Construction and Building Materials 40 (2013) 280–290

Contents lists available at SciVerse ScienceDirect

Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Electrochemical realkalisation of carbonated concretes – Influence 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
Urban and Environmental Engineering Postgraduate Programme, Federal University of Paraíba, 58051-900 João Pessoa, Brazil
b
Federal Institute of Education, Science and Technology of Paraíba, R. Dep. Balduíno M. de Carvalho, 155/1104, 58.036-860 João 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 a b s t r a c t

Article history: This work studies the influence of concrete characteristics, such as cement type and water to cement
Received 22 May 2012 ratio, and concrete cover thickness on the electrochemical realkalisation of carbonated concretes. Results
Received in revised form 6 September 2012 show the treatment efficiency for recovering concrete alkalinity. More time and total electrical charge
Accepted 23 September 2012
passed are demanded in proportion as water to cement ratio decrease, concrete cover thickness increase
Available online 6 December 2012
and when concrete has lower alkalinity reserve. The tendency of reinforcement reaching passive condi-
tion is observed by corrosion potential measurements. For this variable, concretes that demand more
Keywords:
charge and time for realkalisation reach the passive condition in a shorter time. Corrosion current density
Carbonation
Concrete
shows a decrease tendency over time and, although not reaching the level that represents passive condi-
Electrochemical realkalisation tion in most of the cases, it was not far from this reference.
Repassivation Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction As a rehabilitation method or as a preventive treatment, the

Concrete is a material that usually presents high levels of alka-
linity, which helps on the formation and protection of passivation
film on metal surfaces in reinforced concrete structures. Since this
initial condition of high alkalinity and the concentration of depass-
ivating ions below a certain threshold are maintained, corrosion
process does not start [1]. However, this protective film can be bro-
ken down due to carbonation or in the presence of concentrations
of chloride ions higher than a certain critical content [2,3]. In the
specific case of concrete carbonation, the pH goes down due to car-
bonates precipitation as a consequence of hydroxides and other
hydrated phases reaction with carbon dioxide [4].
⇑ Corresponding author at: Federal Institute of Education, Science and Technol-
ogy of Paraíba, R. Dep. Balduíno M. de Carvalho, 155/1104, 58036-860 João 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).
realkalisation method has been used to recover concrete alkalinity
nearby the reinforcing region [5–7]. The advantage of this method
is that when the treatment finishes the system can be unassembled
and concrete structure can follow its role without larger destruc-
tive interventions as in conventional parch repair treatment [8].
Studies about realkalisation treatment which focused on under-
standing the phenomenon characteristics, like transport mecha-
nisms involved [9–14], efficiency on reinforcement repassivation
[15–19], efficiency of different electrolytes on realkalisation [20],
effects on concrete properties [21,22] and side effects [23–26],
have been carried out during the last years.
On site applications were introduced at the end of 1980s and a
significant 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].

0950-0618/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2012.09.076
 P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280–290
On the other hand, the effectiveness of the treatment in repass-
ivating the reinforcement has been questioned [28,29] and,
although some work is being carried out on this specific topic
[30], there is still not a consensus and more research is necessary.
Moreover, the influence of material or structure characteristics on
the method behaviour and its final results was studied at a lower
level [30,31].
Taking into account this gap in knowledge, this work studies the
influence of cement type, water to cement ratio and reinforcement
concrete cover on electrochemical realkalisation of carbonated
concretes and its efficiency 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 so-
dium carbonate solution is the most common electrolyte. An elec-
trical 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 de-
scribed in Eqs. (1) and (2) [10] and it is helped by electro-osmosis
of electrolyte solution [9,11–14]. Additional mass transport by cap-
illary absorption can take place in specific cases where the sub-
strate 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 influence in this process
[9]. As an electrical field 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 þ H2 O þ 2e ! 2OH
2H2 O þ 2e ! 2OH þ H2"
Fig. 1. Simplified design of the electrochemical realkalisation process.
281
At the anode region, hydroxyl ions are oxidised or water is elec-
trolysed, as described in Eqs. (3) and (4) [5], which decreases pH
level in this region.
2OH ! 1=2O2 þ H2 O þ 2e ð3Þ
2H2 O ! O2 þ 4Hþ þ 4e ð4Þ

