Electrochimica Acta 261 (2018) 66e77

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

A comparative study of mild steel passivation embedded in

Belite-Ye'elimite-Ferrite and Porland cement mortars
Guilherme Yuuki Koga a, b, *, Blandine Albert a, Virginie Roche b,
Ricardo Pereira Nogueira b, c
a
LafargeHolcim Research Center, 95 Rue Du Montmurier, 38291 Saint Quentin Fallavier, France
b
LEPMI, UMR5279 CNRS, Grenoble INP, Universit
e de Savoie, Universit

e Joseph Fourier, 1130, Rue de la Piscine, BP 75, 38402 Saint Martin d'H
eres, France
c
Gas Research Center, Khalifa University of Science and Technology, P.O. Box 2533, Abu Dhabi, United Arab Emirates

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

Article history: An extensive experimental program was designed to investigate the passivation of reinforced low
Received 9 November 2017 carbon-release Belite-Ye'elimite-Ferrite (BYF) cement mortars compared to the passivation of reinforced
Received in revised form conventional Portland equivalents (OPC). The influence of formulation parameters such as the water-to-
12 December 2017
cement ratio and the presence of fly ash on the steel rebar passivation was evaluated by conventional
Accepted 18 December 2017
Available online 19 December 2017
corrosion measurements such as corrosion potential readings and linear polarization resistance. Visual
observations were carried out as a complement. A negligible corrosion rate was reached after 28 days
with BYF cement against 14 days with OPC equivalent. This difference is attributed to the pH of the
Keywords:
Passivation
medium in the BYF mortars, which is lower than in the OPC mortars at a very early age, before becoming
Mild steel strongly basic. The exploitation of the Tafel slopes showed that the corrosion current can be evaluated by
Reinforced concrete the Stern and Geary equation with an identical B coefficient for the samples of BYF and OPC basis. Despite
Sulfoaluminate cement some differences compared to the passivation in Portland mortars, the present study clearly points to the
Portland cement BYF mortars intrinsically passivating nature regarding mild steel reinforcing bars.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction properties of fresh (e.g. workability) and hardened concretes (e.g.

Belite-Ye'elimite-Ferrite cements, referred to as BYF, are a
promising lower carbon-release alternative to ordinary Portland
cements (OPC) [1e4]. The base component is a clinker composed of
ye'elimite (Ca4Al6O12(SO4)), belite (Ca2SiO4), and calcium alumi-
noferrite solid solution (Ca2(Al,Fe)2O5), stated here in decreasing
order of content [2]. The clinker production of BYF requires less
limestone in the raw materials, a lower clinkering temperature, and
less energy to be ground compared to Portland clinker
manufacturing [4,5]. Industrial feasibility was checked and in-situ
measurements confirmed overall CO2 savings between 25% and
30% [6]. The partial substitution of BYF cement by supplementary
cementitious materials (SCMs) brings an additional reduction of
the amount of CO2 through the clinker substitution and by the
valorization of waste by-products such as fly ash. Moreover, the
addition of fly ash to cement may improve the engineering
~o Carlos, Department of Mate-
* Corresponding author. Federal University of Sa
rials Engineering, Rod. Washington Luis, km 235, S~
ao Carlos, CEP 13565-905, Brazil.
E-mail address: guilherme.koga@dema.ufscar.br (G.Y. Koga).
mechanical and barrier resistances) [7,8]. However, if BYF is to
replace OPC binders in a wide range of concrete applications, it
must likewise be able to passivate ordinary black steel re-
inforcements. Once embedded in OPC-based concrete, the steel is
spontaneously passivated. The transposition to BYF-based con-
cretes is questionable.
The available literature on the investigation of the corrosion
behaviour of steel embedded in sulfoaluminate cement matrices (to
which BYF family belongs) are scarce and not conclusive [9e11].
Based on visual inspection of the steel reinforcement embedded in
calcium sulfoaluminate (CSA) mortars after 14 years of service,
Glasser and Zhang [9] concluded that steel remains passivated
within the matrix. However, Kalogridis et al. [10] reported that the
lower pH values and the higher average pore diameters of BYF
matrix, compared to Portland one, expose the steel rebar to a
higher corrosion risk, as suggested by corrosion potential readings
and weight loss measurements. Janotka et al. [11] have performed
potentiodynamic polarization measurements using steel bars as
working electrodes immersed in sulfoaluminate-belite mortar ex-
tracts (pH~10.5). In line with Kalogridis et al. [10] results, it was
observed that the steel did not exhibit passivation plateau upon

