Corros Rev 29 (2011): 179190 2011 by Walter de Gruyter Berlin Boston. DOI 10.1515/CORRREV.2011.
008
Electrochemical techniques for the repair of reinforced concrete
suffering carbonation-induced corrosion
Elena Redaelli*, Maddalena Carsana, Matteo
Gastaldi, Federica Lollini and Luca Bertolini
Politecnico di Milano, Department of Chemistry,
Materials, and Chemical Engineering Giulio Natta
Piazza Leonardo da Vinci 32, 20133 Milano, Italy,
e-mail: elena.redaelli@polimi.it
* Corresponding author
Abstract
The use of electrochemical techniques in the repair of rein-
forced concrete suffering carbonation-induced corrosion is
increasing thanks to advantages connected with the possibility
of preserving carbonated concrete and minimising the altera-
tion of the surface, which make these techniques attractive for
facades or monuments that have a high cultural, historical or
architectural value. Electrochemical techniques allow repas-
sivation of the steel through the application of a temporary
or permanent cathodic current. These techniques have been
used for several decades, although some aspects connected
with their application have not been clarified yet. This paper
presents a state-of-the-art on the techniques of electrochemi-
cal realkalisation and cathodic protection used in carbonated
concrete, and describes the recent developments in this field,
with particular reference to experimental investigations and
on-site applications carried out in Italy in recent years.
Keywords: carbonation; cathodic protection; electrochemi-
cal realkalisation; reinforced concrete; repair.
1. Introduction
The repair of reinforced concrete suffering carbonation-
induced corrosion is a problem of great concern due to the large
number of structures, buildings and other artefacts exposed to
the atmospheric environment experiencing this phenomenon.
Steel reinforcement, which is initially passive as a result of the
contact with alkaline hydrated cement paste, starts to corrode
when the carbonation front reaches the rebar depth due to the
reaction with atmospheric carbon dioxide. After corrosion ini-
tiation, the corrosion rate mainly depends on moisture content
in the concrete, being negligible (i.e., lower than 1 mA/m2,
which means roughly 1 m/year) in dry environments (i.e.,
relative humidity lower than 7080%, as in the case of internal
exposure) and higher than 10 m/year in wet environments
(i.e., relative humidity higher than 90% or in the presence
of occasional wetting) (Glass, Page, & Short, 1991). When
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corrosion propagates, the formation of corrosion products at
the steel-concrete interface generates mechanical stresses that
cause cracking of concrete cover, delamination and, eventu-
ally, spalling, as it is depicted in Figure 1 (Bertolini, 2008;
Tuutti, 1982). Each of these phenomena represents a limit state
in the life of the structure, since it is an undesired event that
limits the serviceability and functionality of the structure and
makes an intervention necessary.
The repair of structures suffering carbonation-induced cor-
rosion is traditionally carried out by removing carbonated con-
crete and replacing it with a new alkaline material, typically
a repair mortar that passivates the steel thanks to its cementi-
tious nature. This is referred to as conventional repair. If the
intervention is carried out removing all carbonated concrete
and with care to mortar placement and curing and to the proper
embedment of reinforcement (i.e., proper concrete cover), the
expected service life may be relatively long, also thanks to
the imperviousness of repair mortars, that hinder further car-
bonation (ACI 546R-96, 1996; BRE Digest 444-3, 2000; EN
1504-9, 2009; Schiessl, 1994). However, according to the
depth of carbonation and the thickness of the concrete cover,
it may be required to remove large amounts of concrete. This
operation is usually undesirable due to the massive production
of waste, noise and dust that may affect the serviceability of
the structure, in particular in the presence of large amounts of
carbonated, but structurally sound concrete.
An alternative to conventional repair is provided by electro-
chemical techniques that aim to stop reinforcement corrosion
by applying a cathodic current (Bertolini, Elsener, Pedeferri,
& Polder, 2004; COST 521, 2003; Liu & Shi, 2009). The
application may be temporary, as in the case of electrochemi-
cal realkalisation, or permanent, as in the case of cathodic
protection, and is obtained with an anode usually placed on
the concrete surface and generally connected with a power
supply (Figure 2). Electrochemical techniques do not require
the removal of all carbonated concrete, since the protection
of steel from corrosion is guaranteed by the effects of the
applied current: only already damaged concrete (e.g., cracked
or delaminated) has to be repaired locally. This allows reduc-
ing the consequences connected with concrete removal and
to preserve as much as possible the original concrete. To this
regard, it should be mentioned that in Italy, as well as in many
other European countries, many modern buildings made with
reinforced concrete, even of recent construction, are protected
from demolition or excessive alteration due to their histori-
cal or architectural value, and this aspect may be of primary
importance in the selection of the repair technique. As a con-
sequence, increasing attention is dedicated to the conservation
of reinforced concrete, thanks to the awareness of its peculiar-
ities with respect to more traditional historical materials, such
180 E. Redaelli et al.: Electrochemical techniques in carbonated concrete

