the test
Figure 6. Example of potentiodynamic polarisation curves obtained in
saturated calcium hydroxide solutions with a scan rate of 20 mV/min
[15]
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Detection of steel reinforcement depassivation 611
Figure 7. Relationship between pitting potential of different metals
and chloride concentration determined from potentiodynamic
polarisation tests in saturated calcium hydroxide solutions with
different chloride concentrations [15]
solutions and temperatures. Relationships between pitting
potential and chloride content might also be used to extrapolate
the chloride threshold on the potential, so that the comparison of
different materials can be done on the basis of the critical chloride
content instead of the pitting potential. However, the extrapolated
chloride threshold values should only be used for comparison
purpose. The use of results of potentiodynamic curves to
extrapolate chloride threshold values in real conditions should be
discouraged, not only because of the above mentioned
inadequacy of solutions in simulating concrete and impossibility
in converting concentration values in chloride contents in
concrete, but also because such relationships are affected by
experimental parameters, such as the potential scan rate [12–14].
3.2 Potentiostatic polarisation tests
Potentiostatic polarisation tests consist in the application of a
constant value of potential and monitoring of the corresponding
polarisation current. Usually after the potential is applied, the
chloride content is increased until corrosion initiation is detected
by a sharp increase in Ipol, as shown in Fig. 8. These tests have
been used to compare the resistance to pitting corrosion of
different types of metals compared to carbon steel [15, 16].
Compared to potentiodynamic polarisation tests, they return a
chloride content (although expressed as chloride concentration in
solution) that can be directly used to compare the behaviour of
different materials in different conditions. For instance Fig. 9
shows the concentration of chloride at which depassivation had
occurred on samples polarised at þ200 mV/SCE in solutions with
different values of pH. The potential value of þ200 mV/SCE was
chosen as a conservative value as it was above the maximum
potential value that can be assumed by steel in aerated concrete.
On carbon steel, the chloride threshold was around 0.5% of
chlorides by mass in the solution with a pH of 12.6 (i.e. saturated
calcium hydroxide), while it increased to 7% with a pH of 13.9
(0.8 M sodium hydroxide saturated with calcium hydroxide); at
the same pH values, AISI 304 stainless steel showed chloride
contents of 4.5% and 10%, while on AISI 316 stainless steel
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612 Bertolini and Redaelli
Figure 8. Interpretation of potentiostatic polarisation tests: (a) before corrosion initiation, (b) after corrosion initiation, (c) monitoring of the
polarisation current as a function of the chloride concentration and definition of Clth
corrosion did not initiate even with 10% of chlorides. Although
these values of chloride concentration cannot be converted to
values of chloride threshold in concrete, these tests allow a rapid
evaluation of parameters such as pH value and temperature, that
can be easily controlled in a solution.
4 Tests in concrete
Tests in concrete are expected to be intrinsically more realistic
compared to tests in solution. However, problems may arise from
possible alterations of the steel/concrete interface due to the
execution of the test itself, in particular, in the case of
electrochemical tests. Tests in concrete are more demanding
and time consuming than tests in solution, since they require not
only the preparation of metal samples, but also casting and curing
of concrete or mortar in suitable conditions.
Concrete specimens may be exposed to chloride penetration
by ponding, wet-dry cycles or exposure to natural marine
environments (sometimes the chloride penetration is forced by
migration, but in this case the test set-up should be carefully
designed to prevent that the steel bar could be polarised or
Figure 9. Example of results from potentiostatic polarisation tests in
solutions with different values of pH, for different types of steel. Black
symbols show tests were corrosion initiation was detected and thus
can be considered as an estimation of Clth [15]
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Materials and Corrosion 2009, 60, No. 8
interfered by the current applied to induce the migration of
chlorides) and the chloride content is measured at the depth of
the steel bar at the time when corrosion initiation is detected.
Alternatively, chlorides can be added to the concrete mix;
although this approach is generally considered less appropriate
since steel is not allowed to form a passive film in chloride-free
concrete, it can drastically reduce the time of testing, especially
when impervious concretes are considered. In this case, the
chloride threshold can be detected by comparison of specimens
with higher chloride contents where corrosion initiates and those
with lower chloride contents where corrosion does not initiate.
In concrete specimens, corrosion initiation can be assessed
by visual inspection, i.e. when macroscopic consequences of
corrosion take place (e.g. cracking of concrete, loss of steel mass
or cross section). However, corrosion can be detected only at a
later stage and if chlorides penetrate from the surface, Clth may be
overestimated. Monitoring of electrochemical parameters could
allow detecting corrosion initiation much earlier than macro-
scopic consequences take place.
The exposure conditions of the specimens influence the
moisture content of the concrete and its temperature (as well as
their variations in time) and, thus, may have a remarkable effect
on the chloride threshold. This should be taken into considera-
tion in the interpretation of the results. Sometimes, tests are
made in climatic chambers in order to reproduce constant values
of humidity and temperature. However, often a long time is
required before the concrete reaches an equilibrium condition
with the testing environment.
As a matter of fact, for several reasons, the duration of tests in
concrete is much longer than that of tests in solution, and it is
typically of the order of months or even years.
4.1 Visual inspection and mass loss measurements
The detection of depassivation through direct observation of
the steel surface requires to extract the reinforcement from the
specimen and to determine the chloride content in a concrete
sample collected close to the reinforcement itself. Ideally, if
the aim is the determination of the chloride threshold, this should
be done at the moment of corrosion initiation; however, since the
consequences of pitting initiation are not immediately evident on
the outer concrete surface, in the laboratory this method is usually
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Materials and Corrosion 2009, 60, No. 8 Detection of steel reinforcement depassivation 613