https://doi.org/10.1016/j.electacta.2017.12.128
0013-4686/© 2017 Elsevier Ltd. All rights reserved.
 G.Y. Koga et al. / Electrochimica Acta 261 (2018) 66e77
anodic polarization. The available data are insufficient to an un-
ambiguous conclusion to be drawn upon this issue and an extensive
electrochemical survey is lacking to ascertain whether mild steel
spontaneously passivates or not when embedded in BYF matrices in
normal service conditions.
For a new family of binder arises also the question of the method
of evaluation of the steel corrosion. The suitability of the standards
(e.g. ASTM C876 [12]) and recommendations (e.g. RILEM TC 154-
EMC [13]) to the study the corrosion behaviour of reinforced BYF
structures should be experimentally verified since most of them
have been established for reinforced Portland structures. For
instance, the American Standard ASTM C 876-09 provides a crite-
rion to correlate the risk of corrosion and the potential reading
values. However, this criterion was empirically derived from
chloride-induced corrosion of mild steel embedded in bridges
decks in the USA for specific conditions of Portland concrete type,
layer, and exposition [14e16]. The RILEM TC 154-EMC [13], in turn,
provides recommendations to evaluate the corrosion rate of steel
reinforcement in concrete by means of the linear polarization
resistance method (LPR). In this case, an issue of major concern is
that the conversion of polarization resistance values, R, into
corrosion current densities, icorr, requires the previous knowledge
of the coefficient B of the Stern-Geary relationship (icorr ¼ B/R),
which is related to the Tafel slopes ba and bc [17]. For Portland-
based reinforced structures, B values of 26 and 52 mV for steel in
the active and passive state, respectively, have been recommended
[13], but no reliable information about the B values for reinforced
BYF structures is available.
In this paper, the intrinsic ability of the BYF mortar to effectively
induce mild steel reinforcement passivation was investigated. The
study was conducted at different hydration conditions (water-to-
cement ratio, w/c, of 0.40, 0.50 and 0.67) and in the presence or not
of fly ash (FA), in normal curing and service conditions, that is, in
the absence of chloride or carbonation using OPC equivalents as
reference. Different electrochemical techniques such as corrosion
potential measurements, LPR, and potentiodynamic polarization
curves were used to evaluate the corrosion risk and the corrosion
rate. Coupling different electrochemical techniques provided a
Fig. 1. Steel ribbed rebar used to reinforce mortar samples. Ruler in cm.
67
better understanding of the differences and similarities between
the passivation of the steel reinforcement embedded in BYF and
OPC mortars. Also, the suitability of the current recommendations
and standards to assess the corrosion risk and corrosion rate of the
steel embedded in BYF mortars was discussed.
A last important introductory remark is that, while in the pre-
sent study we focused on the inherent passivating properties of BYF
matrix compared to OPC one, it is, of course, necessary to extend
this study to include the presence of aggressive agents such as
chloride ions and their impact on the BYF matrix performance in
terms of reinforcement corrosion. This is an issue of major concern
and will be a matter of another specific paper.
2. Experimental
2.1. Materials
2.1.1. Steel reinforcement
Thermo-mechanically-treated (TMT) steel ribbed rebars
measuring 14 mm in nominal diameter and 130 mm long were
used as mortar reinforcement, Fig. 1. The chemical composition of
the mild steel used in this study is detailed in Table 1. The values are
the average of four analyses, three at the edge and one at the centre
of cross-section samples, which gave the same chemical composi-
tion considering the precision of the equipment.
Fig. 2a and b show the microstructure of the steel reinforcement,
which is composed of a ductile and tough ferrite (brighter phase)
and pearlite (darker compound) matrix with a high resistant sur-
face rim of tempered martensite. This resulting composite micro-
structure is characteristic of the thermomechanical processing in
which hot steel bars coming out of last rolling mill stands are
quenched through a series of water jets. During such slow cooling,
the heat released from the core tempers the hardened surface while
the core itself turns into ferrite-pearlite aggregates, providing an
optimum combination of high strength, ductility, and bendability.
2.1.2. Cements
An ordinary Portland cement (OPC), designation CEM I 52.5 CE
68 G.Y. Koga et al. / Electrochimica Acta 261 (2018) 66e77

Table 1
Chemical composition of the steel rebar (working electrode) used to reinforce mortars.

Ca Sa Cu Ni Si Cr Mo Mn P V Ti Al Fe
0.21 0.03 0.43 0.21 0.2 0.068 0.041 0.72 0.011 <0.015 <0.010 <0.006 Bal.

Elementary composition determined by spark optical emission spectrometry.

a
Chemical determination by high-frequency furnace and infrared detection.

Fig. 2. Cross-sectional optical micrographs (500x, after Nital 2% etching) taken at a) the core of the sample and b) at the edge. A similar microstructure with equiaxial grains is
observed in longitudinal-section micrographs.