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 phenom-
enon involved, the total charge passed is the variable that strongly
influences 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 to-
wards the reinforcement and play an important role in realkalisa-
tion process [13], some works did not observe this kind of mass
transport [27]. With regards to the contribution of electro-osmotic
flux, the alkaline solution moves from the external anode region to
the cathode region through the concrete pores network [9,12]. This
flux depends on the electrical field applied, but it is mainly influ-
enced 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].
ð1Þ Thus, these conditions need to be favourable for the electro-osmo-
tic flux to happen at a significant level.
ð2Þ Concerning the realkalisation treatment, an important point
would be to know when the realkalisation system can be turned
282 P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280–290

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 proce-
dure was adopted to avoid the wicking effect during the treatment.
3.3. Realkalisation procedures

For realkalisation treatment, an electrical field was generated between the rein-
3. Experimental work forcement (cathode) and an external anode attached to the concrete surface using a
power supply, which was continuously controlled to produce an average cathodic
3.1. Casting and curing concrete specimens
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 sur-
Prismatic concrete specimens with 8  8  8 cm were cast using Brazilian Port-
face of the specimen and the electrolyte was a sodium carbonate (NaCO3) 1 M solu-
land Cements V (high early strength Portland cement – ASTM Type III) and IV (Port- tion, in a similar arrangement as the one presented in Fig. 1.
land pozzolan cement – ASTM Type IP), which physical and chemical characteristics The option for this level of current density and sodium carbonate based electro-
are presented in Table 1 as cements I and II, respectively. In this case, the commer- lyte was a consequence of experiences presented in some previous papers
cial Portland pozzolan cement used incorporated calcined clay as pozzolan addition [5,9,15,19], which show the efficiency of this arrangement without significant risks
in its composition. Water to cement ratios were set at 0.55 and 0.65, comprising to change concrete microstructure.
concrete mixtures and properties presented in Table 2. Coarse aggregate and sand
Based on this set up and on electrical current and potential difference measure-
had 9.5 mm and 4.8 mm maximum diameter, respectively.
ments directly obtained on this circuit to monitor the target current density, it was
Two reinforcement bars with 6.3 mm diameter and 10 cm length were embed- possible to obtain the ohmic resistance of the system. This helped on visualising the
ded in each specimen and were placed respecting 1 or 2.5 cm of concrete cover high initial resistance of the system and its gradual decrease due to the ionic flux
(Fig. 2), comprising the specimens characteristics and codes presented in Table 3. increase.
The option of embedding two bars in each specimen was to consider an arrange-
ment that can take place in field applications. Two reinforced concrete specimens
were cast for each experimental condition. Reinforcements were previously cleaned
3.4. Alkalinity monitoring
by mechanically brushing their surfaces until removing any previous surface oxida-
tion products. Afterwards, these bars had their extremities covered with an insulat-
The system arrangement for the treatment was turned on until the concrete
ing tape, delimiting an intermediate constant exposing area of 6 cm2 (Fig. 2).
reinforcement cover was completely realkalised. This was monitored in two dupli-
Duplicate reinforced specimens were cast to monitor realkalisation of concrete cov-
cate specimens cast with this objective. These specimens were periodically (up to
er as described in Section 3.4.
five times during the treatment period) sliced close to the reinforcements
Furthermore, additional non-reinforced cylindrical specimens (10  20 cm)
(Fig. 3a) using a diamond-based tool under a dry cutting process. This was done ini-
were cast to monitor carbonation front advance during accelerated carbonation
tially after approximately 24 h and 90 h of treatment for more and less porous con-
procedures. All specimens were cured in a wet chamber for 7 days, to represent a
cretes, respectively, and it was followed at shorter intervals of time depending on
condition closer to field applications, and remained in laboratory environment until
the alkalinity advance in the previous measurement. After being sliced, the speci-
completing 180 days, when it is expected that the concrete reach a more stable
mens had their surfaces cleaned with high pressure air jets and then, a 1% thy-
microstructure. During this period, they were covered by a plastic film to avoid