Table 1. Number of cases showing corrosion for different values of chloride content (expressed as % by cement mass) [17]

Chloride range 0.2% 0.20–0.35% 0.35–0.50% 0.50–1.0% 1.0–1.5% 1.5%

Number of cases investigated 99 86 43 105 59 54

Number showing corrosion 2 19 10 34 38 41
Percentage showing corrosion 2.0 22.1 23.3 32.4 64.4 75.9

combined with other measurements that allow to detect the onset
of corrosion by means of non-destructive methods (mainly
electrochemical methods, see section 4.2). Visual inspection
allows to investigate the actual corrosion state of steel, e.g. by
measuring the mass loss, the localisation of the attack and its
maximum penetration; however, it is usually time consuming,
especially because of the time necessary for chloride to penetrate
the concrete cover and also the time required for corrosion to
propagate to a stage where its effects can be observed. This may be
a strong limiting factor in the case of concretes with a high
resistance to chloride penetration.
Direct observation has been used to estimate the chloride
threshold on real structures exposed to marine environments or
de-icing salts: for instance, the correlation between the chloride
content measured close to steel reinforcement and the probability
of corrosion (evaluated as the percentage of corroded surface) that
is shown in Table 1 firstly allowed to consider a value around 0.3%
of chlorides (with respect to cement mass) as an estimation of the
chloride threshold [17].
Figure 10 reports the results of measurements of mass loss
as a function of chloride content in a concrete made with 30% fly
ash cement and shows a value of chloride threshold around 0.5%,
whilst similar specimens made with portland cement had a value
of 0.7% (increasing the fly ash content to 50% caused a further
decrease in the chloride threshold, that was 0.2%) [18]. This result
is an example of the role of pozzolanic additions in determining
chloride threshold. It should be noted that although concretes
containing fly ash cement usually have initiation times higher
than those containing portland cement (due to their higher
resistance to chloride penetration), the reduction of the chloride
threshold can partially mitigate this effect and should be carefully
evaluated.
Direct observation of reinforcement has been used to
evaluate the corroded percentage of steel surface in order to
investigate the effectiveness of cathodic prevention in increasing
the chloride threshold: Table 2 shows the results of long-term
experimental tests on slabs made with ordinary concrete and
subject to ponding cycles and to the application of different
cathodic current density since the beginning of tests (i.e. when
steel was passive). Applying a current density of 0.4 mA/m2, the
chloride threshold was 1.52% (while it was 0.73% in the reference
slab), and when the slab was demolished (after 5 years of tests)
the maximum attack was 1 mm (1.5 mm in the reference) and the
corroded area 0.7% (2.5% in the reference). The results of these
tests also allowed to better quantify the correlation reported in
Fig. 3 [19].