CP2 NF according to the standard NF EN 197-1 [18], and a recently
developed BYF cement were used. The composition of the BYF and
OPC cements and the calculated amount of the clinker phases in the
cements are compiled in Table 2.
2.1.3. Preparation of reinforced mortars
Steel rebars were slightly brushed to remove the heteroge-
neously distributed spots of rust. Mill scale was however kept to
better mimic in-service conditions. After being cleaned in anhy-
drous ethanol, the ends of the rebar were tightly wrapped with
electrical tape before being insulated with epoxy immediately
followed by the application of a heat-shrink tube over it. This
procedure aimed to avoid boundary effects, such as crevice corro-
sion (differential aeration). The final non-insulated area of steel
rebars was about 31 cm2. The rebars were stored in a desiccator
until the production of the reinforced cylindrical mortars. Fig. 3a
illustrates the disposition of the reinforced mortar specimen curing
in the mould and Fig. 3b shows the surface preparation of the rebar
surface and the reinforced mortar specimen.
Six different mortar mixes detailed in Table 3 were used. Each
binder was mixed with water and aggregate according to EN 196-1
[19] and cast in cylindrical moulds containing reinforcements
aligned with the axis of the cylinder. The moulds had a hole in its
bottom to facilitate the placement of the steel rebar before mortar
pouring, as shown in Fig. 3a. The moulds were filled under vibra-
tion. Holed lids were used to cover the top of the moulds and to
keep them hermetically sealed with the steel well aligned. Just after
production and along the tests, the specimens were kept in a 20  C,
95% R.H. controlled chamber to ensure cement hydration while
keeping gaseous dioxygen available at the steel surface.
2.2. Electrochemical measurements in reinforced mortars
Fig. 4 shows the corrosion cell used to carry out electrochemical

Table 2
Characteristics of the binders of the study (Rietveld quantitative phase analysis, readily soluble alkalis, and Blaine specific surface according to NF EN 196-6).

Rietveld Quantitative Phase Analysis

g/100 g

Phases OPC Phases BYF

Alite, Ca3SiO5 60.2 Ye'elimite, Ca4Al6O12(SO4) 31.1

b-Belite, Ca2SiO4 17.9 a0 -Belite, Ca2SiO4 29.0
Ferrite, Ca2(Al,Fe)2O5 10.5 b-Belite, Ca2SiO4 8.0
Aluminate, Ca3Al2O6 5.1 Ferrite, Ca2(Al,Fe)2O5 17.7
Gypsum, CaSO4.2(H2O) 1.8 Anhydrite, CaSO4 6.5
Hemihydrate CaSO4.0.5(H2O) 1.8 Gypsum, CaSO4.2(H2O) 1.5
Calcite, CaCO3 1.5 Periclase, MgO 0.9
Periclase, MgO 0.1 Other phases (inert) 5.9
Free lime, CaO 1.1

Readily Soluble Alkali

K2O 0.77 K2O 0.36

Na2O 0.07 Na2O 0.02

Blaine specific surface (cm2/g) 3680 Blaine specific surface (cm2/g) 4430
 G.Y. Koga et al. / Electrochimica Acta 261 (2018) 66e77 69

Fig. 3. a) Schematic illustration of the process to produce reinforced mortar specimens for electrochemical tests; b) Different steps of preparation of the electrochemical samples
since the surface normalization until the final specimen to be analysed on the right side. WE: working electrode.

Table 3
Mortar mixes used in the production of different reinforced mortars.

Designation Cement (g) Fly ash (g) w/b ratio Sand (g)a Superplasticizerb (%, dry/cement)

OPC (0.50) 450.0 e 0.50 1350 0.00

OPC þ FA 337.5 112.5 0.50c 1350 0.05
BYF (0.40) 511.4 e 0.40 1350 0.30
BYF (0.50) 450.0 e 0.50 1350 0.10
BYF (0.67) 375.0 e 0.67 1350 0.00
BYF þ FA 337.5 112.5 0.50c 1350 0.15
a
Standard sand according to NF EN 196-6.
b
CHRYSO® Fluid Premia 196.
c
w/b ¼ water-to-binder ratio ¼ ratio of mixing water per binder content, with binder ¼ sum of cement and fly ash.

Fig. 4. View of the test set-up used to carry-out electrochemical measurements.