realkalisation occurs on two fronts: from the rebar towards

Figure 1 Evolution of steel corrosion in time during initiation and
propagation phases and consequences of the formation of corrosion
products (Bertolini, 2008).
as stone and brick (De Jonge, 1997; Heinemann, Van Hees, &
Nijland, 2008).
In this paper, included in the special issue dedicated to
Corrosion in Italy, a state-of-the-art on the techniques of
electrochemical realkalisation and cathodic protection in
carbonated concrete will be presented. The main recent find-
ings in this field will be reviewed, with particular reference to
experimental investigations and on-site applications carried
out by the authors in Italy.
2. Electrochemical realkalisation
Electrochemical realkalisation (ER) is a temporary treat-
ment that aims at restoring concrete alkalinity through the
application of a cathodic current and, therefore, at recreating
an environment which is favourable to steel repassivation.
Concrete realkalisation is obtained through the application of
currents of 12 A/m2 with respect to steel surface for a period
ranging from few days to few weeks (Bertolini et al., 2004).
During the treatment, hydroxyl ions are produced at the rebar
surface and, at the same time, an alkaline solution applied
on the surface penetrates the concrete. As a consequence,
the concrete surface and from the concrete surface towards
the reinforcement; when the two fronts overlap, the entire
concrete cover is realkalised (Figure 3).
Compared to conventional repair, ER allows preserving
carbonated concrete, provided it has not been damaged by
steel corrosion, and being a temporary treatment it reduces
the alteration of the concrete surface since the anodic system
is needed only during the application of the current. Typically,
the anodic system is distributed on the concrete surface and
being flexible it can be adapted even on elements of complex
shape, and it is removed at the end of the treatment. The use of
small localised and sacrificial anodes has also been proposed
(Pollet, Guerin, Tourneur, Mahouche, & Raharinaivo, 1997;
Tong, Bouteiller, Marie-Victoire, & Joiret, 2009). For these
reasons, ER is becoming more and more attractive when it
is required to preserve the original aspect of concrete surface
and it can be advantageous compared to conventional repair
in the presence of large amounts of carbonated but sound
concrete and small amounts of cracked concrete to be locally
repaired with mortar.
ER was introduced in Norway in the 1980s (Noteby, 1987;
Vennesland & Miller, 1992) and since then it has mainly
been used in Northern Europe and North America (Elsener,
Zimmermann, Brchler, & Bhni, 1997; Mietz, 1998;
Odden, 1994; Polder & Van den Hondel, 1992; Velivasakis,
Henriksen, & Whitmore, 1998). In Italy only few cases of
application of ER have been reported (Bertolini, Carsana,
& Redaelli, 2006; Bertolini, Carsana, & Redaelli, 2008;
Bertolini, Redaelli, Lattanzi, & Mapelli, 2010), but the inter-
est in its potentialities is increasing, mainly in the field of
cultural heritage. The aim of ER (as of any other repair tech-
nique) is to stop steel corrosion and to avoid the occurrence of
carbonation-induced corrosion for the expected residual life,
typically 1020 years. However, experiences on the long-term
effects of ER treatment are lacking in the scientific literature.
To discuss the effectiveness of ER, data on the effects of the
treatment on concrete alkalinity and on the corrosion condi-
tions of steel will be considered in the following sections and
examples of on-site application of ER carried out in Italy will
be presented.