4.2 Monitoring corrosion potential and corrosion rate

The initiation of pitting corrosion is accompanied by a sudden

Figure 10. Mass loss of rebar as a function of chloride content close to
rebar in concrete made with a 30% fly ash cement and evaluation of
the chloride threshold (defined in this case as the chloride content that
led to a rebar mass loss higher than 0.1% after 4 years of exposure in
the tidal zone) [18]
variation in electrochemical parameters, in particular, a decrease
of the free corrosion potential and an increase of the corrosion
rate of steel [20, 21]. Monitoring these parameters, therefore,
allows to detect the onset of corrosion and, once corrosion has

Table 2. Experimental results from cathodic prevention tests [19]. Current density is referred to steel surface. Corroded area and maximum attack
penetration were evaluated after 5 years of tests

Cathodic current Steel potential Corroded Max attack Chloride content

density (mA/m2) (mV/SCE) area (%) penetration (mm) (% cement mass)

–
100/
200 2.5 1.5 0.73a

0.4
200/
300 0.7 1 1.52a
0.8
300/
450 0.7 0.8 1.49a
1.7
300/
700 0 – 2.38b
4.2
500/
900 0 – 3.46b
a
at the moment of corrosion initiation;
b
maximum value in time.

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614 Bertolini and Redaelli
initiated, prompt analysis of chloride content in the concrete close
to steel surface provides a measure of the chloride threshold. The
measurement of corrosion rate of steel in concrete is usually
based on the linear polarisation method [22] that was applied to
steel in concrete since the eighties [23] and then became one of
the routine laboratory methods to detect steel depassivation. It
should be noted that the linear polarisation method gives an
average value of the corrosion rate, therefore the corrosion rate
can be underestimated if the attack is strongly localised, as in the
case of pitting corrosion.
Measurements of corrosion potential and corrosion rate can
also be used to evaluate the effectiveness of preventative or repair
techniques, such as corrosion inhibitors [24, 25] or corrosion
resistant reinforcement [26], in delaying the onset of corrosion.
However, they cannot be used in the case of steel subjected to
electrochemical repair or preventative techniques, such as
cathodic protection or cathodic prevention, and care should also
be taken in the interpretation of results following the application
of temporary electrochemical techniques, such as electrochemical
chloride removal and realkalisation [27].
When corrosion rate or corrosion potential are monitored, to
detect depassivation due to pitting, threshold values should be
defined. The choice of these threshold values is often based on
experience, and introduces an element of subjectivity in the
determination of the chloride threshold. For corrosion rate
measurements, the threshold is usually fixed between 1 and 2
mA/m2 of corrosion current density (i.e. about 1–2 mm/year of
average corrosion penetration). As far as potential monitoring is
concerned, depassivation is usually detected when the corrosion
potential sharply decreases to values well below
200 mV/SCE.
Figure 11 shows, as an example, the results of a research
aimed at investigating corrosion potential and corrosion rate in
Figure 11. Relationship between corrosion current density and chloride
content in specimens of concretes with 10% silica fume and evaluation
of Clth (defined in this case as the chloride content that led to a
corrosion current density in the range 1–2 mA/m2 during polarisation
resistance tests on well compacted and wet specimens, conditioned at
temperatures of 20–50 8C) [28]
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Materials and Corrosion 2009, 60, No. 8
self-compacting concretes with 10% silica fume cement, with
amounts of added chlorides up to 2%, in different conditions of
exposure. The dashed lines defined the upper limit of the
corrosion current density considering results of tests on different
types of bars and surface treatments. In this case, a chloride
threshold was conventionally defined as the range in the chloride
content where the corrosion rate measured on the dashed
line passed from values lower than 1 mA/m2 to values higher than
2 mA/m2, by considering the corrosion rates measured on
specimens exposed to temperature values ranging from 20 to
508C. Estimated values of chloride threshold were around 0.6–
1.2% by mass of binder for concrete with portland cement and
1.1–2% for concrete with 10% silica fume [28]. However, the
threshold values were affected by the experimental details, since
the considered specimens were kept under moist conditions (so
that the corrosion potential had relatively low values), and the