molphthalein solution was sprayed on them as a pH indicator (Fig. 3b). This
early carbonation.
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
3.2. Accelerated carbonation the previous carbonated area, considering the area in front of the exposed reinforce-
ment length as shown in Fig. 3b, it was possible to monitor the realkalisation ad-
After this initial period of 180 days, the specimens were subjected to acceler- vance in the concrete cover region by means of the ratio between the realkalised
ated carbonation in a saturated carbonation chamber under 75 ± 5% of relative area and the previous carbonated area. This ratio was expressed as a realkalised
humidity and 28.5 ± 1 °C of temperature. The usual accelerated carbonation condi- fraction of the total carbonated area in the cover region. Digital images captured
tions reported in literature with CO2 concentrations below 10% and relative humid- from sliced surfaces obtained for each alkalinity analysis were used for this purpose,
ity between 50% and 65% [33] could not be adopted in this case. During this as represented in Fig 3b.
carbonation period, sacrificial non-reinforced concrete specimens (cylinders) were Complementary pH analyses were also carried out using the following proce-
used to monitor the carbonation front advance. This was done by means of a phe- dures. When all the concrete cover was realkalised and thus the treatment was fin-
nolphthalein test, which is based on a pH indicator (1% phenolphthalein solution) ished, the specimens were broken and samples close to the reinforcement were
that becomes dark pink in environments with pH higher than nine and colourless collected using a diamond-based tool. These samples represent an 8 mm thickness
for lower values of pH. The carbonation front was verified on 1 cm slices cut per- layer nearby the reinforcement surface and were collected for reference (REF), car-
pendicularly to cylinder axis. bonated (CARB) and realkalised (REA) specimens. Additionally, similar samples
Simultaneously to carbonation front advance monitoring, electrochemical mea- were also extracted at three different depth bands (0–8; 8–16 and 16–25 mm with
surements were taken to identify reinforcement depassivation. This was indicated respect to concrete surface) for specimens with 25 mm concrete cover thickness.
by corrosion potentials more electronegative than 350 mV (CSE – copper sulphate After being extracted, these samples were crushed to small pieces (about 2 mm)
electrode) [34] and corrosion current density higher than 0.1 lA/cm2 [35] as com- and were immersed in deionised water for 24 h respecting the 1/1 ratio and stored
mented in Section 3.3. 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 solu-
tion was used to analyse the hydroxide concentration and, consequently, the pH of
Table 1 this equilibrium solution. This extraction procedure is similar to that described by
Chemical composition and physical properties of cements. Castellote et al. [36]. No further mathematical data treatment was adopted to fit
pore-pressing condition as proposed in the same work [36] due to its limited vali-
Composition/property Cement I Cement II
dation. It is clear that this equilibrium solution does not accurately represent the
SO3 (%) 3.19 2.69 concrete porous network solution, but in some way it represents a ‘‘potential’’ alka-
SiO2 (%) 18.96 25.75 linity of the samples and thus it was used only for comparative analysis, in a similar
Al2O3 (%) 3.92 5.44 way to other previous works [37,38].
Fe2O3 (%) 2.95 2.44
CaO (%) 61.06 51.56
MgO (%) 3.08 4.51 3.5. Electrochemical measurements
Na2O (%) 0.15 0.23
K2O (%) 1.03 1.86 Electrochemical measurements were carried out during the carbonation and
Insoluble residue – IR (%) 0.67 16.81 electrochemical realkalisation periods. This was done on single measurements of
Loss on ignition – Li (%) 1.15 4.47 open circuit corrosion potential (Ecorr) and instantaneous corrosion current density
Free CaO 2.96 1.13 (icorr) measurements. A potentiostat, model VMP3 from PAR (Priceton Applied Re-
Blaine (cm2/g) 4020 4670 search), was used to perform these measurements. Linear polarisation technique
Specific density (g/cm3) 3.14 2.97 was used for corrosion measurements. A potential difference of ±10 mV with re-
spect to the free corrosion potential and a scanning rate of 0.17 mV/s were applied.
 P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280–290 283

Table 2
Concrete mixtures and properties.

Concrete C1 C2 C3 C4
Cement type I I II II
Cement (kg/m3) 362 349 360 347
Sand (kg/m3) – maximum diameter 4.8 mm 858 828 853 823
Coarse aggregate (kg/m3) – maximum diameter 9.5 mm 934 902 928 896
Plasticiser (kg/m3) 1.77 – 3.51 –
w/c ratio 0.55 0.65 0.55 0.65
Slump (cm) 6 16 5 9
Compressive strength (MPa) – 90 days 40.2 36.3 28.9 22.3
Absorption (%) 3.14 4.62 4.52 5.67
Water porosity (%) 7.11 10.21 10.04 12.32
Density (g/cm3) 2.26 2.21 2.22 2.17

Fig. 2. Schematic design of concrete specimens.

