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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
281
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.
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.
2H2 O ! O2 4H 4e
4
282
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.
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.
283
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
Table 3
Specimen codes.
Concrete
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).
284
Fig. 6. Progress of the realkalised fraction as a function of the total charge passed.
285
286
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
287
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).
Fig. 11. Comparative corrosion potential for reference (REF), carbonated (CARB)
and realkalised (REA) concrete specimens.
288
Fig. 12. Comparative corrosion current density for reference (REF), carbonated (CARB) and realkalised (REA) concrete specimens.
(a)
(d)
(b)
(e)
(c)
(f)
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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