Construction and Building Materials 40 (2013) 280290

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Construction and Building Materials

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Electrochemical realkalisation of carbonated concretes Inuence of material

characteristics and thickness of concrete reinforcement cover
P.H.L.C. Ribeiro a, G.R. Meira a,b,, P.R.R. Ferreira b, N. Perazzo a
a
b

Urban and Environmental Engineering Postgraduate Programme, Federal University of Paraba, 58051-900 Joo Pessoa, Brazil
Federal Institute of Education, Science and Technology of Paraba, R. Dep. Balduno M. de Carvalho, 155/1104, 58.036-860 Joo Pessoa, Brazil

h i g h l i g h t s
" Pozzolanic addition means more total charge demanded for the treatment.
" Increasing concrete cover thickness will increase total charge for realkalisation.
" Lower water to cement ratio means more total charge demanded for the treatment.
" Reinforcement repassivation can be seen by corrosion potential measurements.
" More charge demanded for realkalisation means a shorter time for repassivation.

a r t i c l e

i n f o

Article history:
Received 22 May 2012
Received in revised form 6 September 2012
Accepted 23 September 2012
Available online 6 December 2012
Keywords:
Carbonation
Concrete
Electrochemical realkalisation
Repassivation

a b s t r a c t
This work studies the inuence of concrete characteristics, such as cement type and water to cement
ratio, and concrete cover thickness on the electrochemical realkalisation of carbonated concretes. Results
show the treatment efciency for recovering concrete alkalinity. More time and total electrical charge
passed are demanded in proportion as water to cement ratio decrease, concrete cover thickness increase
and when concrete has lower alkalinity reserve. The tendency of reinforcement reaching passive condition is observed by corrosion potential measurements. For this variable, concretes that demand more
charge and time for realkalisation reach the passive condition in a shorter time. Corrosion current density
shows a decrease tendency over time and, although not reaching the level that represents passive condition in most of the cases, it was not far from this reference.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Concrete is a material that usually presents high levels of alkalinity, which helps on the formation and protection of passivation
lm on metal surfaces in reinforced concrete structures. Since this
initial condition of high alkalinity and the concentration of depassivating ions below a certain threshold are maintained, corrosion
process does not start [1]. However, this protective lm can be broken down due to carbonation or in the presence of concentrations
of chloride ions higher than a certain critical content [2,3]. In the
specic case of concrete carbonation, the pH goes down due to carbonates precipitation as a consequence of hydroxides and other
hydrated phases reaction with carbon dioxide [4].

Corresponding author at: Federal Institute of Education, Science and Technology of Paraba, R. Dep. Balduno M. de Carvalho, 155/1104, 58036-860 Joo Pessoa,
Brazil. Tel.: +55 83 3246 5124; fax: +55 83 3208 3088.
E-mail
addresses:
gibsonmeira@yahoo.com,
gibson.meira@ifpb.edu.br
(G.R. Meira).
0950-0618/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2012.09.076

As a rehabilitation method or as a preventive treatment, the

realkalisation method has been used to recover concrete alkalinity
nearby the reinforcing region [57]. The advantage of this method
is that when the treatment nishes the system can be unassembled
and concrete structure can follow its role without larger destructive interventions as in conventional parch repair treatment [8].
Studies about realkalisation treatment which focused on understanding the phenomenon characteristics, like transport mechanisms involved [914], efciency on reinforcement repassivation
[1519], efciency of different electrolytes on realkalisation [20],
effects on concrete properties [21,22] and side effects [2326],
have been carried out during the last years.
On site applications were introduced at the end of 1980s and a
signicant number of structures have been treated with this
technique. Some documents report these experiences [15,27] and
show the ability of the technique in recovering protective pH
levels. These studies also show that, even after some years, the
alkalinity remains at high levels, which would be enough to protect
the reinforcement [15].