Table 3 The ohmic drop was compensated and the icorr values were obtained by Stern and
Specimen codes. Geary equation [39]. The measurements set up used a copper sulphate electrode
Concrete Reinforcement concrete cover (mm) Specimen code (CSE) as reference electrode and a stainless steel plate as a counter electrode (Fig. 4).
Regarding electrochemical measurements to indicate reinforcement depassiva-
C1 10 C1/10 tion, this work accepted that icorr values higher than 0.1 lA/cm2 indicate metal
C2 10 C2/10 depassivation, as well as Ecorr values more electronegative than 350 mV (CSE)
25 C2/25 [34,35]. This electrochemical monitoring was continued during 1 year after the
C3 10 C3/10 realkalisation treatment was over. Throughout this period, the specimens were pro-
C4 10 C4/10 tected with a plastic film and stored in a laboratory environment to avoid further
25 C4/25 carbonation.

Fig. 3. Evaluation of the realkalised area – specimen cutting (a) and comparison of areas (b).
284 P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280–290
Fig. 4. Electrochemical measurements.
4. Results and discussion
4.1. Ohmic resistance of the system
The ohmic resistance of the system (reinforcement (cathode)–
concrete–electrolyte–anode) 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 de-
crease during the treatment. As carbonated concretes usually have
higher resistivity [11] and ionic flux is starting, these high values
are expected. As time goes by, the ionic flux 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
difficult. In a similar way, specimens with thicker concrete cover
also present higher ohmic resistance of the system, due to its thick-
er barrier to ionic transport. This makes resistance data for
arrangements with specimens with 25 mm concrete cover thick-
ness 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 frac-
tion of the total carbonated area in the cover region, as described in
Section 3.4.
Results show that concretes made with Portland pozzolan ce-
ment (C3, C4) required more charge to complete concrete realkali-
sation. 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 ac-
count. 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 carbon-
ation (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 conse-
quence of the first aspect, more hydrogen cations are generated in
the anodic region, which contributes to neutralise some of the
hydroxides produced at the cathode region.
The influence of w/c can be observed in Fig. 6. Comparing con-
cretes C1 and C2, it can be seen that concrete C1 need
330 A h=m2concrete to complete realkalisation, in proportion as con-
crete 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) 280–290
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 real-
kalise 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 de-
scribed 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 ad-
vanced towards the concrete surface. This indicates that water
electrolysis in the cathode region was the main phenomenon in-
volved 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 confirmed the efficiency 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 spec-
imen made with cement I present higher realkalised fraction,
which corroborates the point that Pozzolan cement-based speci-
mens 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 identification 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, regard-
ing the polarisation applied during the electrochemical realkalisa-
tion and the chemical equilibrium nearby the reinforcement. As pH
measurements taken from the water equilibrium samples (Sec-
tion 3.2) may not accurately represent the pH in concrete solution
porous network, but helps on relative analysis, the relative alkalin-
ity was adopted in this approach. Two samples were taken for each
analysed condition and the average of each pair of samples was ex-
pressed as a relative alkalinity value in terms of the highest aver-
age pH value observed among all the analysed conditions, which
was 13.4.
For all studied concretes, specimens subjected to electrochemi-
cal realkalisation presented higher alkalinity than carbonated
specimens and quite close to the alkalinity of reference specimens.
This shows the efficiency 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 influence 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 alka-
line 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 con-
crete 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. Further-
more, for REA specimens, the higher total charge demanded to real-
kalise 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 (0–8 mm, 8–16 mm and 16–25 mm). The efficiency 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 behav-
iour is in accordance with a process that starts at reinforcement le-
vel 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 spec-
imens and the classification ranges for these variables regarding
the corrosion process. This classification is based on ASTM C-876
[34] and in previous published papers [35].
Before starting realkalisation procedures, depassivated rein-
forcements 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. How-
ever, these potentials gradually become less electronegative reach-
ing values close to 250 mV (CSE) 1 month after finishing the
treatment and close to 200 mV (CSE) after 2 months. After
6 months, almost all the bars presented potentials less electroneg-
ative than 200 mV (CSE).
By corrosion potential measurements, it is possible to see a ten-
dency of reinforcement reaching the passive condition. This ten-
dency is clearly seen 6 months after the end of the treatment.
Before this period, there are still some values in the zone of uncer-
tain corrosion (Fig. 11).
Considering the corrosion current density, the reinforcements
presented values between 0.6 and 14 lA/cm2 after concrete car-
bonation and saturation. These values increased during the treat-
ment due to the imposed polarisation, but started to decrease
just after turning off the system. It presented some fluctuation dur-
ing 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 previ-
ously explained). This implies in current values significantly lower,
286 P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280–290