amount of air voids at the steel concrete interface was minimised
owing to the use of self-compacting concrete and to the care taken
in the preparation of the specimens. In real structures under real
exposure conditions, the actual values of the chloride threshold
may be lower. This example shows that even results of tests in
concrete should be carefully interpreted before extrapolating
values to be used in the design of real structures.
4.3 Potentiostatic polarisation tests
Potentiostatic polarisation tests in concrete rely on the same
procedures as in solution (see section 3.2), with the difference
that in this case, the reference electrode has to be embedded
inside the specimen as close as possible to the steel bar in order to
reduce the ohmic contributions due to the applied current. This
type of test allows the evaluation of the influence of steel potential
on the chloride threshold, which is believed to be a critical factor,
as shown in Fig. 3.
Potentiostatic polarisation tests have been used to detect
corrosion initiation in specimens with given chloride contents
increasing progressively, but step-wise and slowly (e.g. 100 mV
every day [26]), the value of the applied potential.
Potentiostatic polarisation tests have also been proposed to
evaluate the chloride threshold in the initial chloride-free mortar
specimens, in which chloride penetration was promoted up to the
rebar depth by a relatively high value of water/cement ratio and
low concrete cover [29, 30]. This allowed to investigate the
dependence of chloride thresholds with steel potential in a similar
way as in solution tests, with a relatively short duration (10–
30 days) during which the polarisation effects on the steel/mortar
interface can be neglected. For instance, results shown in Fig. 12
were obtained by polarising the steel bar from þ250 to
650 mV/
SCE (with steps of 100 mV) and measuring the free chloride
content in the mortar at corrosion initiation: for potential values
higher than
200 mV/SCE the chloride threshold was constant,
around 0.5% by cement mass, while for lower potential values the
chloride content increased linearly. These results confirmed the
trend shown in Fig. 3. These data could be useful to find a
correlation between Clth and the moisture content of concrete,
which determines the corrosion potential of passive steel (in the
absence of external polarisation).
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Materials and Corrosion 2009, 60, No. 8
Figure 12. Relationship between potential and chloride threshold
(measured as % by mass of free chlorides) found with potentiostatic
polarisation tests [29]
4.4 Macrocell tests
Macrocell tests are based on the measurement of a galvanic
current (Imacro) circulating between two electrodes, one of which
behaves as anode and the other as cathode. This measurement
can be used to detect steel depassivation: when pitting corrosion
initiates on an electrode, the current exchanged with an electrode
in passive conditions increases due to the potential decrease
associated with pitting corrosion that generates a driving voltage
between the two (i.e. a difference in the corrosion potentials Ecor,1
and Ecor,2), as it has been sketched in Fig. 13. The two electrodes
should be close to each other in order to reduce the ohmic drop
and to maximise the macrocell current. Devices based on the
measurement of macrocell currents have been proposed to detect
the penetration of chlorides in concrete: different electrodes are
placed in the concrete cover at increasing depths and when, as a
consequence of chloride penetration, corrosion initiates on the
most external electrode, a macrocell current is detected between
the electrode and a passive electrode (anode-ladder system [31]).
Figure 14 shows an example of the macrocell current measured
between a steel anode and a stainless steel cathode following
chloride penetration in the 5 mm cover of specimens made with
two different concretes, one with water/cement ratio of 0.7 and
another with w/c of 0.6. In the more porous concrete, where
chloride penetration occurred easily, the steel anode underwent
corrosion initiation as indicated by the increase of the macrocell
current, from negligible values to values of about 20 mA [31].
Although this device does not allow an independent quantifica-
tion of the chloride threshold, it allows to detect or estimate the
Figure 13. Schematic representation of a macrocell between an actively corroding rebar and a passive rebar
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Detection of steel reinforcement depassivation 615
time for depassivation of steel reinforcement in a non-destructive
way. It can be used on real structures within an effective