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P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280290

On the other hand, the effectiveness of the treatment in repassivating the reinforcement has been questioned [28,29] and,
although some work is being carried out on this specic topic
[30], there is still not a consensus and more research is necessary.
Moreover, the inuence of material or structure characteristics on
the method behaviour and its nal results was studied at a lower
level [30,31].
Taking into account this gap in knowledge, this work studies the
inuence of cement type, water to cement ratio and reinforcement
concrete cover on electrochemical realkalisation of carbonated
concretes and its efciency on repassivation of reinforcements.
2. Fundamentals of electrochemical realkalisation
In the electrochemical realkalisation treatment, an external
power supply is connected to the reinforcement (cathode) and to
an auxiliary anode embedded in an external electrolyte (Fig. 1).
The auxiliary anode is usually made of inert titanium mesh and sodium carbonate solution is the most common electrolyte. An electrical current density between 0.8 and 2 A/m2 in respect to
concrete surface is applied to the system for a few days [5], until
the concrete cover is realkalised.
Material realkalisation takes place by hydroxyl generation
around the steel reinforcement due to water electrolysis, as described in Eqs. (1) and (2) [10] and it is helped by electro-osmosis
of electrolyte solution [9,1114]. Additional mass transport by capillary absorption can take place in specic cases where the substrate is not saturated, but this effect is usually bordered to
concrete surface [8]. Mass transport by diffusion can take place,
but it is usually neglected due to its low inuence in this process
[9]. As an electrical eld is on, electro-migration of ions also take
part, making ions move according to their electrical polarity. All
these mechanisms are represented in Fig. 1.

1=2O2 H2 O 2e ! 2OH

2H2 O 2e ! 2OH H2"

At the anode region, hydroxyl ions are oxidised or water is electrolysed, as described in Eqs. (3) and (4) [5], which decreases pH
level in this region.

2OH ! 1=2O2 H2 O 2e

2H2 O ! O2 4H 4e

4


The water electrolysis increases the OH concentration close to

the reinforcement surface and pH reaches a level close to 14 just
after the treatment. In time, pH rises for levels that, theoretically,
are still enough for the steel reinforcement to reach the passive
condition [11]. As hydroxide ions are negatively charged, they
move towards the anode, as well as Na+ ions move towards the
cathode. Considering the differences on ion transport numbers,
about 20% of alkalinity generated in cathode surroundings remains
in this region [8].
Taking into account that water electrolysis is the main phenomenon involved, the total charge passed is the variable that strongly
inuences realkalisation [19]. The number of hydroxides generated
nearby the reinforcement is a consequence of the applied current
during the treatment. It means that, the longer the treatment, more
hydroxides are generated and higher alkalinity levels are reached
at surrounding reinforcement region.
Although electro-osmosis is claimed to transport carbonates towards the reinforcement and play an important role in realkalisation process [13], some works did not observe this kind of mass
transport [27]. With regards to the contribution of electro-osmotic
ux, the alkaline solution moves from the external anode region to
the cathode region through the concrete pores network [9,12]. This
ux depends on the electrical eld applied, but it is mainly inuenced by the zeta-potential [11], which is continuously changing
due to the changes of species in the aqueous phase and consequent
changes of the electrical double layer in the walls of the pores [13].
Thus, these conditions need to be favourable for the electro-osmotic ux to happen at a signicant level.
Concerning the realkalisation treatment, an important point
would be to know when the realkalisation system can be turned

Fig. 1. Simplied design of the electrochemical realkalisation process.

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P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280290

off based on total charge passed or treatment time. Values between

200 and 450 A h/m2 have been reported in literature [32], which
means a period between 8 and 18 days for a current density of
1 A/m2 related to concrete surface. However, as these values also
depend on aspects related to material and structure characteristics,
they can vary in the long term, as discussed in the present work.

After identifying reinforcement depassivation, specimens were removed from

the carbonation chamber, were saturated by immersion in deionised water until
mass stabilisation, which took a maximum period of 7 days. Then, the specimens
were subjected to electrochemical realkalisation treatment. The saturation procedure was adopted to avoid the wicking effect during the treatment.