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 significantly lower and, con-
sequently, a longer residual service life. On the other hand, a ten-
dency of reaching values even lower throughout time is not
rejected.
Similar behaviour about corrosion current measurements after
realkalisation treatment was observed in literature [30]. Concern-
ing this aspect, Redaelli and Bertolini [30] found that although cor-
rosion current density obtained by potentiostatic tests significantly
decreased over time they do not match the condition of passive
steel in alkaline media. On the other hand, no significant amounts
of corrosion products were found on steel surface after breaking
these same specimens, which indicates that this kind of measure-
ment 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 flux 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 flux 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.
 P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280–290
C2/25
Cathode
(a)
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 profiles 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 electro-
chemical realkalisation.
Fig. 13 shows the tendency of reinforcements reaching the pas-
sive condition by drawing tendency lines for corrosion potential.
287
C4/25
Cathode
(b)
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 fitting
the tendency lines. This was done to avoid the strong polarisation
influence just after the treatment. The linear function was the one
that best fitted the presented data. By tendency lines it is possible
to obtain the time required for these values to become less electro-
negative 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 (Sec-
tion 4.3) helps to explain this behaviour. As a consequence, it can
be pointed out that the total charge passed directly influences con-
crete alkalinity and this indirectly influences 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 de-
manded 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 treat-
ment 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.
288 P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280–290