Figure 2 General schematisation of electrochemical techniques applied to reinforced concrete (Bertolini et al., 2004).

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 E. Redaelli et al.: Electrochemical techniques in carbonated concrete 181

Figure 3 Evolution of concrete realkalisation following application of ER treatment (Bertolini et al., 2004).

2.1. Effects of ER on concrete of realkalisation detected through phenolphthalein test (pink

The main effect of ER is the restoration of concrete alkalin-
ity, due partly to the cathodic reaction at steel surface and
partly to the ingress of an alkaline solution from outside. To
this regard, the circulated charge density, i.e., the product
between the applied current density and the duration of the
treatment is usually considered as the main influencing factor.
For instance, the European Standard on realkalisation indi-
cates a circulated charge of 200 Ah/m2 that should be reached
before terminating the treatment (CEN/TS 14038-1, 2004).
This stems from a basic electrochemistry principle, i.e., the
fact that the amount of hydroxyl ions produced at the steel/
concrete interface is proportional to the applied cathodic cur-
rent, and that, after their production, hydroxyl ions contrib-
ute to the current flow, moving towards the anode. This can
be seen, as an example, in Figure 4 that shows the evolution
toning at pH around 9) on a cylindrical specimen subject to
a cathodic current density of 1 A/m2 for different periods of
time: the radial thickness of realkalised concrete increases
with time, reflecting the increase in the amount of alkalinity
produced at the steel surface (Redaelli & Bertolini, 2011a).
Figure 4 also shows the contribution to concrete realkali-
sation of the alkaline solution penetrating from outside, that
results in an external ring coloured by the indicator: also in
this case, the thickness of the realkalised ring increases with
time, however it is not clear whether the applied current plays
a role on the ingress of the alkaline solution, whose mecha-
nism is not completely clear. Although in-depth studies on
the possible mechanisms involved are not available, many
experimental tests indicate that in the presence of an applied
current the penetration of the alkaline solution is higher com-
pared to that expected with mechanisms of diffusion and/or

Figure 4 Evolution of realkalisation fronts detected with phenolphthalein test during the application of 1 A/m2 on the rebar of a specimen
made with a concrete with w/c ratio of 0.55 and slag cement (Redaelli & Bertolini, 2011a).