3.3. Realkalisation procedures

3. Experimental work
3.1. Casting and curing concrete specimens
Prismatic concrete specimens with 8  8  8 cm were cast using Brazilian Portland Cements V (high early strength Portland cement ASTM Type III) and IV (Portland pozzolan cement ASTM Type IP), which physical and chemical characteristics
are presented in Table 1 as cements I and II, respectively. In this case, the commercial Portland pozzolan cement used incorporated calcined clay as pozzolan addition
in its composition. Water to cement ratios were set at 0.55 and 0.65, comprising
concrete mixtures and properties presented in Table 2. Coarse aggregate and sand
had 9.5 mm and 4.8 mm maximum diameter, respectively.
Two reinforcement bars with 6.3 mm diameter and 10 cm length were embedded in each specimen and were placed respecting 1 or 2.5 cm of concrete cover
(Fig. 2), comprising the specimens characteristics and codes presented in Table 3.
The option of embedding two bars in each specimen was to consider an arrangement that can take place in eld applications. Two reinforced concrete specimens
were cast for each experimental condition. Reinforcements were previously cleaned
by mechanically brushing their surfaces until removing any previous surface oxidation products. Afterwards, these bars had their extremities covered with an insulating tape, delimiting an intermediate constant exposing area of 6 cm2 (Fig. 2).
Duplicate reinforced specimens were cast to monitor realkalisation of concrete cover as described in Section 3.4.
Furthermore, additional non-reinforced cylindrical specimens (10  20 cm)
were cast to monitor carbonation front advance during accelerated carbonation
procedures. All specimens were cured in a wet chamber for 7 days, to represent a
condition closer to eld applications, and remained in laboratory environment until
completing 180 days, when it is expected that the concrete reach a more stable
microstructure. During this period, they were covered by a plastic lm to avoid
early carbonation.

3.2. Accelerated carbonation

After this initial period of 180 days, the specimens were subjected to accelerated carbonation in a saturated carbonation chamber under 75 5% of relative
humidity and 28.5 1 C of temperature. The usual accelerated carbonation conditions reported in literature with CO2 concentrations below 10% and relative humidity between 50% and 65% [33] could not be adopted in this case. During this
carbonation period, sacricial non-reinforced concrete specimens (cylinders) were
used to monitor the carbonation front advance. This was done by means of a phenolphthalein test, which is based on a pH indicator (1% phenolphthalein solution)
that becomes dark pink in environments with pH higher than nine and colourless
for lower values of pH. The carbonation front was veried on 1 cm slices cut perpendicularly to cylinder axis.
Simultaneously to carbonation front advance monitoring, electrochemical measurements were taken to identify reinforcement depassivation. This was indicated
by corrosion potentials more electronegative than 350 mV (CSE copper sulphate
electrode) [34] and corrosion current density higher than 0.1 lA/cm2 [35] as commented in Section 3.3.

Table 1
Chemical composition and physical properties of cements.
Composition/property

Cement I

Cement II

SO3 (%)
SiO2 (%)
Al2O3 (%)
Fe2O3 (%)
CaO (%)
MgO (%)
Na2O (%)
K2O (%)
Insoluble residue IR (%)
Loss on ignition Li (%)
Free CaO
Blaine (cm2/g)
Specic density (g/cm3)

3.19
18.96
3.92
2.95
61.06
3.08
0.15
1.03
0.67
1.15
2.96
4020
3.14

2.69
25.75
5.44
2.44
51.56
4.51
0.23
1.86
16.81
4.47
1.13
4670
2.97

For realkalisation treatment, an electrical eld was generated between the reinforcement (cathode) and an external anode attached to the concrete surface using a
power supply, which was continuously controlled to produce an average cathodic
current density of 2 A/m2 in respect to the exposed concrete surface. In this
arrangement, the anodes were made of activated titanium mesh placed on the surface of the specimen and the electrolyte was a sodium carbonate (NaCO3) 1 M solution, in a similar arrangement as the one presented in Fig. 1.
The option for this level of current density and sodium carbonate based electrolyte was a consequence of experiences presented in some previous papers
[5,9,15,19], which show the efciency of this arrangement without signicant risks
to change concrete microstructure.
Based on this set up and on electrical current and potential difference measurements directly obtained on this circuit to monitor the target current density, it was
possible to obtain the ohmic resistance of the system. This helped on visualising the
high initial resistance of the system and its gradual decrease due to the ionic ux
increase.

