Received: 5 April 2019 | Accepted: 25 April 2019

DOI: 10.1002/maco.201910962

ARTICLE

Quantification of Tafel coefficients according to passive/active

state of steel carbonation‐induced corrosion in concrete

Frédéric Duprat1 | Thomas de Larrard1 | Ngoc Tru Vu2

1
LMDC, Université de Toulouse,
Toulouse, France
2
Faculty of Bridge and Roads, National
University of Civil Engineering, Hanoï,
Vietnam
Correspondence
Frédéric Duprat, LMDC, Université de
Toulouse, INSA/UPS, 135 avenue de
Rangueil, Toulouse, F31077 Cedex,
France.
Email: frederic.duprat@insa-toulouse.fr
Statistical quantification of Tafel coefficients is investigated in this study for
isolated steel rebar embedded in concrete. The survey is supported by a wide
experimental campaign carried out earlier to characterize the passive and active
states of carbonation‐induced corrosion of steel. Electrochemical measurements
(polarization resistance, corrosion potential, Tafel coefficients) and gravimetric
estimations of iron loss were regularly conducted over 417 days on 108 concrete
specimens. The statistical analysis reveals that the mean value of Tafel
coefficients, both cathodic and anodic, is higher under active corrosion, which
seems to contradict the general tendency found for chloride‐induced corrosion,
while their coefficient of variation is smaller. The statistical inference was based
on the first step of distributions fitting the experimental data and then on the
second step of goodness‐of‐fit tests. The most suitable of the distributions
proposed were the Burr, Rayleigh, and Gamma distributions. A similar analysis
was made for the corrosion potential and polarization resistance. The findings
of the study will be valuable for probabilistic approaches to corrosion where
probabilistic distributions are required.

KEYWORDS
carbonation‐induced corrosion, concrete, statistical analysis, Tafel slopes

1 | INTRODUCTION with the conservation of electrical charge according to

Due to its crucial importance regarding the durability of
reinforced and prestressed concrete structures exposed to
carbonation, the corrosion of embedded steel reinforce-
ments has become of great interest and is the subject of
much research from both the experimental and modeling
points of view. Two main approaches can be distin-
guished for modeling the propagation of corrosion. The
first is based on the assumption that the corrosion
kinetics is governed by the amount of oxygen at the
cathode. The reduction of oxygen at the surface of
the sound steel sustains the corrosion current, which can
be calculated from the consumed oxygen flow.[1–4] The
second approach is supported by Ohm’s law together
Laplace's law and Butler–Volmer's equations as electrical
boundary conditions at the steel surface.[5–7] The reduc-
tion of oxygen at the cathode is also taken into account by
the limiting corrosion current density at the cathode.[8–10]
Finally, some authors have proposed to combine these
approaches by taking account of the oxygen flow at both
cathode and anode.[11,12] Otieno et al.[13] presented a
critical review of some of these models and recom-
mended, among other needed developments, to account
for the variability of the parameters influencing the
corrosion current thanks to a probabilistic approach,
from the moment that adequate data is available.
Tafel constants occur in Butler–Volmer equations,
governing the polarization of steel and impacting the

Materials and Corrosion. 2019;1–30. www.matcorr.com © 2019 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim | 1
2 |
corrosion kinetics. They are hence significant input
parameters in the models based on the second approach
and in further numerical prediction of the corrosion
process in reinforced concrete structures. Ge et al,[14] for
instance, pointed out from a parametric study that the
cathodic Tafel slope was one of the parameters having
the most influence on the corrosion rate. Four main
regions for the values of Tafel constants have been
described by Song[15] as follows:
● Moderate values of both anodic βa and cathodic βc
Tafel slopes: Steel is in an active state, oxygen
diffusion does not control the corrosion reaction
and the pH value is below 9. Typical expected
ranges would be (in mV/dec) 13 ≤ βa ≤ 17 and
21 ≤ βc ≤ 65.
● A moderate value of the anodic Tafel slope and a high
value of the cathodic one: Steel is in an active state
and the cathodic reaction is under oxygen diffusion
control. Typical expected ranges would be (in mV/
dec) 13 ≤ βa ≤ 17 and βc → ∞.
● A moderate value of the cathodic Tafel slope and high
value of the anodic one: Steel is in a passive state and
the supply of oxygen is sufficient. Typical expected
ranges would be (in mV/dec) βa → ∞ and
21 ≤ βc ≤ 52.
● High values of both cathodic and anodic Tafel slopes:
Steel is in a passive state and the cathodic reaction is
under oxygen diffusion control. Typical expected
ranges would be βa → ∞ and βc → ∞.
Numerous values of Tafel constants are collected and
reported in.[9,10,16] Many of them were proposed in a
modeling framework and none of them was the outcome
of an experimental investigation devoted to carbonation‐
induced corrosion. It is nevertheless interesting to recall
some prominent features that were observed. Experi-
mental values of Tafel slopes obtained on supposed
actively corroding samples, according to the various
studies cited and adding the results of the authors
themselves, may vary from 10 to 1,215 mV/dec for the
cathodic Tafel constant and from to 10 to 1,570 mV/dec
for the anodic Tafel constant. These ranges do not match
the theoretical ones given by Song[15] and are somewhat
more widely spread. Various experimental procedures
were applied to initiate and/or accelerate corrosion
(additional chlorides in mortar or concrete mix or
exposure to sea water, imposed anodic current), and
the steel rebars were embedded in different media
(synthetic pore solution, mortar or concrete). Mortar or
concrete was batched with various cementitious mixes
based on ordinary or blended cement, with various
water/binder ratios. Some specimens were intentionally
DUPRAT ET AL.
precracked or cracked during the development of
corrosion. According to Michel et al,[10] these diverse
experimental factors or situations contribute to the width
of ranges of Tafel constants proposed in the literature.
Other factors affecting the Tafel slopes can be encoun-
tered in the phenomenon of corrosion itself, as men-
tioned by Babaee and Castel[17] from previous studies:
Conductivity, pH and ionic composition of the electro-
lyte, polarization mechanism, corrosion potential, surface
film of mill scale covering the surface of the reinforce-
ment. It would likely be valuable to classify the data
according to these factors so as to derive average
tendencies and specific possible ranges of Tafel constants,
but this would also artificially reduce their variability and
limit their use in modeling when these factors are not
known in advance. Unavoidable uncertainties resulting
from the electrochemical measurements, the assessment
of Tafel constants from these (within the framework of
modeling assumptions), and also the random nature of
the phenomena involved are indeed also responsible for
such a variation in Tafel constants. Hence the notion of
Tafel coefficients rather than Tafel constants should be
introduced, given that these parameters are essentially
randomly variable.
Among the various experimental investigations men-
tioned above, the effective active or passive state of steel
has received little attention. Most of the time it has been
assumed that steel is in the active state. However, in real
concrete structures, the corrosion process generally
involves both passive and active zones of the embedded
reinforcing steel cage. When modeling the corrosion
phenomenon at the structural scale, it is thus necessary
for Tafel coefficients to be supplied for both the passive
and active state.[6] It has to be mentioned that, in some
recent investigations,[16,17] passive and active states of
corrosion were addressed and the experimentally obtained
values of Tafel coefficients were attributed accordingly to
one state or the other. These studies mainly focused on
characterizing the chloride‐induced corrosion of steel
reinforcement for nonusual concretes like low‐calcium
fly ash‐based geopolymer concrete[17] or hybrid fiber‐
reinforced concrete.[16] Cathodic Tafel slopes obtained by
Babaee and Castel[17] varied from 30 to 45 mV/dec for
passive samples and from 106 to 221 mV/dec for active
samples, and the anodic Tafel slope exhibited an infinite
value for passive samples, while it varied from 514 to
1,107 mV/dec for active samples with, again, a possible
trend to infinity. Nguyen et al.[16] did not state the
amplitude of variation of their Tafel slopes and mentioned
only the mean values. From Figure 10 in their paper, it
can be estimated that the cathodic Tafel slope ranged from
2 to 60 mV/dec for passive samples, and from 80 to
125 mV/dec for active samples, whereas anodic Tafel slope
DUPRAT ET AL. | 3

FIGURE 1 Layout of concrete

specimens. Reproduced with
permission,[19] (Copyright 2013, Taylor &
Francis)