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182 E. Redaelli et al.: Electrochemical techniques in carbonated concrete
absorption, and, as a consequence, support the hypothesis
that the applied current forces the solution into the concrete
pores, mainly due to electro-osmotic phenomena (Andrade,
Castellote, Sarra, & Alonso, 1999; Polder & Van den Hondel,
1992). However, other authors have also reported that the
penetration is the same as in natural conditions, i.e., without
applied current (Mietz, 1995). The conditions of humidity
content in the concrete prior to the treatment, to which little
attention is dedicated in the literature, may have an effect on
the ingress mechanism in the initial stages, when concrete sur-
face gets in touch with the solution and, being hygroscopic, it
will suck the solution if its pores are empty, while, if pores are
already soaked with water, a mechanism of pure diffusion is
expected (before the application of the current). However, it
seems unlikely that the initial humidity conditions of concrete
may affect the ingress mechanism in the long term, after the
initial transitory period of wetting.
Recent laboratory tests carried out comparing the penetra-
tion of alkaline solution in specimens of mortar with and
without applied current suggest that the current promotes the
ingress of alkaline solution (Bertolini, Lupica Spagnolo, &
Redaelli, 2012). Tests were performed with two different pH
indicators, phenolphthalein and a commercial indicator which
turns blue for pH values higher than 12, enabling the realkali-
sation due to cathodic reaction to be distinguished from real-
kalisation due to electrolyte penetration. It was observed that
the extent of realkalised area due to electrolyte penetration
was higher when a current was applied, indicating a higher
amount of penetrated solution.
A proper circulated charge density, obtained with an ade-
quate combination between applied current and duration of
treatment, allows obtaining the realkalisation of concrete over
thicknesses of the order of several tens of millimetres, which
are the typical values of concrete cover. However, also param-
eters connected with concrete properties contribute to deter-
mine the realkalisation thickness on both fronts. Concrete
porosity plays an important role, as for all other transport phe-
nomena. For instance, for a given applied current density and
duration, the thickness of realkalised concrete due to cathodic
reaction is higher for concretes with higher water/cement ratio
(Bertolini et al., 2012). For instance, Figure 5 compares the
evolution of realkalisation on concrete with different types of
cement (Redaelli & Bertolini, 2011a), water/cement ratio of
0.55 (shown in Figure 4) and 0.70. The realkalised thickness
around the steel bar (dark grey lines in the lower part of the
Figure) is higher for concrete with w/c of 0.70, which has a
higher porosity compared to concrete with w/c of 0.55. Since
the amount of alkalinity produced by the cathodic reaction
is expected to be the same, being the applied current density
the same, the higher realkalised thickness indicates an easier
transport of hydroxyl ions away from steel surface. Although
phenolphthalein does not allow small pH differences to be
detected, it can be assumed that the local values of pH of real-
kalised areas are slightly lower in the case of w/c of 0.70, due
to a higher dilution of the produced alkalinity. Also realkali-
sation thickness due to the ingress of alkaline solution from
outside is affected by concrete porosity: this is also shown by
the light grey lines in the upper part of Figure 5.
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To this regard, it should also be mentioned that the use of
phenolphthalein, which is very common in practice, as also
suggested by the European Standard on realkalisation (CEN/
TS 14038-1, 2004), only discriminates regions with pH higher
or lower than about 9 and does not allow small variations of
pH values above the threshold of 9 to be detected. Concrete
with pH around 13 is obviously very different (in terms of
protection to steel from corrosion) from concrete with pH
around 10, but after phenolphthalein test their colour is the
same; only a qualitative difference might be evidenced by
a different intensity of the colour. It should always be con-
sidered that a positive phenolphthalein test on concrete does
not necessarily mean that concrete is protected from corro-
sion, since this can only be achieved for pH values of at least
11.5. So, although values of pH higher than 13 are likely to
be reached at the steel surface, the use of phenolphthalein test
to detect realkalised concrete can only give an indication on
the evolution of the treatment; a higher extent of coloured
concrete may be due to a higher porosity of concrete, that pro-
moted the distribution of alkalinity away from its source, and
not necessarily to a higher effectiveness of the treatment. As
a matter of fact, it is expected that the durability of concrete
realkalisation, i.e., its permanence in time, may be reduced
due to possible mechanisms such as, e.g., a new reaction of
carbonation or leaching of alkaline constituents, all of which
are enhanced by an increase of porosity; however, no informa-
tion on this is available in the literature. For instance, it is not
clear if carbonation can further propagate after the treatment,