70 G.Y. Koga et al. / Electrochimica Acta 261 (2018) 66e77
measurements. The steel reinforcement was the working electrode
(WE, 31 cm2 of surface) and the electrolyte the interstitial pore
solution which composition was in equilibrium with the unhy-
drated and hydrated solid and gel phases. The counter-electrode
(CE) was placed so as to wrap the mortar surface which was sur-
rounded by a moist sponge band to ensure proper electrical con-
tinuity. CE was prepared from a co-axial carbon sheet, providing a
uniformly distributed electric field. A saturated calomel electrode
(SCE) was placed perpendicularly to the rebar axis in a hole of
15 mm diameter in CE, being the tip of the SCE reference electrode
in contact with the same pre-wetted sponge that assured electrical
continuity with the counter-electrode.
Electrochemical measurements were regularly performed up to
365 days. At each predetermined age, the specimens were removed
from the humid chamber and connected to the potentiostat. The
samples dedicated to the non-destructive techniques were imme-
diately placed back in the humid chamber after measurement to
allow the hydration process to continue in well-controlled condi-
tions for subsequent measurements. The specimens used in
destructive electrochemical methods were discarded after each
test. A BioLogic potentiostat SP-300 with impedance channels was
used in the present work.
 Corrosion potential measurements: Corrosion potential readings
were recorded versus curing time. The data acquisition and
interpretation were based on the ASTM C876-09 [12] and RILEM
TC 154-EMC [20]. Four different samples were monitored to
assure the repeatability.
 Potentiodynamic polarization curves: Corrosion overall behaviour
of reinforced mortars was evaluated by means of large poten-
tiodynamic polarization. Anodic and cathodic curves were ob-
tained separately using different samples because of the
irreversible changes after such wide polarizations. The polari-
zation of each anodic or cathodic branch started with a small
polarization in the opposite direction (jDEj ¼ 30 mV) before a
10 mV/min scan was applied in the desired direction up to
jDEj ¼ 1000 mV, both with respect to the open circuit potential,
Eocp. The obtained curves were corrected for the iR drop after the
measurements with the help of the electrochemical impedance
spectroscopy. Reproducibility of data was ensured by repeating
the tests three times for each polarization, cathodic and anodic,
Fig. 5. Corrosion potential values of the steel rebar embedded in different mortars. The
horizontal dashed lines represent the potential ranges and the corresponding corro-
sion risks suggested by the ASTM C876 [12]. Points presented as mean values and
standard deviations from four different samples.
using different new samples each time. Corrosion current den-
sity values (icorr) were determined by extrapolating the anodic
and cathodic Tafel's regions on the polarization curves around
Ecorr with the intersection being considered as icorr.
 Linear Polarization Resistance (LPR): LPR measurements were
carried out with a 10 mV/min scan with ±10 mV amplitude scan
around the open circuit potential. The apparent polarization
resistance, Rp(app), was straightforwardly determined from the
DE/Di slope in the linear region of the anodic domain. As dis-
cussed later in the Results and Discussion section, this pro-
cedure differs from the usual one (DE/Di slope determined
around the corrosion potential) due to the high dielectric char-
acteristic of the mortar layer. The real polarization resistance,
Rp(real), was obtained from Rp(app) after correction for the elec-
trolyte resistance, Re (the procedure for the estimation of Re is
described in Section 3.1.3). The repeatability of the LPR curves
was verified by analysing four different samples.
 Visual examination: Visual inspection at 365 days of curing was
used to confirm the electrochemical indications. The specimens
were split along the embedded rebar to observe the steel j
mortar interface.
3. Results and discussion
3.1. Effect of different w/c in BYF (0.40, 0.50 and 0.67) compared to
OPC (w/c ¼ 0.50)
The large number of parameters and the long-term (one year)
analysis would yield a huge number of experiments and related
data to be treated. We hence proceeded to the extensive experi-
mental survey of BYF w/c 0.50 and 0.67 as well as OPC w/c 0.50.
Some complementary less-extensive experiments for the BYF w/c
0.40 have been also performed to extend the information about the
impact of the hydration conditions on the passivation of reinforced
BYF mortars.
3.1.1. Corrosion potential monitoring
Corrosion potential values, Ecorr, measured over 365 days are
shown in Fig. 5. First measurements were conducted just after
demoulding of the samples (24 h after specimen fabrication). The
lines at Ecorr ¼ 126 and 276 mV are intended as eye guides for
the empirical criteria for probability of corrosion suggested by the
ASTM C876 [12]. Their applicability to alternative binders such as
BYF has to be defined.
From Fig. 5, one can see that the initial values for the BYF series
are lower than for the OPC one; the lowest corresponding to the
BYF made with the highest water-to-cement ratio (w/c ¼ 0.67).
Between 1 and 60 days, the potential values increase remarkably
for the four series, probably indicating the formation of a passiv-
ating layer and, therefore, a decrease of the corrosion risk. The
values remain the highest for Portland cement. The threshold
of 126 mV is nevertheless exceeded for all series after 60 days.
Between 60 and 180 days, the increase of the potential values is
more gradual. Potential values then stabilize for the OPC and the
BYF 0.40 mortars but continue to increase for the BYF series 0.50
and 0.67, becoming higher than the OPC and BYF 0.40 after 240
days. The corrosion potential for all the series exceeded the
threshold value of 126 mV after 14 (OPC) and 60 (BYF) days of
fabrication. According to the ASTM C876 criteria, this should
correspond to a lower probability of corrosion. The suitability of the
criteria must nevertheless be confirmed by other measurements
which allow the estimation of the corrosion rate for the BYF-based
specimen.
 G.Y. Koga et al. / Electrochimica Acta 261 (2018) 66e77
3.1.2. Potentiodynamic polarization
Corrosion current density values have been straightforwardly
evaluated from the potentiodynamic polarization curves with the
Tafel method. Fig. 6 shows the cathodic and anodic polarization
curves at 28 days for two reinforced OPC and two reinforced BYF
mortars (in each case, one specimen for the cathodic polarization
and one for the anodic one, all specimens w/c ¼ 0.50). Polarization
curves for BYF (w/c 0.40 and 0.67) and OPC at different curing times
are qualitatively quite similar to those in Fig. 6 and are not shown
here.
Table 4 summarizes the ensemble of results, i.e., Tafel slopes, ba
and bc, and icorr. As previously mentioned, six samples were used
for the measurements, three for the cathodic polarization and three
for the anodic one. The icorr values presented are therefore as the
average (and their standard deviations) of six curves. Anodic and
cathodic Tafel slopes can be compared to the published data for
Portland cement [21e25], in the absence of values for steel
embedded in BYF matrices.
From Table 4, it can be seen that all reinforced samples present
icorr values inferior to 0.1 mA/cm2, from 14 to 365 days, regardless
of the cement type. The cathodic Tafel slopes show an increasing
trend with time, indicating a slight decrease in the cathodic ki-
netics. After 365 days, the values range between 156 and 270 mV/
dec. These results are consistent with the reported values for oxy-
gen reduction in alkaline solutions and for steel embedded in
Portland mortars exposed for up to 12 months to 93% R.H [25,26].
Anodic Tafel slopes also increase with time, suggesting formation
Fig. 6. Semilogarithmic polarization curves of reinforced mortars after 28 days of curing and the respective Tafel extrapolation for a) OPC cathodic branch, b) OPC anodic branch, c)
BYF cathodic branch, and d) BYF anodic branch. Anodic and cathodic curves are obtained separately using different reinforced mortar samples. All samples produced with w/
c ¼ 0.50.
71
and ageing of the passive film, with values after 365 days ranging
between 415 and 680 mV/dec.
Potentiodynamic polarization results confirm that steel rein-
forcement embedded in the BYF mortars exhibit negligible corro-
sion rates as the steel rebar embedded in OPC mortars 14 days after
fabrication up to 365 days. The corrosion process seems not to be
limited by lack of oxygen or moisture content but controlled by the
presence of a passivating layer whose protective character in-
creases with time.
The experimental values of the Tafel slopes allow us to calculate
the coefficient B to be used in the Stern-Geary relationship together
with LPR measurements (a quicker and non-destructive alternative
to the Tafel extrapolations). The values obtained with the BYF vary
between 40 and 72 mV and are close to those obtained with OPC
which vary between 54 and 83 mV. In this sense, it is worth
noticing that the recommended B values for reinforced Portland
concretes seem to be suitable to estimate the icorr values of rein-
forced BYF mortars through the LPR technique.
3.1.3. Linear polarization resistance (LPR)
LPR measurements were performed with the same samples
used for potential readings. Fig. 7 displays the polarization re-
sponses of both OPC and BYF series (w/c ¼ 0.50) at 28 days.
As expected for reinforced steel in concrete, the LPR curves in
Fig. 7a and b are not linear. Indeed, the shape of the curves for both
OPC and BYF series at 28 days is typical of steel passivated in
mortar, when the reference electrode is placed on its surface [27]. In
72 G.Y. Koga et al. / Electrochimica Acta 261 (2018) 66e77