3.4. Alkalinity monitoring

The system arrangement for the treatment was turned on until the concrete
reinforcement cover was completely realkalised. This was monitored in two duplicate specimens cast with this objective. These specimens were periodically (up to
ve times during the treatment period) sliced close to the reinforcements
(Fig. 3a) using a diamond-based tool under a dry cutting process. This was done initially after approximately 24 h and 90 h of treatment for more and less porous concretes, respectively, and it was followed at shorter intervals of time depending on
the alkalinity advance in the previous measurement. After being sliced, the specimens had their surfaces cleaned with high pressure air jets and then, a 1% thymolphthalein solution was sprayed on them as a pH indicator (Fig. 3b). This
colorimetric indicator becomes blue for pH above and around 10.5 and colourless
for lower values of pH, showing the region where concrete alkalinity was recovered.
Taking into account the blue area indicated by the phenolphthalein solution and
the previous carbonated area, considering the area in front of the exposed reinforcement length as shown in Fig. 3b, it was possible to monitor the realkalisation advance in the concrete cover region by means of the ratio between the realkalised
area and the previous carbonated area. This ratio was expressed as a realkalised
fraction of the total carbonated area in the cover region. Digital images captured
from sliced surfaces obtained for each alkalinity analysis were used for this purpose,
as represented in Fig 3b.
Complementary pH analyses were also carried out using the following procedures. When all the concrete cover was realkalised and thus the treatment was nished, the specimens were broken and samples close to the reinforcement were
collected using a diamond-based tool. These samples represent an 8 mm thickness
layer nearby the reinforcement surface and were collected for reference (REF), carbonated (CARB) and realkalised (REA) specimens. Additionally, similar samples
were also extracted at three different depth bands (08; 816 and 1625 mm with
respect to concrete surface) for specimens with 25 mm concrete cover thickness.
After being extracted, these samples were crushed to small pieces (about 2 mm)
and were immersed in deionised water for 24 h respecting the 1/1 ratio and stored
in an atmosphere with nitrogen to avoid further carbonation. After this period, it
was assumed that the medium was close to the equilibrium and the resultant solution was used to analyse the hydroxide concentration and, consequently, the pH of
this equilibrium solution. This extraction procedure is similar to that described by
Castellote et al. [36]. No further mathematical data treatment was adopted to t
pore-pressing condition as proposed in the same work [36] due to its limited validation. It is clear that this equilibrium solution does not accurately represent the
concrete porous network solution, but in some way it represents a potential alkalinity of the samples and thus it was used only for comparative analysis, in a similar
way to other previous works [37,38].

3.5. Electrochemical measurements

Electrochemical measurements were carried out during the carbonation and
electrochemical realkalisation periods. This was done on single measurements of
open circuit corrosion potential (Ecorr) and instantaneous corrosion current density
(icorr) measurements. A potentiostat, model VMP3 from PAR (Priceton Applied Research), was used to perform these measurements. Linear polarisation technique
was used for corrosion measurements. A potential difference of 10 mV with respect to the free corrosion potential and a scanning rate of 0.17 mV/s were applied.

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P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280290

Table 2
Concrete mixtures and properties.
Concrete
Cement type

C1
I

C2
I

C3
II

C4
II

Cement (kg/m3)
Sand (kg/m3) maximum diameter 4.8 mm
Coarse aggregate (kg/m3) maximum diameter 9.5 mm
Plasticiser (kg/m3)
w/c ratio

362
858
934
1.77
0.55

349
828
902

0.65

360
853
928
3.51
0.55

347
823
896

0.65

Slump (cm)
Compressive strength (MPa) 90 days
Absorption (%)
Water porosity (%)
Density (g/cm3)

6
40.2
3.14
7.11
2.26

16
36.3
4.62
10.21
2.21

5
28.9
4.52
10.04
2.22

9
22.3
5.67
12.32
2.17

Fig. 2. Schematic design of concrete specimens.