and what would be the nature of such a reaction in realka-
lised concrete, since portlandite crystals are no longer present
due to the first carbonation process. Experimental tests are
presently carried out to investigate this issue.
The type of cement may also have an effect on the extent of
realkalised concrete: i.e., tests carried out on concrete speci-
mens with the same mix proportions (i.e., the same dosage of
cement, water and aggregate) but two different cement types,
i.e., limestone portland cement and ground granulated blast
Figure 5 Position of internal and external realkalisation fronts
in specimens made with different concrete mixes, after different
durations.
 E. Redaelli et al.: Electrochemical techniques in carbonated concrete
furnace slag cement, showed different realkalised areas. In
particular, concrete with slag cement showed lower internal
realkalised thickness compared to that with limestone port-
land cement. This is usually considered to be related to the
lower initial alkalinity and lower porosity of slag cement
concrete compared to limestone portland cement concrete.
However, the external realkalised thickness was higher for
slag cement concrete. If concrete contains chlorides, even in
small amount, the thickness of realkalisation due to cathodic
reaction is lower compared to chloride-free concrete: this is
also visible in Figure 5 and it can be attributed to the contri-
bution of chloride ions to the transport of current, which is
beneficial in moving chlorides away from steel surface, but
reduces the amount of hydroxyl ions that contribute to the
current, and so the thickness of realkalisation will be more
localised around the steel bar.
The evaluation of the effectiveness of ER cannot neglect
the durability of its effects, i.e., of concrete realkalisation,
since, after the treatment, the concrete will be in contact with
the same environment as before, and thus will be again sub-
ject to carbonation. As it was mentioned earlier, very few data
exist on this issue. The alkaline electrolyte penetrating from
the surface into the concrete pores has a pH of about 10.5, not
exceeding 11, that may not be able to passivate the steel by
itself. On the other hand, the alkaline solution is believed to
buffer pH, hindering further carbonation: indeed, some stud-
ies on realkalised structures demonstrate that the alkalinity of
treated concrete is kept in time (Tong et al., 2009) and that
the sodium carbonate introduced into carbonated zones does
not migrate away at an easily measurable rate (Miller, 1998).
It has also been suggested that ER leads to a densification
of concrete (Banfill, 1997; Yeih & Chang, 2005), especially
around the steel reinforcement, and this is also expected to
prevent future carbonation.
Potentially, a number of side effects may also occur in con-
crete following the application of ER, such as any other elec-
trochemical treatment (Page, 1992). Latent alkali-aggregate
reaction (AAR) may be triggered by the increased amount
of alkali in concrete. This could only occur if aggregates are
susceptible to this attack, and this type of damage has never
been reported in connection with ER treatment (Mietz, 1995);
nevertheless, if the risk of AAR cannot be neglected, lithium-
based electrolytes have been proposed. Also the risk of reduc-
tion of bond strength due to the impressed current should be
considered as potential side effect: this is believed to become
significant above levels of circulated charge much higher
than usually applied. A proper condition evaluation before the
application of the treatment is necessary to prevent these side
effects.
2.2. Effects of ER on steel
Obviously the aim of ER treatment is not the realkalisation
of concrete itself, but rather the interruption of corrosion on
steel reinforcement. As it was mentioned in the previous sec-
tion, according to the theory of corrosion a pH value higher
than 11.5 is necessary to passivate the steel (Pourbaix, 1974),
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183
and such value can be achieved in the vicinity of steel surface
due to the applied cathodic current. Hence, it has often been a
priori assumed that after ER treatment, steel is repassivated.
However, a number of experimental tests that investigated
the corrosion behaviour of steel after the application of ER
showed a different behaviour of steel in realkalised concrete
compared to steel in an originally alkaline concrete. In this
regard, the corrosion conditions of steel before the applica-
tion of the treatment seem to be a key factor. For instance,
Figure 6 shows the values of corrosion rate measured on
steel bars embedded in concrete with different composition,
before and after the treatment, during exposure to a wet envi-
ronment. Corrosion rate was measured through the linear
polarisation resistance technique and expressed as current
density (Andrade & Gonzlez, 1978; Stern & Geary, 1957).
A decrease in the corrosion rate was observed on specimens
that had been exposed to a wet environment for a period of
about three months before and after the application of ER: for
instance, in concrete made with limestone portland cement
and w/c of 0.55, the corrosion rate passed from 11 mA/m2 to
4 mA/m2, in concrete made with limestone portland cement,
w/c of 0.55 and 0.4% of chlorides with respect to cement