Table 4
Values of the electrochemical parameters from Tafel extrapolation of the cathodic and anodic potentiodynamic polarization curves.

Days Sample ba (mV/dec.) bc (mV/dec.) Bc (mV) icorr (mA/cm2)

14 OPC (w/c ¼ 0.50) 364 ± 3 190 ± 5 54 ± 1 0.09 ± 0.01

BYF(w/c ¼ 0.50)a 338 ± 8 156 ± 37 46 ± 8 0.04 ± 0.01
BYF (w/c ¼ 0.67) 360 ± 30 120 ± 10 40 ± 1 0.07 ± 0.01
28 OPC (w/c ¼ 0.50) 410 ± 20 190 ± 10 57 ± 1 0.077 ± 0.003
BYF(w/c ¼ 0.50) 373 ± 50 157 ± 37 48 ± 10 0.05 ± 0.01
BYF (w/c ¼ 0.67) 404 ± 40 150 ± 1 46 ± 2 0.079 ± 0.005
56 OPC (w/c ¼ 0.50) 420 ± 20 220 ± 4 62 ± 1 0.09 ± 0.01
BYF(w/c ¼ 0.50) Not meas. Not meas. Not meas. Not meas.
BYF (w/c ¼ 0.67) 403 ± 20 185 ± 3 55 ± 1 0.10 ± 0.02
84 OPC (w/c ¼ 0.50) 480 ± 10 241 ± 1 69 ± 1 0.06 ± 0.02
BYF(w/c ¼ 0.50) 403 ± 1 165 ± 40 50 ± 9 0.02 ± 0.01
BYF (w/c ¼ 0.67) 424 ± 36 190 ± 30 57 ± 8 0.09 ± 0.01
181 OPC w/c ¼ 0.50)b 470 ± 10 250 ± 10 71 ± 1 0.069 ± 0.003
BYF(w/c ¼ 0.50) 377 ± 8 194 ± 18 56 ± 4 0.056 ± 0.003
BYF (w/c ¼ 0.67) 473 ± 4 200 ± 10 60 ± 1 0.06 ± 0.01
365 OPC (w/c ¼ 0.50) 680 ± 13 270 ± 4 83 ± 12 0.09 ± 0.02
BYF(w/c ¼ 0.50) 415 ± 14 156 ± 10 49 ± 2 0.02 ± 0.01
BYF (w/c ¼ 0.67) 538 ± 16 241 ± 3 72 ± 1 0.066 ± 0.004
a
Measured at 15 days.
b
Measured at 177 days. Not meas. ¼ Not measured.
c
B ¼ (ba.bc/2.303(baþ bc)).