Table 3
Specimen codes.
Concrete

Reinforcement concrete cover (mm)

Specimen code

C1
C2

10
10
25
10
10
25

C1/10
C2/10
C2/25
C3/10
C4/10
C4/25

C3
C4

The ohmic drop was compensated and the icorr values were obtained by Stern and
Geary equation [39]. The measurements set up used a copper sulphate electrode
(CSE) as reference electrode and a stainless steel plate as a counter electrode (Fig. 4).
Regarding electrochemical measurements to indicate reinforcement depassivation, this work accepted that icorr values higher than 0.1 lA/cm2 indicate metal
depassivation, as well as Ecorr values more electronegative than 350 mV (CSE)
[34,35]. This electrochemical monitoring was continued during 1 year after the
realkalisation treatment was over. Throughout this period, the specimens were protected with a plastic lm and stored in a laboratory environment to avoid further
carbonation.

Fig. 3. Evaluation of the realkalised area specimen cutting (a) and comparison of areas (b).

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P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280290

Fig. 4. Electrochemical measurements.

4. Results and discussion

4.1. Ohmic resistance of the system
The ohmic resistance of the system (reinforcement (cathode)
concreteelectrolyteanode) was obtained from electrical current
and voltage measurements and it is represented in Fig. 5. It can
be seen that ohmic resistance starts at high levels but tends to decrease during the treatment. As carbonated concretes usually have
higher resistivity [11] and ionic ux is starting, these high values
are expected. As time goes by, the ionic ux increases as well as
the electrical current, which contributes to lower resistance values.
The ohmic resistance increases for lower w/c ratio concretes
and for concretes made with cement I (C1, C2). This is related to
the lower porosity levels observed (Table 2), which makes ionic
transport in cover layers of concrete during the treatment more
difcult. In a similar way, specimens with thicker concrete cover
also present higher ohmic resistance of the system, due to its thicker barrier to ionic transport. This makes resistance data for
arrangements with specimens with 25 mm concrete cover thickness higher than those with thinner covers for measurements after
stabilisation (see data after 70 h in Fig. 5).

4.2. Total electrical charge passed for completing realkalisation

The total charge capable to realkalise carbonated concrete cover
was monitored by multiplying current density and time. Results

Fig. 5. Ohmic resistance of the system during the treatment.

are presented in Fig. 6, which shows the relationship between total

charge passed (in respect to concrete surface) and realkalised fraction of the total carbonated area in the cover region, as described in
Section 3.4.
Results show that concretes made with Portland pozzolan cement (C3, C4) required more charge to complete concrete realkalisation. It could be expected that, as these concretes presented
higher porosity (Table 2) and lower ohmic resistance, less charge
would be necessary. However, it did not happen and concretes
with pozzolanic addition were harder to be realkalised.
To explain this behaviour, two aspects may be taken into account. First, as concretes made with pozzolan cement have less
alkalinity reserve due to the portladite consumption in pozzolanic
reactions, they tend to reach lower levels of alkalinity after carbonation (see Section 4.4). Thus, comparing concretes without mineral
additions (C1, C2) with those that use Portland pozzolan cement
(C3, C4), the last ones need more total electrical charge passed to
complete the realkalisation of a same thickness of concrete cover.
Furthermore, as more total charge passed is demanded as a consequence of the rst aspect, more hydrogen cations are generated in
the anodic region, which contributes to neutralise some of the
hydroxides produced at the cathode region.
The inuence of w/c can be observed in Fig. 6. Comparing concretes C1 and C2, it can be seen that concrete C1 need
330 A h=m2concrete to complete realkalisation, in proportion as concrete C2 need 240 A h=m2concrete , which means an additional charge
of 90 A h=m2concrete when w/c changed from 0.65 (C2) to 0.5 (C1). As

Fig. 6. Progress of the realkalised fraction as a function of the total charge passed.