ranged from 200 to 1,000 mV/dec for passive samples and 2 | EXPERIMENTAL
from 150 to 205 mV/dec for active samples, except for one INVESTIGATION
point at 600 mV/dec.
In a recent critical review on corrosion rate in The experimental investigation aimed to analyze the
carbonated concrete, Stefanoni et al.[18] identified sys- conditions of effective onset of carbonation‐induced
tematic data collection as being one of the upcoming corrosion for small steel rebar embedded in concrete at
research needs. Such recording of electrical resistivity, controlled cover depth.[19] For the sake of clarity, the
corrosion potential and corrosion rate of the steel, and main features are recalled here. Concrete specimens of
also oxygen diffusion and consumption rate, together dimensions 14 × 12 × 12 cm3 (Figure 1) were cast with
with concrete properties like porosity, would allow the three concrete mixes comprising cement CEM I,
mechanism of steel corrosion (another very notable CEM II or CEM III (Table 1). The steel rebar (usual
research need) to be studied with more insight. Surpris- commercial carbon steel) was laid out by means of PVC
ingly, Tafel slopes do not appear in the data to be tubes fixed on the mold. Before being installed in the
collected, even though they are needed as input mold, each rebar was brushed to eliminate preformed
parameters of models as mentioned above. It is ques- corrosion products, which could have modified the
tionable whether Tafel slopes already obtained in the case gravimetric iron mass loss measured at the end of the
of chloride‐induced corrosion, results undoubtedly test, and then weighed.
known by the authors, would be suitable in the case of After demolding, specimens were wet cured for 7
carbonation‐induced corrosion, because chloride ions act days, stored in the laboratory atmosphere for 1 day, and
beyond the depassivation phase by reducing the concrete then dried at 80°C until an average saturation degree of
resistivity to a certain extent and contributing to the 45% was reached for each specimen. Then 90 specimens
newly formed oxides in the course of corrosion propaga- were placed in an accelerated carbonation chamber
tion, which can modify the polarization behavior of the (labels D15C and D30C) with a dioxide carbon partial
steel.[17] pressure equal to 50% at 20°C whereas 18 specimens
The main goal of the present study is to estimate, remained unexposed (label D15NC). The duration in the
collect, and analyze the Tafel coefficients obtained in the carbonation chamber was adjusted so that the probability
case of reinforced concrete exposed to carbonation. of the cover being fully carbonated was 95% for D15C
Concrete mixes were prepared with three types of specimens and 50% for D30C specimens. The lateral faces
cement, and two cases of cover depth combined with of specimens were coated with epoxy resin to prevent the
precarbonation phases and three exposure conditions
were considered, so as to cover realistic onsite situations
T A B L E 1 Mix proportions
of concrete structures. Electrochemical measurements of
corrosion potential and polarization resistance were Concrete designation
Constituents/
made at different levels of corrosion and Tafel coefficients
properties CI CII CIII
were derived from them. One hundred and eight concrete
probes, each containing small steel rebar, were cast. Type of CEM I CEM II CEM III
Statistics of Tafel coefficients were established consider- cement Unit 52.5R 32.5N 52.5N
ing the passive or active state of the steel. Cement kg/m3 295 430 355
The present study contributes to fairly rich knowledge Sand kg/m3 989 760 957
of Tafel coefficients and its results can be fruitfully Gravel kg/m 3
792 912 765
incorporated and used in advanced modeling of Water L/m3 200 210 199
corrosion.
4 |
ingress of carbon dioxide and to impose uniaxial
carbonation through the controlled cover depth. Three
exposure conditions were then applied to specimens for a
maximum duration of 417 days as follows:
– Similar to XC1 exposure class of EN 206: Specimens
were left in a 10 mm water layer immersing the side
opposite to the cover, in fairly constant conditions of
relative humidity and temperature, leading to a
saturation degree of about 85% in the neighborhood
of the reinforcement.
– Similar to XC4 exposure class of EN 206: The
specimens were subjected to alternating dry (5 days
at RH = 60%, T = 40°C), and wet (2 days at RH =
100%, T = 20°C) periods.
– Natural outdoor exposure conditions (exposed con-
crete surface was vertical and unsheltered).
The flowchart of the experimental campaign can be
seen in Figure 2.
Electrochemical measurements were made by means of
a Gamry System G300, between 83 and 417 days of
exposure, so as to observe various levels of corrosion. A
three‐electrode system was used, comprising a saturated
calomel reference electrode (SCE), a titanium mesh as
counter electrode, both installed on the upper concrete
surface over the rebar (see Figure 1), and the rebar as
working electrode (WE). Measurements were made from
the surface of concrete on the face corresponding to the
controlled cover. The linear polarization resistance (LPR)
method allowed the polarization resistance, Rp, to be
measured providing that the open circuit corrosion
potential Ecorr , corresponding to the stabilized half‐cell
potential in an open circuit measurement, was obtained
beforehand. In LPR, the potential sweep was +/–10 mV
with respect to the corrosion potential at a rate of 0.1 mV/s.
IR compensation based on current interruption was
applied during the test to dynamically correct the
uncompensated electrolyte resistance. The cyclic polariza-
tion test (CPT), with an amplitude of polarization up to
+/–250 mV with respect to the corrosion potential, served
to determine the Tafel coefficients thanks to a curve fitting
procedure. With such a potential sweep, it was possible
that the electrochemical system of the WE might undergo
FIGURE 2 Flowchart of experiments for CI concrete – DxC: x mm cover depth carbonated. (Reproduced with permission,[19] Copyright
2013, Taylor & Francis)
DUPRAT ET AL.
irreversible destruction. The CPT was therefore the last
electrochemical test carried out on specimens and each
pair of Tafel coefficients corresponded to a single specimen
at the end of its testing. This may be deemed as a drawback
of our protocol since it did not enable the change of
corrosion state to be registered and observed for the same
specimen. In a recent study, Nguyen et al. [16] applied a
smaller potential sweep of +/–75 mV in a CPT so as to limit
possible damage after the test and reuse the same specimen,
while maintaining a sweep large enough for the Tafel
coefficients to be extracted. However, those authors did not
compare the resulting Tafel coefficients to those that would
have been obtained under a wider potential sweep to
support their protocol. Babaee and Castel [17] argued that
conducting CPT with overpotential of +/–200 mV three to
five times on the same sample was possible without causing
dramatic deterioration of the electrochemical system. The
current and polarization resistance provided through the
experimental campaign is given by the measuring devices
respectively in A and Ω, and not in A/m2 or Ω/m2 which
are the units usually used, because the effective polarized
area of the rebar is not accurately known. The maximum
polarized area can be taken equal to the contact area
between the rebar and bulk concrete (7.54 cm2).
The amount of iron lost was also found by weighing
the extracted rebar after the electrochemical tests. Mass
loss measurement was performed according to the ASTM
G1‐90 protocol.[20]
3 | ASSESSMENT OF THE TAFEL
COEF FICIE NTS
The electrochemical corrosion cell can basically be seen
as an equivalent electrical circuit comprising three serial
resistance terms R a , R c , and Rcon [21,22] that are part of
the global resistance R cell .
R cell = R a + R c + R con (1)
R a and R c refer to the charge transfer process of the
anodic and cathodic reactions, respectively, while R con
refers to the flow ions through the concrete electrolyte. The
driving cell voltage Ucell is defined as the difference between
DUPRAT ET AL. | 5

the reversible equilibrium potentials of the cathodic (Ec,0 )
and anodic (Ea,0 ) reactions, and is increased by the effective
ohmic drop over the concrete electrolyte (Ucon ).
Ucell = Ec,0 − Ea,0 + Ucon. (2)
are randomly dispersed on the steel surface, the ohmic
drop can be considered negligible because no current
flows through the concrete bulk (Ucon ≈ 0). At free
corrosion potential, anodic and cathodic net currents
are balanced and the corrosion current is

The reversible potentials are expressed as i corr = ia = −ic. (7)

0
ln(10) RT Under the assumption of a microcell corrosion system,
Ea,0 = EFe 2+ / Fe + log (Ksp)
2F the Tafel coefficients can be assessed by fitting the
ln(10) RT experimental polarization curve of the steel. Once Ecorr
+ (14 − pH ) (3)
F and Rp have been acquired, assuming a pair of Tafel
coefficients, the corrosion current is expressed as
and
i corr = B / Rp (8)
ln (10) RT
Ec,0 = EO02 / OH−
+ log(pO2 )
4F where B is the Stearn–Geary coefficient.
ln(10) RT
+ (14 − pH ) (4)
F βa βc
B= . (9)
ln (10) (βa + βc )
where Ksp is the dissolution constant of ferrous hydroxide
(Ksp = 7.94 × 10−16), pO2 is the partial pressure of
dioxygen (pO2 = 0.21), F is the Faraday constant The exchange currents hold
(F = 96485 C ), and R is the perfect gas constant
(R = 8.314 J / K ). With respect to the SCE, i corr
ia,0 = (10)
0
reference potentials are EFe 2+/ Fe = − 687 mV and exp (ln(10) ηa / βa)
EO02 / OH− = + 154 mV .
If polarization is applied to the cell, the potential of and
each reaction shifts to a polarized potential. As both
reactions occur inside the same corrosion cell, the steel i corr
ic,0 = (11)
reinforcement potential, Ecorr takes an intermediate value exp ( −ln(10) ηc / βc )
between the two equilibrium potentials, resulting in the
activation overpotentials ηa = Ecorr − Ea,0 and Experimental and modeled polarization curves ob-
ηc = Ecorr − Ec,0 . If electrode reactions are assumed to tained from the fitting procedure are plotted in Figure 3
be governed by the activation energy of the charge for a specimen taken from the experimental campaign
transfer, the net current density is expressed by the mentioned above. The data reported in Figure 3 were
Butler–Volmer equation for each reaction. derived from Equations (3–11), except Rp and Ecorr , which
were measured previously. It can be seen that experi-
⎛ η ⎞ mental and modeled curves almost overlap each other.
ia = ia,0 exp ⎜ln(10) a ⎟ (5) Conversely, when anodic and cathodic areas are
⎝ βa ⎠
remote due to local differences in the electrochemical
state of the steel, galvanic corrosion takes place in a
and
corrosion macrocell, and the ohmic drop can no longer
be ignored. Because of the network of electrically
⎛ η⎞
ic = −ic,0 exp ⎜ −ln(10) c ⎟ (6) connected reinforcing steel bars and the inhomogeneous
⎝ βc ⎠ condition states of both concrete and steel (due to
concrete moisture, pH of the pore solution, quality of
where ia,0 and ic,0 are the exchange current densities, and the steel‐concrete interface, dioxygen content, cover
βa and βc are the Tafel coefficients. depth, cracking, etc.) macrocell and microcell systems
The importance of the ohmic drop depends on the are combined in concrete structures most of the time, in a
type of corrosion cell. In the case of uniform corrosion general macrocell system where electrical coupling exists
where microscopic adjacent anodic and cathodic areas between active and passive uniform corrosion systems,
6 |
FIGURE 3 Polarization curve of the steel (specimen 629)
which are mutually polarized.[6,23] Anodic and cathodic
polarizations are possible for each active or passive area
but, because of the difference between the corrosion
potentials (Ecorr, A in active area is much lower than Ecorr, P
in passive area) the active area undergoes anodic
polarization while the passive area undergoes cathodic
polarization. The steel equilibrium potentials for each
area (EP for the passive area and EA for the active area)
are such that the macrocell current intensity im remains
the same under cathodic or anodic polarization.
Ucon = im R con = EP − EA.
As polarized steel surfaces generally have various
extents, anodic and cathodic net currents are no longer
balanced. According to Laurens et al.,[6] the corrosion
current can be expressed as
jcorr = im / AA + i micro/ AA = jm + jmicro
where AA is the extent of the active area and i micro is the
residual microcell current intensity. Butler–Volmer
equations apply for each area
jA = jm = jcorr, A [exp (ln(10) ηA / βa, A)
− exp ( −ln(10) ηA / βc, A) ]
and
DUPRAT ET AL.
jP = jcorr, P [exp (ln(10) ηP / βa, P ) − exp ( −ln(10) ηP / βc, P ) ]
(15)
where
ηA = EA − Ecorr, A (16)
and
ηP = EP − Ecorr, P (17)
(12)
The residual microcell current results from the
difference between the total anodic current and the net
anodic current.[6]
The Tafel coefficients introduced in Equations (14)
and (15) relate to the passive or active state of the steel. It
is not straightforward to assess the effect of the ohmic
drop from a CPT, because the steel gives a global
(13) response to the polarization. The classical representation
of a polarization curve shown in Figure 3 thus remains
the same whatever the state of the steel and, if no change
occurs except that the state of the steel shifts from passive
to active, the corrosion point is expected to be localized in
a more anodic region (decrease of Ecorr and increase of
i corr ) which could correspond to a decrease of the anodic
Tafel coefficient, whereas the cathodic Tafel coefficient
(14)
varies only slightly. This is illustrated in Figure 4 for two
probes of the experimental campaign. The translation of
the corrosion point towards the anodic region from the
DUPRAT ET AL.
FIGURE 4 Polarization curves. A: Active steel (specimen 505), P: passive steel (specimen 521)
passive state (P) to the active state (A) is clearly visible.
The change in the Tafel coefficients also complies with
the generally expected trend. This motion from point P to
point A was also shown in the case of chloride‐induced
corrosion,[16] in a more pronounced manner regarding
the deviation in the corrosion current and corrosion
potential between the passive and active state. As far as
the fitting procedure is concerned, it can be seen that
there is a slight discrepancy between the modeled
polarization curve and the experimental one in the case
of the active state (A) compared to the passive state (P),
where the modeled curve is, on the contrary, very close to
the experimental one. Such an observation is not
systematic and the quality of the fitting generally does
not depend on the steel state, providing that the extent of
the experimental region experiencing the Tafel electro-
chemical behavior of steel is large enough. Chang
et al.[23] reported that the passive film of oxide formed
around the rebar could have a nonnegligible effect on the
corrosion process and makes the polarization curve
deviate from its theoretical shape given by Equation
(15). Similarly, the growth of the layer of corrosion
products, together with the various oxides formed during
the corrosion process, may affect the polarization
behavior of steel and consequently the values of the
Tafel coefficients.[24] In the present study, the maximum
exposure time of the concrete specimens to natural (not
accelerated) conditions of corrosion was 417 days. The
corrosion layer was thus very thin at the end of this time
| 7
and it can be judged that case (A) in Figure 4 is a fairly
good example of the maximum deviation that was
observed in this study between modeled and experi-
mental polarization curves and, in most cases, this
deviation remains acceptable.
Fitting the steel polarization curve is a usual and
convenient way to estimate the Tafel coefficients,[23] but
other electrochemical results can also be used, in
combination with modeling. In Michel et al.[10] the
experimental corrosion current i corr , derived from the
polarization resistance, and corrosion potential Ecorr were
targeted in a fitting procedure where comprehensive
finite element modeling of the experiment was proposed.
Tafel coefficients were adjusted so that the computed
values of i corr and Ecorr matched experimental values. In
this study i corr was estimated by Equation (8) with the
Stearn–Geary coefficient B = 26 mV while the value of B
calculated according to Equation (9) with the adjusted
Tafel coefficients varied from 2.2 to 30.9 mV. There is
hence a slight divergence and final results do not concord
perfectly with the initial assumption. In our case, no
additional assumption was needed before the fitting
procedure. Jiang et al.[24] proposed estimating the sum
β = βa + βc from experimental results of i corr versus time
for three different concrete mixes. An analytical model of
i corr was developed, accounting for the electrical resistiv-
ity of the concrete and the W/C ratio, under the following
assumptions: Microcell corrosion system with equal
activated anodic and cathodic surfaces, and equal degrees
8 |
of corrosion control by both the anode and the cathode,
implying that λ a = λ c ≈ 0.5, where λ a = βa/ (βa + βc ) and
λ c = βc / (βa + βc ). These assumptions are not very well
suited to our case and particularly the latter as the mean
values of λ a and λ c are 0.67 and 0.33, respectively.
4 | DISTINCTION B ETWEEN
A C T I V E A N D PA S S I V E C O R R O S I O N
STATES
As mentioned earlier, it is necessary to use consistent
values of Tafel coefficients for the active and passive
states of the steel when the aim is to model the overall
phenomenon of corrosion in concrete structures where
macrocell systems have developed. Looking at the shape
of the steel polarization curves obtained by a CPT is not
totally suitable for this purpose as it remains similar
whatever the state of the steel (passive or active). Criteria
other than this shape, based on electrochemical proper-
ties likely to change depending on the steel state, must
then be resorted to to properly distinguish the passive
from the active state. The link between the electrochemi-
cal properties of steel not coated in concrete and corrosion
activation has been under investigation for several decades
and recommendations have been proposed for testing and
interpreting measurements.[25–27] Half‐cell potential (cor-
rosion potential), corrosion rate, concrete resistivity, and
polarization resistance are the main properties usually
estimated to characterize the corrosion activation. The use
of the gradient of corrosion potential rather than its
absolute value is also recommended by Elsener et al. [28]
for detecting the corrosion spot location in dense
reinforcement grids. Nevertheless, the random nature of
the phenomenon, together with experimental uncertain-
ties, hinders any deterministic decision on the steel state
from the values of electrochemical properties. Recommen-
dations proposed in the literature hence mention a level of
corrosion risk or corrosion probability as proposed in
ASTM C876‐09 [25] and Vennesland et al.[27] Some of them
are reported in Table 2.
T A B L E 2 Corrosion risk according to corrosion parameters
RILEM[27]
Net corrosion current Yearly corrosion rate Concrete resistivity
jcorr (μA/cm2) Vcorr (mm/y) ρcon (kΩ.m)
<0.1 <0.001 >100
0.1–0.5 0.001–0.005 50–100
0.5–1 0.005–0.01 10–50
<1 >0.01 <10
Abbreviation: SCE: saturated calomel reference electrode.
DUPRAT ET AL.
Nguyen et al.[16] classified their samples with respect to
the corrosion potential as passive when Ecorr > −100 mV/
SCE and active when Ecorr < −300 mV/SCE. However,
the use of half‐cell potential (corrosion potential) as a good
indicator of corrosion activity has recently been criti-
cized[29] in the case where a macrosystem of corrosion can
occur, for instance, in a grid of interconnected rebars.
Published recommendations have mostly been based on
experimental investigations involving a single steel bar.
Sassine et al.[29] pointed out that a corrosion potential
higher than –128 mV/SCE could be due either to a
complete passive steel reinforcement or to corrosion onset
associated with a macrocell system having a large cathode‐
to‐anode surface ratio, resulting in high corrosion kinetics.
In contrast, a low corrosion potential may be associated
with a macrocell system having a small cathode‐to‐anode
surface ratio, resulting in slow corrosion kinetics. A
realistic reinforcement layout was used in this study,
which allowed rebars to be isolated or connected.
Moreover, electrochemical properties indicate an
instantaneous state of corrosion at the time when the
test is performed whereas the effective state of corrosion
results from an additive process where favorable condi-
tions must be brought together (depassivation, moisture,
presence of oxygen at the cathode). From this viewpoint,
the iron mass loss would provide consistent evidence of
corrosion activity if measured over a given time in
conjunction with electrochemical properties. Unfortu-
nately, its measurement is rather complex and laborious, and
it thus be performed only under laboratory conditions.
Derived from the concepts of probability of detection and
probability of false alarm an approach was proposed
assessing the probabilities of right or wrong alarm to
establish a correlation between the effective state of
corrosion, measured by the iron mass loss, the polarization
resistance Rp and/or corrosion potential Ecorr .[19] Thanks to
this approach, threshold values for these electrochemical
properties were suggested so that the probability of a right
alarm (PRA) was maximum, allowing the effective onset of
corrosion to be identified with a minimum probability of a
wrong alarm (PWA). For example, according to Rp,
ASTM[25]
Half‐cell potential
Ecorr (mV/SCE) Corrosion risk
>–128 Negligible
Low (uncertain)
Moderate (uncertain)
<–278 High
DUPRAT ET AL. | 9