Fig. 7. Experimental polarization curves around Eocp for a) reinforced OPC mortar, and b) reinforced BYF mortar. Measurements carried out at 28 days of curing using jDEj ¼ 20 mV
and scan rate of 10 mV/min.

these conditions, it senses the capacitive response of the subjacent
mortar layer which is dominated by the low-frequency transients
produced by the sudden application of the polarization at the
beginning of the scan. These transients have been associated with
the capacitive response of the mortar [27,28]. As the potential ramp
gets closer to the open circuit potential (Eocp), the current density
presents a linear behaviour, which means that the potential scan
rate allows the current response to approximate that of steady-
state conditions. For potentials beyond Eocp, the measured slope
of current density vs. potential, Rp, has been considered to as the
sum of Rp,true and Re [28], being Re taken as the real axis interception
of the high-frequency loop d assimilated to the dielectric response
of the mortar layer d of the Nyquist electrochemical impedance
diagram [29], as illustrated in Fig. 8.
The corrosion current density, icorr, is then calculated over 365
days according to the Stern-Geary equation [30]:
RpðrealÞ ¼ Rp  Re
!
B h i tlement which generates local low pH values at the steel j mortar
icorr ¼ mA=cm2
RpðrealÞ
As mentioned before, B values used for OPC mortars seem to be
also suitable for BYF cements. The icorr values have thus been
calculated from LPR measurements, taking B ¼ 26 mV and
assuming a maximum error factor of two [13], and they were
compared with those obtained directly by Tafel extrapolation
(Table 5). Good agreements between the values from the two
methods are observed. LPR measurements are more interesting to
obtain instantaneous icorr values as the method is non-destructive
and quick compared to the Tafel method.
Fig. 9 shows the evolution of the corrosion current density (icorr)
over time. The values can be compared to the RILEM recommen-
dations [13]. Values of icorr below 0.1 mm/cm2 correspond to negli-
gible corrosion rates while values between 0.1 and 0.5 mA/cm2
correspond to low corrosion level.
The icorr values decrease sharply during the first 7 days, being
the highest for the BYF (w/c ¼ 0.67) while the values are similar for
the others BYF and OPC series. Although further research is needed
(1) to understand this difference, a reasonable explanation is that
higher w/c ratios possibly induces bleeding water and plastic set-
(2) interface [31,32].
 G.Y. Koga et al. / Electrochimica Acta 261 (2018) 66e77 73

Fig. 8. Determination of Re from the Nysquist diagram for a) reinforced OPC mortar, and b) reinforced BYF mortar.

Table 5
Comparison between the corrosion current densities, icorr, calculated from LPR and obtained by Tafel extrapolation.

Samples Method icorr, 102 (mA/cm2)

14 days 28 days 84 days ~181 days 365 days

OPC (w/c ¼ 0.50) LPR 8.1 ± 0.4 6.8 ± 0.4 7.2 ± 0.9 6.1 ± 0.9 4.9 ± 0.5
Tafel 9±1 7.7 ± 0.3 6±2 6.9 ± 0.3 9±2
BYF (w/c ¼ 0.50) LPR 10 ± 2 8±1 6±1 6±1 6±1
Tafel 5±1 4±1 3±1 5.6 ± 0.3 3±1
BYF (w/c ¼ 0.67) LPR 13 ± 03 10 ± 2 8±2 6±1 5±1
Tafel 7±1 7.9 ± 0.5 9±1 6±1 6.6 ± 0.4

corrosion risk levels indicated by the corrosion potential mea-

surements, Fig. 5, performed on the same samples at the same
curing times. The corrosion level is then negligible after one or
several weeks, depending on the cement type and water-to-cement
ratios.

3.1.4. Impact of the addition of fly ash

Fig. 9. Indication of the variation of icorr with time for reinforced BYF and OPC cement
mortars. The values are calculated from LPR measurements and Stern-Geary rela-
tionship, taken B ¼ 26 mV. Points are presented as mean values and standard de-
viations from four different samples.
Corrosion current densities for the four series continue to
decrease between 7 and 28 days, but more gradually and then
stabilized more or less between 28 and 365 days. Despite the initial
differences among the samples, the icorr finally reaches similar
values after 120 days, indicating negligible corrosion rates for all
investigated specimens.
Before reaching a negligible corrosion level, the LPR results
show that the initial icorr values are superior to 0.1 mA/cm2, corre-
sponding to non-negligible corrosion rates. This is in line with the
The addition of fly ash (FA) had no significative impact on the
corrosion-related parameters, Ecorr and icorr, for the OPC samples
(Fig. 10a and c, respectively). OPC samples with FA showed steady
potential values slightly higher than in the absence of FA and clearly
and permanently in the low-risk range, with corrosion current
values almost identical to the ones in the absence of FA all over the
365 days of testing.
It is worth noticing however that, for the BYF matrices, even if
no clear corrosion tendency has been identified, the effect of the
presence of FA was not negligible as for the OPC. As seen in Fig. 10b,
the increase of Ecorr with time was much less pronounced than in
the absence of FA and the final values were only slightly higher than
the threshold of the intermediate/unknown corrosion risk. In a
similar tendency, icorr values in the presence of FA (Fig. 10d),
although still low, have shown a slight but monotonic increase with
time reaching the lower limit of the uncertainty domain. No
significative corrosion attack has nevertheless been identified after
visual observation as shown in the next section.
Another interesting effect of the FA additions is on the electro-
chemical response of the cementitious bulk (i.e. of the mortar
resistance, Re). For OPC samples with no FA, the Re increases by a
factor of 5 between 1 and 365 days, whereas for OPC samples with
FA addition, the factor is about 37 (Fig. 11a). Similar trends have
been reported [33,34] and related to the pozzolanic reaction which
decreases the porosity and the connectivity of pores. Also, fly ash
may be used as fine granulates and upon hydration it has the
74 G.Y. Koga et al. / Electrochimica Acta 261 (2018) 66e77