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) 280–290 289

Table 4 [4] Taylor HFW. Cement chemistry. 2nd ed. United Kingdom: Thomas Telford;
Relationship between total charge passed, relative alkalinity and estimated depolar- 1997.
isation time. [5] Mietz J. Electrochemical rehabilitation methods for reinforced concrete
structures – a state of the art report. London: European Federation of
Specimen Total electrical charge Relative Estimated Corrosion Publications; 1998.
codes passed (A h=m2concrete ) alkalinity after depolarisation time [6] Chatterji S. Simultaneous chloride removal and realkalisation of old concrete
ERA (days) structures. Cem Concr Res 1994;24:1051–4.
[7] Mattila JS, Pentti MJ. The performance of different realkalisation methods. In:
C1/10 328 0.952 98 Dhir RK, Jones MR, editors. Concrete repair, rehabilitation and
C2/10 238 0.924 66 protection. London: E & Fn Spon; 1996. p. 483–91.
C2/25 401 0.966 59 [8] Polder RB, Van den Hondel HJ. Electrochemical realkalisation and chloride
C3/10 360 0.924 115 removal of concrete – state of the art, laboratory and field experience. In:
C4/10 310 0.904 73 RILEM international conference on rehabilitation of concrete structures.
C4/25 499 0.918 65 Melbourne: RILEM; 1992. p. 135–47.
[9] Banfill PFG. Features of the mechanism of re-alkalisation and desalination
treatments for reinforced concrete. In: Swamy RN, editor. International
5. Conclusions conference on corrosion and corrosion protection of steel in
concrete. Sheffield: Sheffield Academic Press; 1994. p. 1489–98.
[10] Bertolini L, Bolzoni F, Elsener B, Pedeferri P, Andrade C. Electrochemical
Water electrolysis seems to be the main reason for the electro- realkalisation and chloride removal in reinforced concrete buildings. Mater
chemical realkalisation of carbonated concretes in this study, Constr 1996;46:45–55.
which is deduced from the outline of the realkalised area advance [11] Andrade C, Castellote M, Sarría J, Alonso C. Evolution of pore solution
chemistry, electro-osmosis and rebar corrosion rate induced by
during the treatment.
realkalisation. Mater Struct 1999;32:427–36.
The influence of water to cement ratio on this treatment happens [12] Castellote M, Llorente I, Andrade C. Influence of the external solution in the
in an inverse way to the ohmic resistance of the system, the time re- electro-osmotic flux induced by realkalisation. Mater Constr 2003;53:101–11.
[13] Castellote M, Llorente I, Andrade C, Turrillas X, Alonso C, Campo J. In-situ
quired by the treatment and the total charge passed. It means that
monitoring the realkalisation process by neutron diffraction: electro-osmotic
as w/c increases, the ohmic resistance decreases, as well as the time flux and portlandite formation. Cem Concr Res 2006;36:791–800.
to complete the treatment and the total electrical charge passed. [14] Castellote M, Llorente I, Andrade C, Turrillas X, Alonso C, Campo J. Neutron
The influence of cement type happens on concrete alkalinity, to- diffraction as a tool to monitor the establishment of the electro-osmotic flux
during realkalisation of carbonated concrete. Physica B 2006;385–
tal charge passed required for completing the treatment and con- 386:26–528.
sequently on the time demanded for it, as well as on the time [15] Odden L. The repassivating effect of electro-chemical realkalisation and
demanded for reinforcement to reach a passive condition. The chloride extraction. In: Swamy RN, editor. International conference on
corrosion and corrosion protection of steel in concrete. Sheffield: Sheffield
use of pozzolanic addition in cement contributed for longer periods Academic Press; 1994. p. 1473–88.
of realkalisation as a consequence of its lower alkalinity reserve [16] González JA, Cobo A, González MN, Otero E. On the effectiveness of
due to portlandite consumption in pozzolanic reactions, as well realkalisation as a rehabilitation method for corroded reinforced concrete
structures. Mater Corros 2000;51:97–103.
as for higher total charge passed to complete the treatment. This [17] Elsener B. Half-cell potential mapping to assess repair work on RC structures.
lower alkalinity has consequences for reinforcement repassivation Constr Build Mater 2001;15:133–9.
tendencies, demanding a longer time to reach this condition or [18] Miranda JM, González JA, Otero E, Cobo A. Consideraciones sobre la
repasivación–rehabilitación de las estructuras corroídas de concreto armado
tendency.
In: Castro P, Moreno E, editores. VII Congreso Latinoamericano de Patología de
The concrete cover thickness influences the time demanded for la Construcción – IX Congreso de Control de Calidad en la Construcción –
completing the realkalisation process. A thicker concrete cover de- CONPAT. Mérida: ALCONPAT; 2003. p. VII 41–8.
[19] Yeih W, Chang JJ. A study on the efficiency of electrochemical realkalisation of
mands more time and, consequently, more charge to produce en-
carbonated concrete. Constr Build Mater 2005;19:516–24.
ough alkalinity for the whole concrete cover region. On the other [20] Araújo FWC. A study on the repassivation of carbonated concretes steels