T A B L E 3 Threshold values of electrochemical properties The surface density of iron mass loss in Table 3 was
determined under the assumption that the total interface
Reference properties for
area between steel and concrete (7.54 cm2) was uniformly
estimating PRA and PWA
corroded, which visual inspection proved was obviously
Rp Ecorr Rp , Ecorr not the case for many specimens once the embedded
Rp, th (Ω) 5,500 8,250
rebar was extracted from the concrete. Nevertheless,
because no measurement of the area of rusted zones was
Ecorr, th (mV/SCE) –365 –365
envisaged, the aforementioned assumption was adopted.
∆m iron, th (mg/cm2) 10.61 9.95 9.95 In the present study, several criteria were taken into
PRA 0.755 0.815 0.796 account to decide whether an experimental set of Tafel
95% confidence interval [0.631; [0.615; [0.686; coefficients of a given specimen was to be attributed to a
0.878] 0.921] 0.906] passive or active state of corrosion. As none of these
PWA 0.254 0.256 0.218 criteria was expected to be fully consistent, due to the
95% confidence interval [0.196; [0.196; [0.162; lack of a direct link with the cumulative corrosion state,
0.313] 0.308] 0.274] they were used in a combined way. Various combina-
Abbreviations: PRA: probability of a right alarm; PWA: probability of a tions, as well as single criteria, reported in Table 4, were
wrong alarm; SCE: saturated calomel reference electrode. considered. The yearly corrosion rate Vcorr was estimated
from the iron mass loss and the corrosion current jcorr
PRA is the probability that Rp ≤ Rp, th knowing that was determined by Equation (8), accounting for a global
∆m iron ≥ ∆m iron, th . The latter condition can be seen as the polarization of the steel surface. The theoretical iron
effective onset event provided that iron mass loss is mass loss ∆mth,iron was estimated under the assumption
cumulatively determined and not expressed as a corrosion of a uniform loss over the rebar and a corrosion depth of
rate. The results obtained in Duprat and Vu[19] were 11.6 μm/year for a corrosion current of 1 μA/cm2. It was
completed in the present study by adding the second set of assumed that the theoretical corrosion onset time was the
data identified in the cited study by a principal component time needed for the carbon dioxide to reach the
analysis. They are reported in Table 3. It can be seen in this reinforcement according to the Hyvert carbonation
table that Ecorr, th (–365 mV/SCE) appears somewhat low model.[30] Carbonation times are reported in Table 5.
compared to the ASTM reference value in Table 2 for a high The efficiency and feasibility of using the proposed
probability of corrosion (–278 mV/SCE). Nonetheless, in the combinations to classify an experimental pair of Tafel
case of isolated rebar with an incipient corrosion spot, coefficients (as representing a passive or active state of
Sassine et al.[29] reported a similar value (–330 mV/SCE) steel) were judged with respect to the coherence that
obtained with the same experimental procedure, i.e. half‐ combined criteria showed with each other. So, the
potential measurement from the concrete surface. number Nc of cases where the same classification was

T A B L E 4 Criteria and combinations of corrosion state classification

Designation Comment Combination giving active state

C‐m‐E Iron mass loss and corrosion potential ∆m iron > 9.95 mg/cm2, Ecorr < –365 mV/SCE
C‐m‐R Iron mass loss and polarization resistance ∆m iron > 10.61 mg/cm2, Rp < 5,500 Ω
C‐E‐R Corrosion potential and polarization resistance Ecorr < –365 mV/SCE, Rp < 8,250 Ω
C‐m‐E‐R Iron mass loss, corrosion potential, and polarization ∆m iron > 9.95 mg/cm2, Ecorr < –365 mV/SCE, Rp < 8,250
resistance Ω
C‐m‐j Iron mass loss and corrosion current ∆m iron > 9.95 mg/cm2, jcorr > 0.1 µA/cm2
C‐m,th‐j Theoretical iron mass loss and corrosion current ∆m iron,th > 9.95 mg/cm2, jcorr > 0.1 µA/cm2
C‐m‐V Iron mass loss and yearly corrosion rate ∆m iron > 9.95 mg/cm2, Vcorr > 0.001 mm/y
C‐E‐R‐j Corrosion potential, polarization resistance, and corrosion Ecorr < –365 mV/SCE, Rp < 8,250 Ω, jcorr > 0.1 µA/cm2
current
C‐j‐V Corrosion current and yearly corrosion rate jcorr > 0.1 µA/cm2, Vcorr > 0.001 mm/y
C‐m‐j‐V Iron mass loss, corrosion current, and yearly corrosion rate ∆m iron > 9.95 mg/cm2, jcorr > 0.1 µA/cm2,
jcorr > 0.001 mm/y
Abbreviation: SCE: saturated calomel reference electrode.
10 | DUPRAT ET AL.