Fig. 10. Effect of addition of fly ash in the corrosion potential (A, B) and corrosion current density (C, D) of reinforced OPC and BYF mortars.

Fig. 11. Impact of the addition of FA on the mortar resistance values of a) reinforced OPC specimens, and b) reinforced BYF specimens.

capability of partially obstructing voids and pores. Even before
reacting, fly ash particles that are composed of cenospheres (hollow
spheres) can modify the dielectric behaviour of a material in which
they are incorporated [35].
Considering the samples based on BYF cements, Fig. 11b, for
samples with no FA addition, the resistance increases by a factor of
about 10 from 1 day to 365 days of curing whereas, for BYF samples
with FA, the factor is about 70. It is hard to find an explanation in
the literature as the data on the role of fly ash blended to BYF or CSA
cements are still limited. A study pointed out that FA may accelerate
the formation of ettringite, Ca6Al2(SO4)3(OH)12.26H2O, yielding to a
denser microstructure which could explain, in part, the initial in-
crease of Re observed [36]. At longer-term, fly ash can be expected
to remain inert particles due to the absence of portlandite, Ca(OH)2,
known to initiate pozzolanic reactions. But this assumption is
contradicted by a recent study showing the contribution of fly ash
in the hydration process of CSA cement [37].
In any case, because of the non-negligible resistance of the
mortar compared to the measured polarization resistance from LPR
in presence of fly ash, the correct IR compensation becomes
mandatory to estimate the icorr even when the steel rebar is highly
passivated.
3.2. Visual examination
Different electrochemical measurements point out that the
corrosion of the steel embedded in the BYF and OPC mortars is
negligible. Additional reinforced mortar samples were made and
split after 365 days of curing to observe the presence of any
corrosion product.
For OPC specimens with and without FA, no visible corrosion
product is observed, as seen in Fig. 12a and b. Similarly, no corrosion
 G.Y. Koga et al. / Electrochimica Acta 261 (2018) 66e77
products are observed after splitting reinforced BYF with w/c of
0.40, 0.50, and containing FA (Fig. 12c, d, and f, respectively). For
these samples, the active corrosion during the first days of hydra-
tion is not enough to promote visible “rust” after 365 days of the
survey. These observations confirm the fact that the corrosion rate
of the steel rebar embedded in OPC and BYF cement mortars drops
rapidly ensuring steel protection since early ages.
Some signs of corrosion are found on the steel rebar surface
embedded in BYF (w/c ¼ 0.67) mortar for 365 days, Fig. 12e. Pre-
sumably, the corrosion spots were certainly formed at early age
while the pH of the pore solution is below 12. It is interesting to
note that the corrosion products are exclusively concentrated at the
lower half of ribs of the rebars. This observation points out that
steel j mortar interface is one of the most dominant influencing
parameters together with pH [38]. The ribs regions are more prone
to present higher density of metallurgical defects and residual
stress from the thermomechanical processing and heat treatment.
Additionally, porosity and bleeding may be more pronounced at
lower rib region due to the casting direction [31].
4. Final remarks
4.1. Suitability of the current practices to assess steel corrosion in
BYF mortars
Both the increase of Ecorr during hydration (cf Fig. 5, indication of
Fig. 12. Steel j mortar interfaces, after 365 days, of a) OPC (w/c ¼ 0.50), b) OPC þ FA, c) BYF (w/c ¼ 0.40), d) BYF (w/c ¼ 0.50), e) BYF (w/c ¼ 0.67), and f) BYF þ FA.
75
a decrease of corrosion risk) and the decrease of icorr (cf Fig. 9,
decrease of the corrosion rates) suggest the formation of an effec-
tive passivating layer on the reinforcing steel surface embedded in
BYF matrices used in the present study. The presence of this passive
layer is also consistent with the results from polarization curves. In
addition, the usual evaluation criteria (ASTM C876 and RILEM) for
the Portland cement matrices appear to be applicable for the BYF
cement matrices of our study, as shown in Fig. 13 by the good
correlation between the Ecorr and icorr,LPR. Indeed, as it clearly ap-
pears from the figure, the points for all different samples merge in a
single cloud indicating that the higher the corrosion potential, the
lower the corrosion current density with values in overall good
agreement with the ones stated in the usual procedures.
This means that the survey and study of the corrosion behaviour
of steel embedded in reinforced BYF matrices are possible with the
current standards (e.g. ASTM C876 [12]) and recommendations (e.g.
RILEM TC 154-EMC [13]) in the same conditions and with the same
assessment criteria. Furthermore, the B value required to calculate
the corrosion current density from LPR measurements is quite the
same for the BYF-based samples than for the OPC ones.
4.2. Influence of the pore solution chemistry on steel passivation
The time required for steel passivation is an indicator of the
protectiveness ability of the interstitial pore solution. The pore