mass, it changed from 20 mA/m2 to 8 mA/m2 and in con-
crete made with slag cement and w/c of 0.55 from 12 mA/m2
to 4 mA/m2. In these cases, although the values after the
treatment cannot be considered negligible, the effect of the
treatment in reducing corrosion activity of steel is evident.
Some other specimens were exposed to the wet environment
for a period of a year before the treatment, in order to pro-
mote some pre-corrosion of steel bars, which is what may be
expected to occur in real structures before the application of
ER treatment. In this case, the corrosion rate measured after
ER was even higher than before: i.e., it passed from 13 mA/m2
to 24 mA/m2 in concrete with w/c of 0.7 without chlorides and
from 26 mA/m2 to 42 mA/m2 in concrete with the same w/c
and 0.4% of chlorides (Figure 6). This effect was also con-
firmed on similar specimens exposed to a dry environment
Figure 6 Average values of corrosion rate of steel measured with
polarisation resistance technique, in a wet environment, before
and after ER treatment, for different concrete mixes (Redaelli &
Bertolini, 2011a).
184 E. Redaelli et al.: Electrochemical techniques in carbonated concrete
(Redaelli & Bertolini, 2011a). It should be noted that poten-
tial measurements carried out on the same specimens showed
that steel potential increased in all cases after the treatment,
which would suggest changes towards repassivation. It should
also be noted that the evaluation of corrosion conditions of
steel after the application of electrochemical treatments by
means of electrochemical technique has been questioned
(Mietz, 1998). So the increase of corrosion rate may be due
to unsuitability of linear polarisation technique, however it is
not clear why the increase is observed only on pre-corroded
steel. Also to this regard, further tests are being carried out to
clarify these aspects. It should also be noted that the increase
in corrosion rate after ER treatment has also been reported by
direct measurements of weight loss (Kubo, Sawada, Page, &
Page, 2008). It has even been suggested that ER may only be
effective as a preventative measure against corrosion, before
the carbonation front reaches the steel or for steel repassiva-
tion at an early corrosion stage (Gonzlez, Cobo, Gonzlez,
& Otero, 2000).
In those cases when the effectiveness of ER in reducing
corrosion rate has been assessed, the circulated charge is an
important factor in determining the level of protection reached
by the steel: for instance, Figure 7 shows the current density
measured during potentiostatic anodic tests with an applied
potential value of 150 mV vs. SSC, on specimens subject
to ER with applied current of 0.5 A/m2 for different periods
(7, 14 and 21 days), i.e., different circulated charge density
(84, 168 and 252 Ah/m2). The polarisation current measured
during polarisation tests may be used to discriminate condi-
tions of passivity (expected low values of current density)
from conditions of activity (high values of current density).
The current measured during potentiostatic tests was around
2000 mA/m2 for the reference specimens (i.e., active steel in
carbonated concrete), and decreased to 40, 4 and 2.5 mA/m2
increasing the circulated charge density from 84 to 252 Ah/m2
(Bertolini et al., 2012). The reduction of the measured current
density obtained increasing the duration indicates a beneficial
Figure 7 Current density measured during anodic potentiostatic
tests on specimens subject to ER treatment with different durations
(7, 14 and 21 days) and on the reference specimen (Ref). Applied
potential value: +150 mV vs. SSC (Bertolini et al., 2012).
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effect of the applied cathodic current, which is consistent with
the theory of corrosion, i.e., with the progressive beneficial
effect of an applied cathodic current in the protection of steel
from corrosion. These results are in agreement with similar
tests that were previously reported (Mietz, 1995).
It should be observed that, also from the point of view of the
steel behaviour, possible side effects of ER can be considered.
These are mainly related to possible induction of hydrogen
embrittlement on high strength steel. Since the application of
high cathodic currents may promote hydrogen evolution at the
steel surface, ER is considered unsuitable in the case of pre-
stressed structures with high strength steel (COST 534, 2009).
2.3. On-site applications in Italy
An on-site application of ER was done on the church of S.
Antonio abate in Valmadrera, in Italy. The church was built
in 19261930 and includes a bell tower, in the upper part
of which is located a small circular temple made of eight
columns overhung by a dome (Bertolini et al., 2008). All
the columns are made of reinforced concrete and they are
hollow: the thickness of the concrete wall ranges from 55 mm
to 78 mm. Owing to its high historical value and architec-
tural significance, the church is part of the Italian National
Cultural Heritage. A preliminary survey showed that cracks,
delaminations and spalling of the concrete cover were pres-
ent on the columns (Figure 8). Afterwards, measurements of
Figure 8 View of reinforced concrete columns on the bell tower
of the church of S. Antonio abate in Valmadrera (Bertolini et al.,
2008).
 E. Redaelli et al.: Electrochemical techniques in carbonated concrete 185