T A B L E 5 Accelerated carbonation time (d)
Cover depth, Cover depth,
Concrete mix 15 mm 30 mm
CEM I 15 62
CEM II 4 16
CEM III 10 43
established by each of the combined criteria, for a given
set of experimental data, over the total number of
experimental sets Nt was expressed as the frequency of
correct classification frc = Nc / Nt .
5 | R E S U L T S AN D A N A L Y S I S
5.1 | Classification of experimental sets
The efficiency of combined criteria expressed as the
frequency of correct classification is reported in Table 6 for
the various exposure conditions and concrete mixes. It can be
seen that the range of frequency of correct classification is
rather wide, from a minimum value of 0% to a maximum
value of 93%. For the same exposure condition, the difference
with respect to the concrete mix can reach almost 25% (XC1,
C‐E‐R‐j). There can also be a marked variation, of more than
29% according to the exposure condition, in the average
value of frc for the three concrete mixes (C‐m‐V). A relevant
combination of criteria for the classification of Tafel
coefficients would be likely to result in a reasonably high
value of frc together with a low variation according to the
concrete mix and exposure conditions. In this regard, C‐E‐R
would appear to be the best choice.
Further, it can be noted that combined criteria where
the corrosion current is involved are globally not
satisfactory. The threshold value of 0.1 μA/cm2 is,
however, recognized as being the transition point from
passive to active corrosion and is used for calibrating
impressed direct current in experimental investiga-
tions.[10] The assumptions of a charge transfer process
and uniform corrosion allowing Equation (8) and (9) to
be established are probably not fully realistic. Even at the
small scale of the specimen (rebar length is 2 cm) and
although the corrosion stage in question is at its very
onset, a macrocell corrosion system seems to take place,
implying that Equation (8) no longer applies. This is
confirmed by the fact that combining the theoretical iron
mass loss with the corrosion current (C‐m,th‐j) leads to a
higher frequency of correct classification than combining
the experimental iron mass loss with the corrosion
current (C‐m‐j). In the first combination, both corrosion
current and iron mass loss are determined to assume a
uniform corrosion system as the experimental mass loss
results from nonuniform corrosion and is, on average,
about 1.3 times greater than the theoretical one.
5.2 | Analysis and discussion
An experimental set of values has been classified with
respect to the combined criteria C‐E‐R. The statistical
moments obtained from these sets are reported in Tables
7 and 8, where no distinction is made according to the
concrete mix as it was observed previously that the
average variation of frc was less than 15% between
concrete mixes for the same exposure condition.
As far as the Tafel slopes are concerned (Table 7) it
can be seen that the coefficient of variation is very large,
varying from about 45−105% depending on the exposure
conditions. There is no significant difference regarding

T A B L E 6 Frequency of correct classification (%)

Exposure condition Concrete mix C‐m‐E C‐m‐R C‐E‐R C‐m‐E‐R C‐m‐j C‐m,th‐j C‐m‐V C‐E‐R‐j C‐j‐V C‐m‐j‐V
XC1 CEM I 83.4 90.0 77.8 73.3 40.0 58.6 74.1 48.6 16.7 16.7
CEM II 70.5 76.4 86.1 64.7 45.2 68.0 56.7 54.8 8.0 8.0
CEM III 81.8 84.8 88.9 75.8 24.2 50.0 79.3 30.6 6.9 6.9
All concrete mixes 78.4 83.5 84.3 71.1 36.2 58.3 69.8 44.1 9.9 9.9
XC4 CEM I 80.5 83.3 86.1 69.4 62.9 65.5 30.0 65.7 0.0 0.0
CEM II 77.8 72.2 86.1 72.2 60.0 72.4 36.7 57.1 6.9 6.9
CEM III 80.6 55.6 72.2 55.6 41.2 78.6 53.3 55.9 0.0 0.0
All concrete mixes 79.6 70.4 81.5 65.7 54.8 72.1 40.0 59.6 2.3 2.3
Outdoor CEM I 69.7 69.7 88.9 60.6 25.9 54.2 93.1 44.4 20.8 20.8
CEM II 80.5 80.5 91.7 75.0 35.7 47.8 90.0 39.3 30.4 30.4
CEM III 80.5 80.6 83.3 66.7 37.9 58.3 76.7 37.9 16.7 16.7
All concrete mixes 77.1 77.1 88.0 67.6 33.3 53.5 86.5 40.5 22.5 22.5
All exposures and concrete mixes 78.4 76.8 84.6 68.1 42.2 61.8 65.3 48.6 10.9 10.9
DUPRAT ET AL. | 11

T A B L E 7 Statistical results for Tafel slopes (V/dec)

Exposure Passive anodic Passive cathodic Active anodic Active cathodic

condition Statistics Tafel slope βa,P Tafel slope βc,P Tafel slope βa,A Tafel slope βc,A
XC1 Mean 0.577 0.222 0.988 0.473
Coeff. of variation 70.6% 74.3% 44.3% 53.3%
10% percentile 0.175 0.099 0.216 0.118
90% percentile 1.028 0.478 1.554 0.781
XC4 Mean 0.516 0.174 0.875 0.515
Coeff. of variation 64.6% 67.0% 69.4% 83.1%
10% percentile 0.120 0.092 0.181 0.126
90% percentile 0.953 0.291 1.504 0.957
Outdoor Mean 0.950 0.235 0.770 0.452
Coeff. of variation 93.3% 71.2% 71.6% 51.7%
10% percentile 0.225 0.092 0.130 0.108
90% percentile 2.214 0.494 1.726 0.763
All exposures Mean 0.637 0.218 0.868 0.473
Coeff. of variation 89.6% 72.5% 61.8% 71.7%
10% percentile 0.174 0.096 0.191 0.121
90% percentile 1.245 0.440 1.526 0.852
Number 140 152 102 110

T A B L E 8 Statistical results of half‐cell potentials (mV/SCE) and polarization resistances (kΩ)

Exposure Passive corrosion Passive polarization Active corrosion Active polarization

condition Statistics potential Ecorr, P resistance Rp,P potential Ecorr, A resistance Rp,A
XC1 Mean –147.6 40.262 –514.4 3.772
Coeff. of 86.6% 73.2% 18.1% 60.5%
variation
10% percentile –325.9 12.794 –675.9 1.168
90% percentile 22.1 78.426 –424.5 7.505
XC4 Mean –139.3 27.379 –480.2 2.965
Std deviation 72.7% 62.4% 12.8% 56.9%
10% percentile –282.9 11.146 –562.1 1.284
90% percentile –15.7 54.302 ‐405.4 6.137
Outdoor Mean –105.9 50.686 –480.8 3.432
Coeff. of 116.7% 63.0% 12.7% 53.5%
variation
10% percentile –321.6 14.159 –579.8 1.193
90% percentile 37.8 98.147 –404.5 6.114
All exposures Mean –126.5 42.466 –491.1 3.296
Coeff. of 96.6% 70.9% 15.0% 58.6%
variation
10% percentile –314.5 12.138 –585.5 1.214
90% percentile 26.2 85.989 –407.5 6.328
Number 162 151 112 112
12 | DUPRAT
the coefficient of variation depending on either the
branch concerned (anodic or cathodic) or the exposure
condition. In contrast, there is a tendency for the
coefficient of variation to be more pronounced in the
case of the passive state of corrosion, except for the XC4
exposure, where the opposite occurs. A consequence of
the widespread of the Tafel coefficients is that domains of
strong likelihood (say 80% interval between 10% and 90%
percentiles) globally overlap, more or less, whatever the
exposure condition, the branch or the corrosion state.
Considering all the exposure conditions, the overlap
between passive and active corrosion states appears
larger for the anodic Tafel coefficient (0.8–2.1 V/dec)
than for the cathodic one (0.2–0.9 V/dec). The same
values of the Tafel coefficients can hence be attributed to
both passive and active states of corrosion and more
probably for the anodic one. It is nevertheless worth
noting that the mean value of the Tafel coefficients
generally increases from the passive to the active state of
corrosion except for the outdoor exposure condition. This
observation goes against the assumption made earlier,
and confirmed experimentally in Figure 4 for two
separate specimens, that a decrease of the anodic Tafel
slope together with a fairly constant cathodic slope would
characterize the shift from the passive to active corrosion
state. Generally speaking, a rise in Tafel slopes may be
caused by a limitation of charge transfer rate, which can
occur, for instance, in the case of the anodic coefficient by
FIGURE 5 Fictitious polarization curves deduced from average values of electrochemical properties. A: Active steel, P: passive steel
ET AL.
the presence of an oxide layer at the surface of the steel,
formed under active corrosion.[17] On the other hand, as
the experiment for measuring the Tafel slopes implies the
irremediable ruin of the corrosion system due to the high
imposed potential sweep, it was not possible to confirm
this shift. Steel polarization curves based on average
values of Tafel slopes, corrosion potential, and polariza-
tion resistance for all the exposure conditions are plotted
in Figure 5, where it can be clearly seen that corrosion
states are differentiated.
Tafel coefficients obtained in the present study also
exhibit a certain discrepancy in terms of mean value and
coefficient of variation with regard to those obtained by
previous studies conducted with a similar determination
procedure, as shown in Table 9, where all the results of
each study are merged (RC and HybRC, loaded and
unloaded in Nguyen et al.,[16] PCC and GPC in Babaee
and Castel[17]). Beyond the fact that the applied potential
sweep for determining the Tafel coefficients was much
smaller in Nguyen et al.[16] or Babaee and Castel,[17]
which could have contributed to this finding, the
difference in mean values and coefficients of variation
can result from the origin of corrosion on the one hand
and from the criterion for distinguishing passive and
active states of steel on the other. Published results of
Tafel coefficients under carbonation‐induced corrosion
are very scarce, rendering uneasy the comparison of
mean values with those obtained under chloride‐induced
DUPRAT ET AL.
T A B L E 9 Tafel coefficients obtained in present and previous studies
Passive anodic
Reference Statistics Tafel slope βa,P
Present study Mean 0.637
Coeff. of variation 89.6%
Nguyen et al.[16] Mean 0.562
Coeff. of variation 37.5%
Babaee and Castel [17]
Mean ∞ 0.037
Coeff. of variation ∞ 14.7%
corrosion. When corrosion is induced by chloride ingress,
and in the case of single rebar, the presence of chlorides
is a major environmental constraint acting at every stage
of corrosion. This dominant parameter tends to mask the
effect of other parameters and, in consequence, the
scatter on Tafel slopes remains moderate. In contrast,
when corrosion is induced by carbonation, no single
parameter is dominant and all implied parameters can
influence the variation of Tafel slopes in the same
proportion. In Babaee and Castel[17] corrosion was not
initiated for specimens corresponding to the passive state
of steel as it was initiated by immersion in a chloride
solution for specimens corresponding to the active state,
and then activated by wet/dry cycles. In Nguyen et al.[16]
corrosion was initiated for all specimens by an external
ponding dam containing chloride solution at the concrete
surface and then activated by emptying/refilling the
ponding dam with solution. Measurements were made
periodically and the distinction between passive and
active states of steel was decided according to the
corrosion potential, all specimens experiencing a corro-
sion potential in the range ]–300; –100[ mV/SCE being
discarded. In both of these previous studies, the samples
were clearly differentiated according to the state of the
steel and specimens in an uncertain state were not
considered whereas, in our case, all specimens were
classified as corresponding to a particular state of the
steel. Although the distinction of the steel state is clearly
shown in Figure 5 it is not so significantly reported in the
mean values of Tafel coefficients.
As far as the electrochemical properties are concerned
(Table 8) it is noteworthy that the coefficients of variation
of the polarization resistance are on average similar
(53–73%) to those of the corrosion potential (13–117%),
and are more reduced for both in the active than in the
passive corrosion state. This was not observed for the
Tafel coefficients. Threshold values used for the classifi-
cation in the passive and active states led to a wider range
of possible values in the passive state for the corrosion
potential and an even wider one for the polarization
| 13
Passive cathodic Active anodic Active cathodic
Tafel slope βc,P Tafel slope βa,A Tafel slope βc,A
0.218 0.868 0.473
72.5% 61.8% 71.7%
0.198 0.180 0.102
21.5% 22.4% 9.5%
0.609 0.150
36.9% 38.8%
resistance, as shown by the 10% and 90% percentiles. In
the same way, there was no overlap between passive and
active domains for any electrochemical property. As
already mentioned regarding the Tafel coefficients, the
mean values of polarization resistance and corrosion
potential clearly differentiate the passive from the active
state of corrosion, as depicted in Figure 5.
5.3 | Statistical analysis
All computations of this part were performed with
Matlab tools. Statistical inference from collected data is
all the more precise when the number of data items is
large. Merging data from various exposure conditions is
thus a good option concerning that goal. When deciding
whether data merging is relevant, classical statistical tests
are useful. The Student test and Fisher–Snedecor test aim
to test whether two samples relate to a single population
of the same mean or same variance, respectively. As these
tests optimally apply only to a normal distribution, their
use could be unsatisfactory in our case, where very few
values of 10% and 90% percentiles match those of normal
tails. The two‐sample Kolmogorov‐Smirnov test and
the Wilcoxon–Mann–Whitney test are more generally
applicable. The first is based on the maximum absolute
difference between the observed cumulative density
functions and it tests whether samples come from the
same population (null hypothesis). The second is based
on the number of times one sample precedes the other in
an ordered arrangement of the elements and indicates
whether samples relate to a single population having the
same median (null hypothesis). Probability values of the
tests are reported in Tables 10 and 11. It can be seen that,
for the Tafel coefficients, the null hypothesis is some-
times rejected at the 5% significance level by one or the
other test, or by both, implying that data of the
corresponding experimental sets should be considered
separately and not merged in a larger sample. However,
as there are no reference distributions of Tafel slopes in
the literature, it does not seem convenient for practical
14 | DUPRAT ET AL.