P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280290

commented by Bertolini et al. [27], concretes with lower w/c need

a higher total charge passed to complete the treatment and thus,
under the same current density, the treatment takes longer to realkalise a given concrete cover thickness. In the case of concretes C3
and C4, there is a similar behaviour with a difference of about
50 A h/m2.
Concretes with higher reinforcement cover thickness need more
charge passed to complete realkalisation. Although this seems to
be an obvious aspect, it was not measured in previous papers. It
was necessary to change total charge passed from 240 to
400 A h=m2concrete when increasing reinforcement concrete cover
from 1 to 2.5 cm for concrete C2, which means an increase of more
than 66% in total charge. For concrete C4, it took place in a similar
way. The total charge increased from 310 to 500 A h=m2concrete ,
which means an increase of more than 61%. This is related to the
amount of OH ions that need to be generated to realkalise the
whole concrete cover thickness.
4.3. Visual monitoring of realkalisation front advance
Fig. 7 shows the advance of the realkalised fraction in concrete
cover region during the treatment based on digital images, as described in Section 3.4. C4/25 specimen was taken as reference to
this purpose. By Fig. 7, it can be clearly seen that the realkalisation
process started near to the reinforcement and progressively advanced towards the concrete surface. This indicates that water
electrolysis in the cathode region was the main phenomenon involved in concrete cover realkalisation in this experiment. It is also
noticed that the treatment increases concrete alkalinity in the
whole concrete cover, including the layers close to the concrete
surface. This behaviour was observed for all studied concretes
and conrmed the efciency of electrochemical realkalisation
treatment.
Fig. 8 compares the realkalised fraction of concrete specimens
made with the different cements used in this work and shows that,
for a similar total charge passed (about 350 A h=m2concrete ), the specimen made with cement I present higher realkalised fraction,
which corroborates the point that Pozzolan cement-based specimens reached lower levels alkalinity during carbonation and need
more charge to restore a similar level of alkalinity.
4.4. Relative alkalinity changes due to the treatment
Additional alkalinity measurements were carried out aiming to
help on the identication of concrete alkalinity changes nearby the
reinforcement and in the outer layers. Reference (REF), carbonated
(CARB) and realkalised (REA) concrete specimens were considered
for this purpose.
Fig. 9 compares the alkalinity of concrete samples extracted
nearby the reinforcement for REF, CARB and REA specimens. In
the last case, samples were extracted 30 days after the treatment
with the objective of representing a more stable condition, regarding the polarisation applied during the electrochemical realkalisation and the chemical equilibrium nearby the reinforcement. As pH
measurements taken from the water equilibrium samples (Section 3.2) may not accurately represent the pH in concrete solution
porous network, but helps on relative analysis, the relative alkalinity was adopted in this approach. Two samples were taken for each
analysed condition and the average of each pair of samples was expressed as a relative alkalinity value in terms of the highest average pH value observed among all the analysed conditions, which
was 13.4.
For all studied concretes, specimens subjected to electrochemical realkalisation presented higher alkalinity than carbonated
specimens and quite close to the alkalinity of reference specimens.
This shows the efciency of the treatment in recovering the