hand, this contributes for a shorter time demanded for reaching through chemical realkalisation technique. São Paulo: Polytechnic School –
electrochemical stabilisation, which can be explained by the higher University of São Paulo; 2009. PhD Thesis [in Portuguese].
[21] Banfill PFG. Re-alkalisation of carbonated concrete: effect on concrete
levels of alkalinity reached nearby the reinforcement. properties. Constr Build Mater 1997;11:255–8.
Taking into account the efficiency of the method about rein- [22] Glass GK, Buenfeld NR. The inhibitive effects of electrochemical treatment
forcement reaching the passive condition, it is possible to say that applied to steel in concrete. Corros Sci 2000;42:923–7.
[23] Banfill PFG. Re-alkalisation of reinforced concrete: present problems and
the tendency of reaching this condition is clearer for corrosion po- future possibilities. In: Dhir RK, Jones MR, editors. Concrete repair,
tential measurements. For corrosion current density measure- rehabilitation and protection. London: E & Fn Spon; 1996. p. 473–81.
ments, although it is not clear, they tend to decrease over time, [24] Miller JB. Structural aspects of high powered electro-chemical treatment of
reinforced concrete. In: Swamy RN, editor. International conference on
reaching values not far to this reference and longer service life corrosion and corrosion protection of steel in concrete. Sheffield: Sheffield
periods for the structure. However, more monitoring time and fur- Academic Press; 1994. p. 1499–514.
ther research are necessary to analyse if it is possible to confirm a [25] Miller JB. The perception of the ASR problem with particular reference to
electrochemical treatments of reinforced concrete. In: EUROCORR 97 –
similar tendency with this parameter and if corrosion current rate
corrosion of reinforcement in concrete – monitoring, prevention and
could be suitable for this purpose. rehabilitation. Trondheim: EFC; 1997, p. 141–9.
[26] Banfill PFG, Al-Kadhimi TKH. The effects of re-alkalisation and chloride
removal on alkali-silica expansion in concrete In: EUROCORR 98 – solution to
Acknowledgments corrosion problems. Utrecht: EFC; 1998.
[27] Bertolini L, Carsana M, Redaelli E. Conservation of historical reinforced
The authors thank the Brazilian Research Agency (CNPq) for concrete structures damaged by carbonation induced corrosion by means of
electrochemical realkalisation. J Cult Herit 2008;9:376–85.
supporting this research and the engineering electrochemical lab-
[28] Miranda JM, González JA, Cobo A, Otero E. Several questions about
oratory of the Federal University of Campina Grande for helping on electrochemical rehabilitation methods for reinforced concrete structures.
alkalinity analysis. Corros Sci 2006;48:2172–88.
[29] Bastidas DM, Cobo A, Otero E, González JA. Electrochemical rehabilitation
methods for reinforced concrete structures: advantages and pitfalls. Corros
References Eng Sci Technol 2008;43:248–55.
[30] Redaelli E, Bertolini L. Electrochemical repair techniques in carbonated
[1] Broomfield JP. Corrosion of steel in concrete: understanding, investigation and concrete. Part I: Electrochemical realkalization. J Appl Electrochem
repair. London: E & Fn Spon; 1997. 2011;41:817–27.
[2] Tuutti K. Corrosion of steel in concrete. Sweden: CBI; 1982. [31] Van den Hondel AWM, Polder RB. Laboratory investigation of electrochemical
[3] Bentur A, Diamond S, Berke NS. Steel corrosion in concrete – fundamentals and realkalisation of reinforced concrete. In: EUROCORR 98 – Solution to corrosion
civil engineering practice. London: E & Fn Spon; 1997. problems. Utrecht: EFC; 1998.
290 P.H.L.C. Ribeiro et al. / Construction and Building Materials 40 (2013) 280–290
[32] Bertolini L, Elsener B, Pedeferri P, Polder RB. Corrosion of steel in concrete:
prevention, diagnosis, repair. Weinheim: Wiley-VCH Verlag GmbH & Co.;
2004.
[33] Pauletti C. Estimate of natural carbonation of cement based materials based on
accelerated tests and prediction models. Porto Alegre: Federal University of
Rio Grande do Sul; 2009. PhD Thesis [in Portuguese].
[34] American Society for Testing Materials – ASTM C-876. Standard test for half-
cell potentials of uncoated reinforcing steel in concrete. Annual Book of ASTM
Standards. Philadelphia: ASTM; 1999.
[35] Andrade C, Alonso C. On-site measurements of corrosion rate of
reinforcements. Constr Build Mater 2001;15:141–5.
[36] Castellote M, Alonso C, Andrade C. Determination of the OH content in the
aqueous phase of hardened cementitious materials by an empirical leaching
method. Mater Constr 2002;52:39–56.
[37] Oliveira CTA. Pore water of pastes made with slag cement. São Paulo:
Polytechnic School – University of São Paulo; 2000. PhD Thesis [in Portuguese].
[38] Räsänen V, Penttala V. The pH measurement of concrete and smoothing
mortar using a concrete powder suspension. Cem Concr Res 2004;34:813–20.
[39] Andrade C, Alonso C. Corrosion rate monitoring in the laboratory and on-site.
Constr Build Mater 1996;10:315–28.
[40] Martínez I, Andrade C, Castellote M, Viedma PG. Advancements in non-
destructive control of efficiency of electrochemical repair techniques. Corros
Eng Sci Technol 2009;44:108–18.