T A B L E 10 Kolmogorov dependence‐test results (probability %) between exposure conditions

Tafel coefficients Corrosion potential Polarization resistance

Exposure conditions βa,P βc,P βa,A βc,A Ecorr, P Ecorr, A Rp,P Rp,A
XC1 and XC4 80.7 17.5 1.0 47.0 65.5 13.8 4.6 9.5
XC1 and outdoor 13.9 54.9 0.6 88.7 12.2 33.8 7.6 9.3
XC4 and outdoor 3.2 9.3 30.8 81.9 3.8 89.2 0.0 47.2

use to attempt to distinguish distributions with respect to ⎛ N ⎞

the exposure condition of the concrete surface. So, θˆ = arg min ⎜⎜ −∑ ln fX (x i|θ ) ⎟⎟. (19)
θ ⎝ ⎠
irrespectively of the output of hypotheses, test data was i =1

globally gathered together for all exposure conditions for

the goodness‐of‐fit tests.
The results of statistical dependence tests carried out
for the electrochemical properties were similar to those
obtained for the Tafel coefficients: The null hypothesis is
rejected in some cases but, for the sake of simplicity, the
data sets corresponding to the various exposure condi-
tions have been brought together. Moreover, pooling data
also gives the opportunity to work with samples of more
than 100 values, which is a convenient size for statistical
inference.
The statistical inference was conducted in two stages
for each marginal distribution of the eight quantities of
interest. The first stage was to fit observations to a
theoretical distribution, determining the distribution
parameters by the maximum likelihood estimation
(MLE). The principle of MLE is to determine the
parameters (expectation, variance, shape, and scale
factors, etc., denoted θ ) so that they maximize the
likelihood function LN (x|θ) which, if the observations x
are independent, can be expressed as
N
LN (x|θ ) = ∏ fX (x i|θ)
i =1
The second stage consists in assessing how various
distributions can faithfully represent the observations
according to specific goodness‐of‐fit tests. The Kolmogor-
ov–Smirnov test and the χ2 test were applied in the
present study. These are efficient tests, widely used in the
literature.[36] The nonparametric Kolmogorov–Smirnov
test is based on the maximum distance DN between the
expected cumulative distribution function FX and the
observed one FO .
DN = max|FX (x i ) − FO (x i )|. (20)
xi
The Kolmogorov–Smirnov metric is λ = NDN . If
x1,… , xN is a random sample of X whose cumulative
distribution function is FX , an upper limit exits for λ
depending on N and a given confidence level α . For
instance, if N > 40 then λ = 1.22 for α = 0.95
(P (λ ≤ 1.22) = 0.95). In the χ2 test the data is grouped
into Nb bins and the chi‐square metric χ 2 is computed.
Nb
(18)
χ2 = ∑ (Oi − Ei )2 / Ei (21)
i =1

where Oi is the observed count and Ei is the expected

where fX (x i|θ ) is the theoretical probability density
count, derived from the theoretical distribution, for bin i .
function evaluated at the observation x i . Usually and
In both tests, the null hypothesis is that the data comes
equivalently, the log‐likelihood is minimized and the best
estimate θ̂ holds from the predetermined distribution. If this is the case,

T A B L E 11 Wilcoxon–Mann–Whitney dependence‐test results (probability %) between exposure conditions

Tafel coefficients Corrosion potential Polarization resistance

Exposure conditions βa,P βc,P βa,A βc,A Ecorr, P Ecorr, A Rp,P Rp,A
XC1 and XC4 62.4 14.6 2.6 62.3 76.8 1.5 20.7 12.4
XC1 and outdoor 2.9 78.3 5.4 65.3 6.3 6.6 23.9 71.7
XC4 and outdoor 1.9 9.2 3.9 8.4 9.4 0.0 97.6 32.4
DUPRAT ET AL. | 15

T A B L E 12 Expected distributions

Distribution Density probability function Parameters

a : log mean, − ∞ < a < +∞
Lognormal (LN)
fX (x | a, b) =
1
xa 2π
exp ( −(ln x − a)2
2b2 ), x > 0 b: log std. dev., b > 0
a : scale param. a > 0
Weibull (WB)
fX (x | a, b) =
b
a
x b −1
()
a
exp (− ( ) ), x > 0
x b
a
b: shape param. b > 0
Generalized extreme value (GEV) 1 ⎛⎜ x − a ⎞⎟−1−1/ c ⎛ ⎛ x − a ⎞⎟−1/ c ⎞ a : loc. param., − ∞ < a < +∞
fX (x | a, b, c ) = 1+c exp ⎜−⎜1 + c ⎟,
b ⎝ b ⎠ ⎝ ⎝ b ⎠ ⎠ b: scale param., b ≥ 0
−∞ < x < +∞ c : shape param.,
− ∞ < c < +∞
a : loc. param., − ∞ < a < +∞
Extreme (EX) 1
fX (x | a, b) = b exp ( ) exp (−exp ( ) ),−∞ < x < +∞
x−a
b
x−a
b
b: scale param., b ≥ 0
a : scale param., a > 0
Rayleigh (RA)
fX (x | a) =
x
a2
exp (− ( ) ), x ≥ 0
x
2a
2

a : scale param. a > 0

Gamma (GA) fX (x | a, b) =
1
abΓ(b)
x b −1exp ( − ), x > 0
x
a
b: shape param., b > 0
Burr (BU) −c −1 a : scale param., a > 0
fX (x | a, b, c ) =
bc
a
x b −1
()
a (1+( ) )
x b
a
, x>0
b: first shape param., b > 0
c : second shape param., c > 0
Beta (BE) fZ (z | a, b) =
1
z a −1 (1 − z )b −1, 0 < z < 1 a : first shape param., a > 0
Β(a, b)
b: second shape param., b > 0

the metrics should be distributed according to the
Kolmogorov or χ2 distribution, respectively. The prob-
ability of exceeding the metrics (p value) is then
compared to the accepted confidence risk (1 − α ) (or
significance level) with a minimum value of 5%.
The various theoretical candidate distributions are
reported in Table 12. Some of them are usual for material
properties, like the Weibull, Lognormal or Beta distribu-
tions. The Beta distribution is particularly useful due to
its simultaneously bounded and flexible nature.[32]
Generalized extreme value and extreme distributions
are usually dedicated to modeling loads or natural actions
on structures, like traffic loads or snow action.[33] The
Rayleigh distribution is rather used for space‐variant
phenomena like wind action.[34] The Gamma and Burr
distributions are convenient in economics[35] or engi-
neering for time‐variant phenomena.[31,38] In Table 12,
the Beta distribution is presented in its standardized
form. It can be easily adapted to any range ] x1, x2 [ by
writing z=(x − x1)/(x2 −x1). The bounds can be deter-
mined according to the data and, for instance, simply
equal the empirical min Omin and max Omax . Never-
theless, there is no physical reason to limit the support of
distribution functions, except for data that cannot be
negative. x1 was therefore stated at zero for the Tafel
coefficients and polarization resistance, and at
x1 = Omin − ksO for the corrosion potential. Similarly to
the latter value of x1, x2 was stated at x2 = Omax + ksO ,
where sO is the empirical standard deviation. Such an
interval is intended to be reasonably broad enough to
simulate unlimited support. Expected counts Ei in
Equation (21) and thereafter the goodness‐of‐fit, depend
upon the value of k . This was consequently determined
so that Ei did not vary by more than 5% for each bin when
k was changed to k + 1. For cases of data where the Beta
distribution was one of the best fitted, k was equal to 2.
The two stages of the statistical inference were applied
to the Tafel coefficients, corrosion potential, and polar-
ization resistance. Candidate distributions selected if the
goodness‐of‐fit tests did not reject the null hypothesis
(p > 5%) were then ranked according to the score Sgof .
pChi2 − 0. 05 pKolm − 0.05 |EX − mO|
Sgof = + −
0.05 0.05 mO
| VX − sO| |X − O10%|
− − 10%
sO O10%
|X90% − O90%|
− . (22)
O90%
This score compares selected distributions according
to their closeness to the empirical values of mean (mO ),
standard deviation (sO ), 10% percentile (O10%) and 90%
percentile (O90%). In Equation (23), the first two terms
16 | DUPRAT ET AL.

T A B L E 13 Goodness‐of‐fit results (two best candidate distributions)

Parameters

Data Dist. a b c pChi2 pKolm EX VX X10% X90% Sgof

βa, P (V/dec) BU 0.702 2.017 1.538 0.600 0.749 0.685 0.657 0.189 1.301 24.8
GA 0.374 1.832 0.484 0.335 0.684 0.506 0.167 1.359 14.1
βc, P (V/dec) BU 0.142 3.630 0.635 0.139 0.921 0.224 0.308 0.089 0.383 18.0
LN −1.724 0.639 0.197 0.152 0.212 0.156 0.078 0.405 4.7
βa, A (V/dec) RA 0.696 0.347 0.252 0.873 0.456 0.320 1.495 9.1
WB 0.975 1.905 0.183 0.280 0.865 0.473 0.299 1.511 6.5
βc, A (V/dec) GA 0.204 2.412 0.270 0.764 0.492 0.317 0.154 0.917 18.2
BE 1.967 12.323 0.269 0.762 0.492 0.317 0.154 0.919 18.1
Ecorr, P (mV/SCE) GEV −164.5 125.8 −0.369 0.082 0.369 −126.8 120.7 −287.4 27.7 7.1
BE 7.619 7.932 0.056 0.227 −126.9 120.7 −284.5 31.2 3.6
Ecorr, A (mV/SCE) GEV −504.4 80.1 −0.543 0.287 0.951 −490.9 73.8 −591.9 −403.3 22.7
EX −456.7 59.645 0.209 0.659 –491.1 76.5 −590.9 −407.0 15.3
Rp, P (kΩ) WB 46.616 1.578 0.224 0.525 41.849 27.117 11.202 79.075 12.7
BE 1.774 6.107 0.139 0.524 42.200 26.273 11.728 79.232 11.0
Rp, A (kΩ) WB 3.726 1.817 0.545 0.524 3.312 1.888 1.080 5.897 19.2
BE 2.088 5.470 0.524 0.432 3.319 1.836 1.106 5.893 16.9
Abbreviation: SCE: saturated calomel reference electrode.