maintenance management of concrete structures, subject to
chloride bearing environments.
Figure 13 shows that the measured macrocell current also
contains a cathodic contribution due to the cathodic reactions
occurring on both electrodes (active and passive), and, therefore,
cannot be interpreted as an anodic current on the active electrode.
So the value of Imacro cannot be used directly to quantify the
corrosion rate of the electrode where corrosion was initiated.
5 Final remarks
Nowadays, although the main factors affecting the chloride
threshold have been widely investigated and some of them are
well recognised, a quantification of chloride threshold values is
still often rather difficult, and this can be partly due to the
different experimental methods that have been used to determine
this parameter, both in the laboratory and on real structures.
Indeed, even though the recently developed design methods
for service life prediction of structures in chloride-bearing
environments require the knowledge of the chloride threshold for
pitting corrosion initiation, neither any standardised method nor
any generally accepted laboratory procedure is available for the
evaluation of the chloride threshold. In particular, in the context
of a probabilistic design method, such as the FIB Model code for
service life design [32], it would be useful to define a reliable
technique that allows a rapid evaluation of the chloride threshold,
as well as of its variability, in order to estimate a probability
distribution of Clth depending on the composition of concrete and
the exposure conditions.
All tests for the determination of chloride threshold rely on
the detection of steel depassivation, which can itself be
approached in different ways, the most frequently used of which
have been discussed in this paper.
In electrochemical tests in solutions simulating the concrete
pore liquid, such as potentiodynamic and potentiostatic polarisa-
tion tests, the current exchanged at the sample surface is
monitored and, when it increases sharply, steel depassivation is
detected, allowing the determination of either a pitting potential
value or a threshold chloride concentration. Tests in solutions
have been essential for a rapid evaluation of the resistance to
pitting corrosion, allowing a preliminary evaluation of the role of
the type of material, of environmental parameters and of the
effectiveness of preventative techniques (such as cathodic
prevention or corrosion inhibitors). However, they do not allow
an evaluation of the chloride threshold in concrete, since chloride
ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
616 Bertolini and Redaelli
Figure 14. Experimental results of macrocell current and detection of
corrosion initiation [31]
concentrations in solutions cannot be directly converted to
chloride contents in concrete, and, moreover, they may not be
representative of the real conditions of a reinforcing bar in
concrete.
Compared to tests in solutions, tests in concrete are more
time consuming, since they require casting and curing of
specimens and chloride analyses of concretes close to steel when
depassivation occurs, and also because the involved phenomena
require longer durations to take place (penetration of chlorides in
concrete and changes at the steel/concrete interface). However,
tests in concrete are more representative of real conditions, in
particular, in considering the role of the steel-concrete interface.
In tests in concrete steel depassivation is rarely determined
by direct visual observation of the surface of the reinforcement.
More often, it is detected with electrochemical (non-destructive)
methods, such as monitoring corrosion potential and corrosion
rate.
The determination of chloride threshold is carried out either
by measuring the chloride content when steel depassivation is
detected by corrosion rate and/or potential monitoring in initial
chloride free specimens subjected to chloride penetration, or by
comparing corrosion rates of specimens with different amounts
of mixed-in chlorides. Potentiostatic polarisation tests have also
been suggested to measure the chloride threshold as a function of
steel potential. Although these tests can only be carried out in
samples of porous mortar with low cover to steel, in order to allow
chloride penetration during the polarisation test itself, they allow
to plot the correlation between the steel potential and the chloride
threshold, and thus could be used to correlate Clth to changes in
the moisture content of concrete.
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(Received: February 12, 2009) W5276
(Accepted: February 25, 2009)
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