285

concrete alkalinity, as observed in previous works [15,19,27]. On

the other hand, it can also be noticed the inuence of the cement
type. Both concretes C3 and C4 presented lower values for REF,
CARB and REA specimens. This can be explained by its lower alkaline reserve (see Fig. 9, reference samples), which makes them
reach lower levels of alkalinity during carbonation and after
realkalisation.
There are also differences of alkalinity between specimens made
with the same concrete mixture and different reinforcement concrete covers (C2/10, C2/25 and C4/10, C4/25). These differences
can be related to the skin effect for REF and CARB specimens, which
leads to differences on concrete microstructure in outer layers and
also makes the carbonation of this concrete region easier. Furthermore, for REA specimens, the higher total charge demanded to realkalise a thicker reinforcement concrete cover generates more OH
ions at the reinforcement surrounding region (see Section 4.2).
Fig. 10 shows average relative alkalinities at three different
depth bands for concrete specimens C2/25 and C4/25, in a similar
way as Fig. 9. These depth bands are related to concrete surface
distance (08 mm, 816 mm and 1625 mm). The efciency of
the treatment for recovering concrete alkalinity can be noticed
even at layers close to concrete surface. However, the alkalinity
nearby the reinforcement, after the treatment, is a bit higher than
that observed at the outer layers for C2/25 specimen. This behaviour is in accordance with a process that starts at reinforcement level and progressively advances towards the specimen surface (see
Fig. 7).
4.5. Electrochemical parameters and tendency of reaching passive
condition
Figs. 11 and 12 show the comparative behaviour of corrosion
potential (Fig. 11) and corrosion current density measurements
(Fig. 12) during the experiment, considering REF, CARB, REA specimens and the classication ranges for these variables regarding
the corrosion process. This classication is based on ASTM C-876
[34] and in previous published papers [35].
Before starting realkalisation procedures, depassivated reinforcements presented corrosion potentials ranging between 535
and 640 mV (CSE) due to carbonation and saturation of concrete
specimens. At the end of the treatment, corrosion potential drops
to strongly negative values due to the imposed polarisation. However, these potentials gradually become less electronegative reaching values close to 250 mV (CSE) 1 month after nishing the
treatment and close to 200 mV (CSE) after 2 months. After
6 months, almost all the bars presented potentials less electronegative than 200 mV (CSE).
By corrosion potential measurements, it is possible to see a tendency of reinforcement reaching the passive condition. This tendency is clearly seen 6 months after the end of the treatment.
Before this period, there are still some values in the zone of uncertain corrosion (Fig. 11).
Considering the corrosion current density, the reinforcements
presented values between 0.6 and 14 lA/cm2 after concrete carbonation and saturation. These values increased during the treatment due to the imposed polarisation, but started to decrease
just after turning off the system. It presented some uctuation during the depolarisation period and only 1 year after the treatment
the corrosion current indicated a tendency of stabilisation of its
values. Measurements after 6 months were not taken due to a
potentiostat fault at that time.
Fig. 12 shows that, although only some bars presented values
below 0.1 lA/cm2, which indicates the passive condition, most of
the bars reached the low corrosion current level after 12 months
(6-month measurements were not taken for this variable as previously explained). This implies in current values signicantly lower,

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P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280290

Fig. 7. Visual monitoring of realkalisation front advance during the treatment (case of the C4/25 specimen) 88.5 h (a); 123.5 h (b); 142 h (c); 183.5 h (d) and 207.5 h (e).

which means a metal dissolution rate signicantly lower and, consequently, a longer residual service life. On the other hand, a tendency of reaching values even lower throughout time is not
rejected.
Similar behaviour about corrosion current measurements after
realkalisation treatment was observed in literature [30]. Concerning this aspect, Redaelli and Bertolini [30] found that although corrosion current density obtained by potentiostatic tests signicantly
decreased over time they do not match the condition of passive
steel in alkaline media. On the other hand, no signicant amounts

of corrosion products were found on steel surface after breaking

these same specimens, which indicates that this kind of measurement could not be suitable for monitoring the effectiveness of steel
repassivation. However, this aspect is not still a consensus [40].
The lack of an effective electro-osmotic ux has been reported as
the reason for not reaching the effectiveness of reinforcement
repassivation in some cases [40]. Considering the present work,
the electro-osmotic ux was not clearly observed, but the levels
of corrosion current density even not being enough to reach the
passive condition in most cases, were quite close to this reference.

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P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280290

C2/25

C4/25

Cathode

Cathode

(a)

(b)

Fig. 8. Differences on realkalised fraction for specimens made with cements I and II and subjected to a similar total charge passed.

Fig. 9. Relative alkalinity nearby the reinforcement for reference (REF), carbonated
(CARB) and realkalised (REA) concrete specimens.

(a)

(b)

Fig. 10. Relative alkalinity proles in concrete cover for reference (REF), carbonated
(CARB) and realkalised (REA) concrete specimens C2/25 (a); C4/25 (b).

This way, further research is necessary to clarify the interpretation

and applicability of corrosion current measurements after electrochemical realkalisation.
Fig. 13 shows the tendency of reinforcements reaching the passive condition by drawing tendency lines for corrosion potential.