(where pChi2 and pKolm are respectively the p values of χ2
and Kolmogorov–Smirnov tests) contribute to the dis-
tribution being favored and the last four contribute to it
being discarded. The two best‐fitted distributions to-
gether with their parameters are reported in Table 13.
Histograms corresponding to the distribution of highest
score can be seen in Figure 6.
It can be seen in Table 14 that distributions from the
exponential family are most suitable according to the Sgof
score for all quantities of interest except for the Tafel
coefficients in the case of the passive state of corrosion,
where the Burr distribution is preferable. For every
quantity studied, two or more distributions are almost
equally convenient. When the mean and variance of the
output of a corrosion model are sought, where these
quantities are needed, the use of either of the feasible
distributions is likely to lead to the same result. However,
in a reliability approach, where distribution tails may
significantly contribute to the result, it is obvious that the
choice of the distributions is a real concern.
The statistical analysis previously carried out was
preceded by a classification procedure to distinguish the
data with respect to the steel corrosion state they are
supposed to pertain to. For the data significantly
modified by the steel state the effect of this latter should
appear when looking at a histogram of mixed data
covering the two possible states, passive or active, where
two distinct modes should be visible. This can be seen in
Figure 7 for the corrosion potential where two peaks are
clearly drawn, whereas only one peak and shape of the
plateau are formed in Figure 8 for the polarization
resistance. To identify the modes, a mixture probability
distribution expressed as
fX , M (x ) = αfX , P (x | θP ) + (1 − α ) fX , A (x | θA) (23)
can be suitably used in a statistical analysis of the data,
where the distributions parameters θP and θA, referring
respectively to passive or active state of corrosion, and the
proportion factor α are determined by the MLE
procedure. The distributions fX , P and fX , A are often
chosen of the same type for the sake of simplicity.[37] In
our study the Normal and General Extreme Value
distributions for the corrosion potential, and the Weibull
and LogNormal distributions for the polarization resis-
tance were tested against data provided by the experi-
mental campaign. The fitted distribution parameters are
given in Table 14, where it can be noticed that EX and
VX defining the modes of each electrochemical quantity
are close to each other whatever the assumed distribu-
tions. Moreover these values are also very similar to those
obtained after having separated the data as a function of
the steel corrosion state and presented in Table 13, when
considering the same type of distribution. Consequently
it can be noted on the one hand that the MLE procedure
is satisfactory to extract the distributions corresponding
to passive or active corrosion state of steel from the global
experimental set of corrosion potentials or polarization
DUPRAT ET AL. | 17

FIGURE 6 Histograms of data and best‐fitted distributions

18 | DUPRAT ET AL.

T A B L E 14 Distributions parameters obtained by MLE from the global samples and comparison with Table 13

Parameters θP or θA

Data Dist. fX a b c EX EX (Table 13) VX VX (Table 13) α

Ecorr, P (mV/SCE) GEV −170.1 142.8 −0.443 −133.3 −126.8 133.3 120.7 0.403
N −102.0 107.3 −102.0 107.3 0.478
Ecorr, A (mV/SCE) GEV −509.6 84.1 −0.398 −465.8 −490.9 79.8 73.8 0.403
N −465.0 93.8 −465.0 93.8 0.478
Rp, P (kΩ) WB 39.135 1.251 36.443 41.849 29.314 27.117 0.334
LN 3.638 0.627 46.285 32.137 0.502
Rp, A (kΩ) WB 3.274 1.913 2.905 3.312 1.580 1.888 0.334
LN 1.241 0.812 4.811 4.652 0.502
Abbreviations: MLE: maximum likelihood estimation; SCE: saturated calomel reference electrode.

(a) (b)

FIGURE 7 Experimental histogram and mixed (a) or separated (b) distributions of Ecorr

(a) (b)

FIGURE 8 Experimental histogram and mixed (a) or separated (b) distributions of Rp

DUPRAT ET AL. | 19

(a) (b)

FIGURE 9 Experimental histograms of βa (a) and βc (b)

As far as the Tafel coefficients are concerned, no

T A B L E 15 Pearson correlation coefficient visible tendency allowing to discriminate distinct modes
Passive state Active state is emphasized in Figure 9. It would have been then of
limited interest to perform a statistical analysis of the
βc Ecorr Rp βc Ecorr Rp sample as a whole. This confirms that a specific
βa 0.368 –0.111 –0.013 0.784 0.114 0.014 procedure merging Tafel coefficients, corrosion potential,
–0.438 –0.179
and polarization resistance was needed to properly
βc 0.144 0.074
discern the data as a function of the steel corrosion state.
ECorr 0.406 0.523
In the perspective of using the studied distributions in
modeling and random simulation, a major concern is also
to assess whether a correlation exists between data so as
to combine this information with the knowledge of
marginal distributions. The most common approach
regarding correlation is based on the Pearson product–
moment correlation coefficient. Considering two samples
of data, X and Y , the Pearson correlation coefficient is
written as

so, XY
ρXY = (24)
so, X so, Y

FIGURE 10 Samples of βc and βa for passive or active
corrosion state
resistance, and on the other hand that the procedure
proposed for discriminating the corrosion states accord-
ing to the thresholds based on the optimum probability of
right alarm and reported in Table 3 is relevant.
where so, XY is the empirical covariance, and so, X and so, Y are
the empirical variances of X and Y . When the corelation
coefficient is less than 0.3, X and Y can be supposed
stochastically independent and the correlation may be
ignored in a simulation procedure. In Table 15, it can be
seen that a positive nonnegligible correlation exists between
the Tafel coefficients on one side (Figure 10) and the
corrosion potential and polarization resistance on the other
side (Figure 11). There is hence a trend for both quantities of
each pair to deviate simultaneously in the same way with
respect to their mean value. The corrosion potential and
polarization resistance are fair indicators of instantaneous
corrosion activity in the case of a single rebar, if moisture and
oxygen access conditions remain constant in the bulk
concrete: their values are rather high under the passive
20 | DUPRAT
state, and low under the active state of steel as the corrosion
proceeds, as shown in Figure 3 in Angst et al.[39] and in
Figure 11 of the present paper. To a certain extent, their
random variation is then influenced and stochastically linked
by these conditions. The Tafel coefficients govern the
sensitivity of the corrosion system to polarization of the
steel. Under the same absolute polarization, anodic and
cathodic currents are all the more pronounced when the
Tafel coefficients are low. A nonnegligible correlation
coefficient between Tafel coefficients indicates that the
condition state of the corrosion system during the polariza-
tion test may influence the response (in terms of averages) of
the system in the same way under either anodic or cathodic
polarization. This is all the more visible when the system is
in an active state of corrosion, without, however, being
clearly under anodic or cathodic control. In the case of
chloride‐induced corrosion such correlation coefficients were
not observed in the literature.
6 | C ON C LU S I O N
Little attention is paid in the literature to the Tafel
coefficients related to carbonation‐induced corrosion even
though such corrosion affects most concrete structures. A
much more prominent effort has been dedicated to the
corrosion rate estimation.[18] With a view to predicting the
corrosion propagation in reinforced concrete structures,
advanced modeling has recently been developed, based on
Butler–Volmer equations and considering boundary condi-
tions on both passive and active steel.[6] This type of
modeling is promising as it is theoretically able to represent
macrosystems of corrosion, provided that realistic values of
ET AL.
FIGURE 11 Samples of Ecorr and Rp
for passive or active corrosion state
Tafel coefficients are introduced in the boundary conditions.
Tafel coefficients are thus crucial parameters for the
prediction of corrosion. In the present study, a broad
experimental campaign established probability distributions
for the major electrochemical properties of steel: anodic and
cathodic Tafel coefficients, corrosion potential, and polariza-
tion resistance. Active and passive states of carbonation‐
induced corrosion were considered. As none of the
experimental specimens could, a priori, be known to be in
a passive or active state of corrosion, several combinations of
criteria based on the outcomes of electrochemical tests were
used, in the aim of properly differentiating the corrosion
states, and ranked according to a so‐called frequency of
correct classification. Data samples were then extracted from
this classification and statistical inference was performed on
them. Compared to published results related to chlorination‐
induced corrosion,[16,17] mean values of the Tafel coefficients
obtained in the present study are significantly higher, as are
their coefficients of variation. Some possible reasons for this
finding have been discussed in detail. A broad variety of
marginal probability distributions have been proposed, fitted
and tested against experimental data. Pearson correlation
coefficients were additionally computed and revealed that
anodic and cathodic Tafel coefficients were not stochastically
independent. The outcomes of the present study will permit
future models of corrosion to be easily enriched by placing
them in the framework of probabilistic approaches, which
are a rational way to account for the random nature of
corrosion.
ORCID
Frédéric Duprat http://orcid.org/0000-0001-6979-4652
DUPRAT ET AL.
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How to cite this article: Duprat F, de Larrard T,
Vu NT. Quantification of Tafel coefficients
according to passive/active state of steel
carbonation‐induced corrosion in concrete.
Materials and Corrosion. 2019;1–30.
https://doi.org/10.1002/maco.201910962
22 | DUPRAT ET AL.