solution chemistry affects the initial rate of the oxide film growth so
76 G.Y. Koga et al. / Electrochimica Acta 261 (2018) 66e77
Fig. 13. Experimental correlation between Ecorr and icorr obtained by LPR, taking B
equal to 26 mV. Points of all sample series plotted regardless curing time.
that differences in the electrochemical responses can be ascribed to
the differences of the electrolyte upon hydration [39,40].
The interstitial solution during the hydration of the Portland
cement rapidly becomes highly alkaline, reaching pH values above
13 after the first minutes. This strongly alkaline medium is known
to promote the formation of a passivation layer which assures
negligible corrosion rates. The corrosion potential values measured
correspond well to a low corrosion risk and the current density to
negligible corrosion rates.
The results of the first week after the fabrication of the samples
indicate, however, the possibility of a slight corrosion to take place
due to the time needed to form a sufficiently protective layer. The
reinforced OPC mortars require 2 days to their icorr values to reach
the transition between passive and active corrosion (0.1 mA/
cm2  icorr  0.2 mA/cm2) and 7 days to reach values below 0.1 mA/
cm2. Similarly, Poursaee and Hansson [41] have shown that the
time required for the corrosion rate of steel in Portland mortar to
drop to a rate typically considered to be passive is approximately 7
days and that it continues to decrease slowly for a long period.
For the BYF cement, the pH of the interstitial solution is less
alkaline during the first hours (around 10.5) and then it increases
sharply. Fig. 14 shows the pH evolution over 1440 min (1 day) for
BYF and OPC pore extracts.
The initial lower pH values could be an explanation for the initial
lower corrosion potential values and higher current density
compared to the OPC samples. The electrochemical responses
(corrosion potential measurements and LPR curves) confirmed that
the initial low alkalinity of BYF matrices may expose the steel
reinforcement to a higher corrosion risk and higher corrosion rate
compared to OPC analogous. However, the subsequent increase of
pH after the first hours assures the protection of the steel
embedded in BYF mortars thanks to the formation of an effective
passive layer as for the reinforced Portland mortars.
Thus, the scenario seen for the BYF matrices of this study is as
follows: a non-passivating pore solution at very early age (initial
few hours) turning into a protective electrolyte within the hydra-
tion progress. It is also worth mentioning that the different possible
pH values depending on the composition of the BYF cements and
the progress of the hydration reactions may be an explanation of
the controversial conclusions found for different studies in the
literature about steel corrosion in CSA or BYF cement matrices
Fig. 14. pH evolution over one day (1440 min.) of pore solutions extracted from BYF
(w/c of 0.50 and 0.67) and OPC (w/c ¼ 0.50) cement pastes.
[9e11].
5. Conclusions
 The results pointed out that mild steel effectively passivates in
BYF cement mortars. The time required for the corrosion current
density to drop to values typically considered to be passive
(<0.1 mA/cm2) was approximately 28 days regardless the w/c
ratio and fly ash additions. Corrosion potential took even longer
time to reach the values related to low probability of corrosion
(Ecorr > 126 mV/SCE), especially for BYF þ FA.
 Cathodic Tafel slopes were ranged between 156 and 270 mV/dec
which are consistent with the reported Tafel slopes for oxygen
reduction. Anodic Tafel slopes, after 365 days, were ranged be-
tween 415 and 680 mV/dec. It was found that ba increases with
time (formation and ageing of the passive film). Calculation of
the B values from experimental Tafel slopes showed that the
recommended values (26 mV for active and 52 mV for passive
states) are a reasonable choice for reinforced BYF as for OPC
mortars.
 Visual inspection indicated that the corrosion rates of steel
embedded in OPC and BYF drop quickly to negligible values and
no corrosion products are visible after 365 days, except for BYF
(w/c ¼ 0.67). In this case, the local low pH and the bleeding
surrounding the ribs of the steel rebar embedded in BYF (w/
c ¼ 0.67) mortars generated non-negligible initial corrosion
rates for a sufficient period to form visible corrosion products.
Steel was however fully passivated after 28 days and the
corrosion products observed after 365 days are attributed to the
active initial period.
 Good agreement between the electrochemical techniques and
visual inspections indicated that the ASTM C876 and RILEM
recommendations can be used to assess the corrosion of steel in
reinforced BYF cement mortars. Some controversial aspects of
steel protection in sulfoaluminate matrices were discussed.
Acknowledgements
The authors gratefully acknowledge the financial support of the
Brazilian institution CNPq (grant number 229886/2013-2), of the
French institution ANRT (grant number 2013/1440), and of the
 G.Y. Koga et al. / Electrochimica Acta 261 (2018) 66e77
LafargeHolcim group.
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