Fig. 11. Comparative corrosion potential for reference (REF), carbonated (CARB)
and realkalised (REA) concrete specimens.

Average values and standard deviations representative of each

set of reinforcements used for each experimental condition were
considered and only the measurements taken after around 10 days
after turning off the electrical arrangement were used for tting
the tendency lines. This was done to avoid the strong polarisation
inuence just after the treatment. The linear function was the one
that best tted the presented data. By tendency lines it is possible
to obtain the time required for these values to become less electronegative than 200 mV (CSE), which is the reference assumed for
the passive condition.
These values are presented in Table 4. A relationship between
total charge passed and time for reinforcement repassivation could
be observed. For same concretes, a higher charge passed means
less time for reinforcement to reach the passive condition. The
higher total charge demanded (Section 4.2) and the higher relative
alkalinity for specimens with higher concrete thickness (Section 4.3) helps to explain this behaviour. As a consequence, it can
be pointed out that the total charge passed directly inuences concrete alkalinity and this indirectly inuences the time required for
reaching the passive condition.
Comparing concretes made with cements I (C1, C2) and II (C3,
C4), it can be seen that although concretes made with cement I demanded lower total charge passed, they presented shorter time for
reaching the passive condition. This can be explained by the fact that
these concretes presented higher relative alkalinity after the treatment and thus presented better conditions to repassivation. In other
words, concretes made with Portland pozzolan cement (II) demand
more time for reaching the passive condition of reinforcements.

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Fig. 12. Comparative corrosion current density for reference (REF), carbonated (CARB) and realkalised (REA) concrete specimens.

(a)

(d)

(b)

(e)

(c)

(f)

Fig. 13. Assessment of depolarisation time by means of corrosion potential.

P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280290

Table 4
Relationship between total charge passed, relative alkalinity and estimated depolarisation time.
Specimen
codes

Total electrical charge

passed (A h=m2concrete )

Relative
alkalinity after
ERA

Estimated
depolarisation time
(days)

C1/10
C2/10
C2/25
C3/10
C4/10
C4/25

328
238
401
360
310
499

0.952
0.924
0.966
0.924
0.904
0.918

98
66
59
115
73
65

5. Conclusions
Water electrolysis seems to be the main reason for the electrochemical realkalisation of carbonated concretes in this study,
which is deduced from the outline of the realkalised area advance
during the treatment.
The inuence of water to cement ratio on this treatment happens
in an inverse way to the ohmic resistance of the system, the time required by the treatment and the total charge passed. It means that
as w/c increases, the ohmic resistance decreases, as well as the time
to complete the treatment and the total electrical charge passed.
The inuence of cement type happens on concrete alkalinity, total charge passed required for completing the treatment and consequently on the time demanded for it, as well as on the time
demanded for reinforcement to reach a passive condition. The
use of pozzolanic addition in cement contributed for longer periods
of realkalisation as a consequence of its lower alkalinity reserve
due to portlandite consumption in pozzolanic reactions, as well
as for higher total charge passed to complete the treatment. This
lower alkalinity has consequences for reinforcement repassivation
tendencies, demanding a longer time to reach this condition or
tendency.
The concrete cover thickness inuences the time demanded for
completing the realkalisation process. A thicker concrete cover demands more time and, consequently, more charge to produce enough alkalinity for the whole concrete cover region. On the other
hand, this contributes for a shorter time demanded for reaching
electrochemical stabilisation, which can be explained by the higher
levels of alkalinity reached nearby the reinforcement.
Taking into account the efciency of the method about reinforcement reaching the passive condition, it is possible to say that
the tendency of reaching this condition is clearer for corrosion potential measurements. For corrosion current density measurements, although it is not clear, they tend to decrease over time,
reaching values not far to this reference and longer service life
periods for the structure. However, more monitoring time and further research are necessary to analyse if it is possible to conrm a
similar tendency with this parameter and if corrosion current rate
could be suitable for this purpose.
Acknowledgments
The authors thank the Brazilian Research Agency (CNPq) for
supporting this research and the engineering electrochemical laboratory of the Federal University of Campina Grande for helping on
alkalinity analysis.
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