APPENDIX

T A B L E A1 Outdoor exposure condition — Concrete CI

Anodic Cathodic Iron mass Corrosion

Cover Specimen Tafel slope Tafel slope βc loss Δm iron potential Ecorr Polarization
condition reference Time (d) βa (V/dec) (V/dec) (g) (mV/SCE) resistance Rp (Ω)
D15NC 23 417 ∞ (11.092) 0.206 0.004 –85.4 68,292
28 162 ∞ (1011) 0.395 0.047 –262.9 45,120
30 417 n. m. n. m. n. m. –90.3 40,705
42 216 0.263 0.124 0.023 –363.7 8,443
63 417 n. m. n. m. n. m. –143.9 25,181
74 162 n. m. n. m. 0.010 –290.1 43,389
D15C 1 216 0.212 0.141 0.032 –322.2 22,833
5 417 0.757 0.429 0.045 –524.6 2,222
7 197 0.190 0.147 0.027 –442.5 3,867
9 162 3.377 0.458 0.042 –381.4 28,181
15 389 0.390 0.393 0.027 –123.3 5,610
16 162 n. m. n. m. 0.020 –351.5 19,164
18 382 1.395 0.422 0.027 –69.1 53,604
19 197 2.006 0.719 0.064 –407.1 4,618
25 417 1.255 0.577 0.044 –513.3 2,452
27 375 0.698 0.308 0.031 –63.3 63,228
41 382 0.569 0.395 0.014 22.5 81,005
43 375 0.263 0.192 0.210 –133.6 11,472
58 216 1.029 0.232 0.088 –338.5 26,353
59 417 0.765 0.513 0.042 –579.8 1,689
83 382 0.338 0.310 0.049 –31.7 20,055
D30C 4 197 0.534 0.110 0.018 26.2 20,1267
6 382 2.037 0.488 0.023 –59.2 59,278
10 216 0.086 0.059 0.030 –65.2 206,233
12 417 ∞ (11.181) 0.304 0.015 –386.8 4,165
13 375 1.005 0.092 0.019 33.7 60,287
20 417 0.200 0.904 0.047 –448.4 5,322
26 389 0.836 0.139 0.031 –3.7 69,600
36 389 1.211 0.379 0.026 –10.3 131,075
44 197 0.090 0.094 n. m. –60.0 225,979
47 162 n. m. n. m. 0.011 –40.5 33,932
61 162 2.496 0.448 0.067 –339.1 16,500
65 417 1.673 0.153 0.010 –124.9 5,809
103 216 0.629 0.091 0.027 57.8 174,422
104 382 ∞ (10 ) 15
0.181 0.019 129.5 3,677
105 375 3.278 0.388 0.032 –79.5 56,865
DUPRAT ET AL. | 23

T A B L E A2 Outdoor exposure condition — Concrete CII

Anodic Cathodic Iron mass Corrosion

Cover Specimen Tafel slope Tafel slope βc loss Δm iron potential Ecorr Polarization
condition reference Time (d) βa (V/dec) (V/dec) (g) (mV/SCE) resistance Rp (Ω)
D15NC 126 216 0.134 0.185 0.017 –133.5 77,779
134 162 ∞ (1014) 0.381 0.029 15.3 56,711
136 417 0.666 0.165 0.028 –66.5 33,080
144 162 n. m. n. m. 0.006 27.7 2,628
145 417 0.247 0.158 0.004 –113.3 45,637
147 417 0.649 0.254 0.013 –142.5 29,933
D15C 112 216 4.631 0.306 0.047 –235.7 49,564
115 162 1.247 0.591 0.087 –361.1 14,349
116 417 0.694 0.366 0.044 –507.2 2,914
118 375 0.273 0.165 0.047 –147.1 41,713
119 382 0.402 0.399 0.086 –175.8 1,893
123 375 0.503 0.049 0.026 40.7 2,791
124 417 2.292 0.178 0.046 –347.4 9,415
127 216 0.649 0.172 0.029 –203.6 101,017
132 382 0.596 0.520 0.055 –425.4 3,083
135 417 0.712 0.388 0.061 –558.0 1,302
138 382 0.512 0.518 0.067 –145.0 27,409
140 162 n. m. n. m. 0.050 –432.2 7,261
141 389 0.417 0.154 0.057 –52.5 27,250
143 197 ∞ (1014) 0.098 0.027 –272.9 46,426
146 197 9.391 0.117 0.024 –39.7 169,450
D30C 110 216 5.807 0.169 0.020 –47.8 94,330
111 375 0.253 0.043 0.010 –12.7 31,187
113 417 ∞ (1015) 0.200 0.050 –151.1 44,842
114 162 n. m. n. m. 0.027 –91.4 107,857
120 197 1.083 0.109 0.014 –54.1 198,137
121 417 1.128 0.196 0.014 –231.4 21,383
125 216 0.796 0.133 0.028 –126.9 85,647
128 375 0.676 0.066 0.016 16.2 31,633
129 382 0.448 0.076 0.021 34.5 93,155
130 417 1.753 0.171 0.035 –227.7 18,898
131 197 0.294 0.173 0.043 –46.2 115,580
133 162 ∞ (109) 0.891 0.081 –130.5 43,058
137 389 0.649 0.172 0.037 –59.7 23,361
139 389 0.427 0.063 0.028 54.1 38,229
142 382 1.307 0.221 0.027 –73.1 61,256
24 | DUPRAT ET AL.

T A B L E A3 Outdoor exposure condition — Concrete CIII

Anodic Cathodic Iron mass Corrosion

Cover Specimen Tafel slope Tafel slope βc loss Δmiron potential Ecorr Polarization
condition reference Time (d) βa (V/dec) (V/dec) (g) (mV/SCE) resistance R p (Ω)
D15NC 150 162 ∞ (14.150) 0.537 0.061 –35.5 41,960
157 417 0.678 0.149 0.027 –203.7 41,532
158 417 3.617 0.421 0.016 –108.6 5,416
161 417 0.776 0.195 0.053 –203.5 9,747
168 216 0.654 0.122 0.005 38.2 114,357
178 162 n. m. n. m. 0.047 –167.1 8,139
D15C 148 375 0.451 0.540 0.058 –115.7 47,931
149 382 0.550 0.290 0.047 7.8 76,304
151 417 1.540 0.649 0.087 –457.2 1,471
153 162 n. m. n. m. 0.050 –404.5 5,433
163 417 ∞ (10 ) 15
0.165 0.056 –511.2 2,709
165 216 1.264 0.934 0.148 –297.5 3,045
166 162 0.506 0.522 0.118 –548.3 4,192
169 375 0.885 ∞ (1015) 0.097 –106.9 11,120
171 197 0.133 0.104 0.035 –446.4 4,512
172 417 0.125 0.109 0.095 –583.2 680
175 389 0.505 ∞ (10 ) 15
0.068 –89.5 54,424
176 197 0.748 0.547 0.013 –448.0 6,114
177 417 1.316 0.728 0.080 –511.2 1,193
179 216 0.123 0.113 0.020 –281.9 13,397
181 382 0.738 0.327 0.022 –93.8 7,298
D30C 117 216 ∞ (10 ) 15
0.347 0.028 –231.3 22,744
122 162 2.214 0.733 0.095 –321.4 12,012
152 216 0.796 0.240 0.046 –210.8 27,480
154 197 0.677 0.110 0.007 37.6 127,606
155 382 0.648 0.139 0.009 45.8 47,651
156 375 0.560 0.183 0.026 –45.5 77,691
159 389 ∞ (10 ) 15
0.142 0.019 112.0 123,300
160 382 1.020 0.108 0.024 118.3 34,104
162 197 0.756 0.132 0.009 –63.0 97,429
164 382 0.530 0.218 0.027 –49.8 94,794
167 389 0.670 0.168 0.018 91.3 160,015
170 417 1.285 0.420 0.025 –212.5 4,709
173 417 1.480 0.162 0.028 –166.8 7,062
174 162 n. m. n. m. 0.019 –84.1 49,985
180 375 0.225 0.134 0.015 –3.2 45,182
DUPRAT ET AL. | 25

T A B L E A4 Exposure condition similar to XC4 — Concrete CI

Anodic Cathodic Iron mass Corrosion

Cover Specimen Tafel slope Tafel slope βc loss Δm iron potential Ecorr Polarization
condition reference Time (d) βa (V/dec) (V/dec) (g) (mV/SCE) resistance Rp (Ω)
D15NC 307 83 0.474 0.205 0.002 56.5 6,817
308 290 0.450 0.153 0.011 6.9 32,114
312 290 ∞ (10 ) 8
0.144 0.008 –105.5 30,436
313 248 0.130 0.177 0.049 –136.3 2,174
319 290 0.416 0.124 0.002 –15.1 68,082
324 262 1.086 0.221 0.017 –93.6 13,849
D15C 301 83 1.232 0.518 0.109 –336.8 1,480
302 241 0.149 0.109 0.099 –555.5 1,415
303 83 1.323 0.530 0.084 –284.6 6,334
304 241 0.920 0.632 0.101 –548.4 988
310 83 0.158 0.077 0.056 –365.0 6,132
311 255 1.001 0.801 0.135 –545.6 1,457
315 255 0.156 0.128 0.121 –570.7 705
317 248 0.910 0.792 0.143 –418.0 2,894
318 262 0.134 0.112 0.124 –538.8 1,642
321 248 0.783 0.515 0.111 –528.5 1,696
323 290 0.110 0.108 0.182 –554.8 1,406
328 290 0.911 0.663 0.114 –571.4 1,887
329 248 0.849 0.513 0.116 –565.7 923
332 290 0.730 0.504 0.118 –597.0 1,477
333 248 0.535 0.337 0.122 –514.2 2,538
D30C 334 262 1.589 1.199 0.113 –554.8 1,192
305 262 0.695 0.142 0.030 –70.6 22,900
306 83 0.874 0.068 0.062 32.5 6,920
309 290 0.593 0.395 0.131 –484.2 2,886
314 241 0.093 0.101 0.094 –124.5 100,886
316 241 0.441 0.098 0.007 –382.2 6,441
320 255 0.144 0.148 0.090 –205.2 13,718
322 255 0.819 0.286 0.036 –334.7 8,002
325 248 0.459 0.281 0.128 –514.6 2,424
326 262 0.730 0.213 0.074 –468.5 6,364
327 290 0.559 0.322 0.134 –497.4 4,012
330 269 0.574 0.202 0.025 –148.2 46,679
331 83 0.656 0.238 0.035 –277.6 18,334
335 290 1.169 0.243 0.128 –426.7 3,346
336 269 0.929 0.507 0.016 –510.4 2,992
26 | DUPRAT ET AL.

T A B L E A5 Exposure condition similar to XC4 — Concrete CII

Anodic Cathodic Iron mass Corrosion

Cover Specimen Tafel slope Tafel slope βc loss Δm iron potential Ecorr Polarization
condition reference Time (d) βa (V/dec) (V/dec) (g) (mV/SCE) resistance Rp (Ω)
D15NC 413 290 0.120 0.120 0.010 –192.2 55,281
415 290 0.328 0.091 0.031 –68.1 36,744
420 290 0.786 0.177 0.020 –20.9 41,012
422 248 0.120 0.102 0.042 –93.5 10,962
424 83 0.298 0.048 0.006 –4.7 4,372
436 83 0.480 0.047 0.011 27.7 2,628
D15C 401 241 0.509 0.328 0.101 –449.8 2,264
405 290 0.723 0.367 0.116 –536.1 2,623
408 262 0.799 0.561 0.074 –411.0 4,902
409 269 0.680 0.247 0.064 –448.1 7,325
412 262 0.837 0.487 0.087 –482.9 3,741
414 248 0.667 0.508 0.147 –476.4 3,596
417 255 0.617 0.335 0.091 –502.3 6,006
419 290 0.673 0.381 0.109 –512.4 2,944
425 83 1.932 0.608 0.092 –297.3 3,829
427 241 2.343 1.942 0.224 –502.5 2,065
429 255 0.954 1.238 0.115 –523.9 3,085
430 83 ∞ (10 ) 9
0.698 0.079 –290.8 14,476
431 290 1.025 0.432 0.104 –561.7 3,957
434 269 0.830 0.503 0.068 –467.7 6,489
435 269 0.574 0.949 0.093 –390.6 6,184
D30C 402 255 0.959 0.279 0.081 –419.0 3,424
403 262 0.438 0.206 0.068 –283.5 13,788
404 241 0.752 0.253 0.102 –408.6 5,877
406 241 0.582 0.282 0.116 –387.1 2,825
407 262 3.301 5.817 0.091 –343.0 7,586
410 262 0.397 0.085 0.012 –63.8 52,277
411 248 0.153 0.125 0.009 –205.7 47,410
416 248 1.543 0.098 0.041 –66.4 17,881
418 262 0.540 0.120 0.017 –52.1 28,348
421 290 0.388 0.170 0.085 –268.5 9,510
423 255 0.318 0.138 0.021 –209.5 14,811
426 83 0.195 0.297 0.001 –116.1 56,530
428 83 0.846 0.324 0.031 –300.2 17,319
432 290 0.742 0.250 0.087 –221.2 6,529
433 290 0.693 0.258 0.118 –407.0 4,451
DUPRAT ET AL. | 27

T A B L E A6 Exposure condition similar to XC4 — Concrete CIII

Anodic Cathodic Iron mass Corrosion

Cover Specimen Tafel slope Tafel slope βc loss Δm iron potential Ecorr Polarization
condition reference Time (d) βa (V/dec) (V/dec) (g) (mV/SCE) resistance Rp (Ω)
D15NC 508 83 ∞ (1012) 0.015 0.002 –17.8 3,326
510 290 0.467 0.115 0.015 –166.1 12,935
511 290 0.516 0.100 0.017 –249.5 12,083
521 248 0.907 0.157 0.033 –334.2 35,090
529 290 0.791 0.151 0.007 1.1 4,623
534 83 0.395 0.032 0.007 –29.7 15,561
D15C 502 241 0.223 0.165 0.055 –408.8 1,080
505 248 0.242 0.194 0.071 –529.1 2,106
506 269 1.974 1.026 0.145 –524.4 1,625
507 262 1.275 0.798 0.078 –416.6 1,634
509 248 0.256 0.213 0.109 –586.7 1,964
513 83 0.291 0.288 0.067 –344.7 4,376
514 290 0.913 0.575 0.088 –471.1 1,918
519 255 1.494 0.916 0.127 –471.8 1,323
522 262 1.117 0.526 0.447 –544.5 1,893
523 255 1.025 0.664 0.133 –448.2 1,470
524 241 3.916 2.583 0.086 –424.3 2,422
531 290 0.958 0.417 0.089 –461.1 1,574
533 290 0.741 0.401 0.102 –408.8 1,483
535 269 0.879 0.565 0.088 –514.0 2,376
536 83 0.665 0.466 0.033 –366.6 2,530
D30C 501 241 0.480 0.237 0.043 –220.8 12,644
503 255 0.715 0.165 0.021 –201.8 4,078
504 241 1.017 0.484 0.115 –369.9 4,302
512 262 0.346 0.147 0.017 –213.4 3,431
515 262 0.938 0.160 0.002 –193.3 11,166
516 83 0.344 0.155 0.031 –118.7 27,881
517 290 0.604 0.267 0.062 –432.6 4,184
518 269 0.571 0.133 0.058 –114.7 1,598
520 248 0.629 0.158 0.043 –201.6 10,648
525 255 ∞ (10 ) 15
0.162 0.046 –351.5 4,086
526 83 0.540 0.092 0.093 –65.9 7,020
527 269 1.790 0.422 0.060 –499.5 2,615
528 290 0.905 0.270 0.044 –444.4 2,642
530 290 1.021 0.199 0.067 –130.5 3,311
532 248 1.478 0.563 0.152 –429.1 3,003
28 | DUPRAT ET AL.

T A B L E A7 Exposure condition similar to XC1 — Concrete CI

Anodic Cathodic Iron mass Corrosion

Cover Specimen Tafel slope Tafel slope βc loss Δm iron potential Ecorr Polarization
condition reference Time (d) βa (V/dec) (V/dec) (g) (mV/SCE) resistance Rp (Ω)
D15NC 601 109 0.149 0.125 0.001 –199.0 11,817
604 350 0.308 0.096 n. m. –100.9 44,406
616 295 0.207 0.100 n. m. –194.1 14,136
619 109 0.315 0.008 n. m. 20.3 30,911
628 350 0.921 0.126 0.038 –28.7 72,850
633 350 0.556 0.221 0.043 –48.7 47,845
D15C 602 309 1.297 0.624 0.053 –512.3 4,460
605 350 1.064 0.392 0.341 –421.1 9,819
606 350 1.111 0.600 0.081 –443.1 4,984
607 109 1.277 0.635 0.016 –493.3 12,717
608 302 0.354 0.395 0.043 –290.5 6,034
609 295 0.324 0.348 0.013 –279.2 7,603
612 132 0.333 0.276 0.037 –235.5 30,918
614 302 1.854 0.656 0.091 –431.1 2,729
617 350 1.436 0.716 0.091 –513.6 7,732
623 329 0.625 0.307 0.075 –385.5 12,778
625 109 0.282 0.199 0.040 –468.5 9,515
626 132 1.314 0.268 0.049 –429.4 18,795
627 329 0.494 0.286 0.035 –327.1 10,929
629 309 0.601 0.285 0.072 –373.3 11,308
634 295 0.189 0.123 0.012 –325.4 16,470
D30C 603 132 0.522 0.275 0.039 –49.0 164,924
610 329 0.113 0.128 0.018 –102.3 51,411
611 309 0.530 0.212 0.024 –67.1 86,075
613 302 0.967 0.445 0.109 –527.5 3,114
615 295 0.078 0.103 n. m. –95.9 52,227
618 309 0.570 0.163 0.013 –144.4 25,634
620 302 1.013 0.224 0.020 –62.1 46,572
621 350 0.779 0.433 0.117 –388.6 8,148
622 109 0.200 0.157 n. m. –205.0 98,972
624 309 1.772 0.529 0.090 –426.7 4,481
630 350 0.768 0.192 0.044 –348.6 17,361
631 350 ∞ (10 ) 15
0.480 0.063 –148.8 52,160
632 295 0.218 0.135 0.023 –190.0 59,078
635 132 0.226 0.124 0.019 –244.0 103,753
636 109 0.660 0.175 n. m. –417.4 190,490
DUPRAT ET AL. | 29

T A B L E A8 Exposure condition similar to XC1 — Concrete CII

Anodic Cathodic Iron mass Corrosion

Cover Specimen Tafel slope Tafel slope βc loss Δm iron potential Ecorr Polarization
condition reference Time (d) βa (V/dec) (V/dec) (g) (mV/SCE) resistance Rp (Ω)
D15NC 701 350 0.309 0.156 0.034 2.2 83,878
711 350 0.590 0.139 0.026 26.3 44,905
715 109 0.075 0.102 0.003 –44.4 6,460
719 350 2.206 0.287 n. m. –123.9 35,107
727 295 0.271 0.082 n. m. 96.5 9,942
729 109 0.135 0.070 0.019 –45.3 8,055
D15C 703 350 1.348 0.748 0.130 –467.8 5,757
705 350 1.013 0.475 0.109 –459.1 2,500
708 302 0.738 0.370 0.083 –488.3 3,080
709 329 0.757 0.293 0.074 –346.5 8,867
712 309 1.161 0.451 0.095 –529.2 2,256
713 132 0.509 0.297 0.067 –385.1 9,985
714 302 0.340 0.213 0.089 –197.7 20,201
717 309 0.263 0.162 0.095 –466.0 3,160
718 109 0.271 0.180 0.038 –415.3 9,390
721 295 0.779 0.348 0.086 –547.2 3,765
724 350 1.095 0.591 0.120 –491.2 2,134
725 132 0.390 ∞ (10 ) 9
0.063 –305.1 24,380
733 309 1.583 0.540 0.091 –589.5 1,474
735 295 0.193 0.112 0.052 –461.3 1,206
736 109 1.590 0.390 0.033 –406.7 9,067
D30C 702 329 ∞ (10 ) 15
0.190 0.077 –542.6 2,140
704 350 0.250 0.120 0.115 –697.5 2,204
706 109 0.066 0.097 0.003 –115.8 51,924
707 302 0.174 0.130 0.026 –203.0 33,197
710 329 ∞ (1015) 0.315 0.092 –661.8 1,653
716 302 1.272 0.166 0.054 –674.1 1,234
720 309 ∞ (1015) 0.146 0.067 –678.5 1,415
722 309 ∞ (1014) 0.115 0.062 –630.2 1,112
723 329 0.428 0.171 0.047 –234.1 24,713
726 109 ∞ (10 ) 9
0.360 0.006 –215.6 37,834
728 350 1.027 0.336 0.112 –587.2 2,251
730 132 0.176 0.145 0.038 –126.6 46,632
731 132 0.201 0.183 0.062 –189.0 22,788
732 295 1.340 0.615 0.050 –691.7 1,512
734 295 0.158 0.103 0.032 –657.1 563
30 | DUPRAT ET AL.

T A B L E A9 Exposure condition similar to XC1 — oncrete CIII

Anodic Cathodic Iron mass Corrosion

Cover Specimen Tafel slope Tafel slope βc loss Δm iron potential Ecorr Polarization
condition reference Time (d) βa (V/dec) (V/dec) (g) (mV/SCE) resistance Rp (Ω)
D15NC 802 350 0.651 0.117 n. m. 3.4 174,680
809 350 1.182 0.095 0.015 105.3 4,339
813 350 0.299 0.105 0.056 129.6 38,818
816 109 0.816 0.137 0.009 64.7 29,150
829 295 0.375 0.113 n. m. 76.3 10,514
833 109 1.042 0.070 0.006 –2.9 14,360
D15C 801 309 0.844 0.590 0.072 –340.9 13,938
804 295 0.207 0.173 0.032 –447.4 3,583
805 109 1.712 0.878 0.009 –349.3 52,165
807 329 1.086 0.724 0.079 –426.9 6,315
808 350 0.884 0.559 0.093 –482.5 52,27
814 109 0.995 0.793 0.019 –387.8 12,199
818 132 1.274 0.787 0.038 –318.5 35,866
819 309 1.241 1.037 0.067 –456.5 7,264
820 302 1.137 0.922 0.077 –428.0 7,353
821 350 1.061 0.828 0.087 –457.5 4,362
823 295 0.374 0.277 0.011 –364.8 5,606
827 329 0.909 0.750 0.052 –437.7 6,461
828 302 0.754 0.678 0.070 –393.3 7,745
831 132 0.938 0.530 0.058 –286.1 42,290
836 350 0.864 0.588 0.088 –463.1 5,284
D30C 803 350 0.664 0.196 0.062 –253.3 30,689
806 350 0.629 0.311 n. m. –364.1 6,614
810 295 0.625 0.135 0.019 –243.2 34,949
811 350 1.224 0.476 0.070 –322.3 14,243
812 302 0.488 0.215 0.024 –45.5 79,046
815 109 0.680 0.223 0.011 –197.2 29,381
817 302 0.468 0.188 0.040 –37.7 27,760
822 309 0.404 0.221 0.059 –234.3 12,667
824 309 0.823 0.289 0.062 –269.3 32,299
825 350 0.372 0.195 0.091 –216.9 39,742
826 132 0.650 0.159 0.036 –63.4 43,755
830 109 0.980 0.126 0.029 –11.72 208,127
832 132 0.848 0.196 0.043 –21.41 54,238
834 295 0.650 0.198 0.016 –184.1 27,015
835 309 0.730 0.238 0.056 –115.6 16,912