carbonation depth, steel potential and thickness of concrete

cover were carried out. Carbonation depth showed a very
uneven distribution: the thickness of the carbonated concrete
ranged from 1 mm to 55 mm (equal to the whole thickness
of the concrete wall). Similarly, the thickness of the concrete
cover showed an irregular distribution. It was decided to
make an intervention on the columns in order to stop steel
corrosion, by applying ER treatment with a current density
of 0.8 A/m2 for 21 days. Figure 9 shows the potential of steel
measured with internal reference electrodes during and after
the application of the current: the steel reached very nega-
tive potential values, between -1 and -2 V vs. CSE. After the
end of the treatment, the steel potential increased and reached
potential values of about -350 mV vs. CSE more than a month
after the end of the treatment. Phenolphthalein tests on cores
taken from the columns indicated complete alkalinity of con-
crete, mainly due to the cathodic reaction which had a domi-
nant effect compared to the ingress of alkaline electrolyte.
A trial application of ER was also carried out on the pillars
of the church of Santa Maria dellAnnunciata at the San Carlo
Borromeo hospital in Milan that was designed by the architect
Gio Ponti and was built in 19641967 (Bertolini et al., 2010).
The structure of the church is made of reinforced concrete;
externally the walls are covered with ceramic tiles, while the
pillars are in fair-faced concrete. The pillars showed deterio-
Figure 10 View of corrosion-induced damage on a reinforced con-
ration phenomena due to reinforcement corrosion (Figure 10).
crete pillar of the church of Santa Maria dellAnnunciata at the San
In this case, a study aimed at comparing the effectiveness of Carlo Borromeo hospital in Milan (Bertolini et al., 2010).
different repair strategies on selected areas of the pillars was
carried out. The evolution of the ER treatment was evaluated
with potential measurements and phenolphthalein tests on Although it is usually believed that ER treatment does not
concrete cores (Figure 11). Comparing the potential of steel require any monitoring after application, in the opinion of the
in different areas of the pillars (Figure 12), it can be observed authors it is advisable not only to check its proper functioning
that, whilst reference non-treated concrete is characterised during and at end of current application, but also to anticipate
by higher steel potential values compared to realkalised con- future monitoring. While the measurement of corrosion rate
crete, the potential decrease observed after artificial wetting on-site is rather complex, the corrosion potential is easier to
of concrete surface (simulating wetting from the rain) is lower detect, also with embedded reference electrodes that allow
in realkalised concrete, indicating a lower effect of humidity a continuous monitoring. Nevertheless, as it was mentioned
which is consistent with steel repassivation. earlier, potential measurements after electrochemical treat-
ments are not easy to interpret and may not be directly related
to corrosion conditions of steel reinforcement. Anyway,
investigations carried out on real structures may be helpful in
the understanding of effects of ER treatment, in particular in
the long-term.

3. Cathodic protection

Cathodic protection (CP) is a permanent technique that

Figure 9 Steel potential measured on the eight columns (AH)
before, during and after the treatment of realkalisation (Bertolini
et al., 2008).
applies current densities around 510 mA/m2 with respect to
steel surface, much lower compared to that used in ER. CP
of steel in concrete was initially introduced in the 1970s to
stop chloride-induced corrosion on highway bridges contami-
nated by de-icing salts (Lazzari & Pedeferri, 2006; Stratfull,
1974); in this field, as well as for structures and buildings
exposed to marine environments, CP is recognised as the only
repair technique that can stop chloride-induced corrosion
(Wyatt, 1993). Initially CP was not applied on carbonated
concrete, that was considered much less aggressive compared

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186 E. Redaelli et al.: Electrochemical techniques in carbonated concrete

Figure 11 Phenolphthalein tests carried out on cores taken in two adiacent areas from a pillar of the church of Santa Maria dellAnnunciata
at the San Carlo Borromeo hospital in Milan: before (A) and after (B) realkalisation (Bertolini et al., 2010).

to chloride-contaminated concrete, and the repair of carbon-
ated concrete was carried out in the conventional way, that
was considered more than suitable. P. Pedeferri, in the 1990s,
introduced advantages of CP in carbonated concrete explain-
ing that it acts with a mechanism similar to ER, which he
called continuous realkalisation. The small cathodic cur-
rent provided by CP may, in time, promote realkalisation of
a thin layer of concrete surrounding the steel bars in carbon-
ated concrete, inducing steel repassivation (Pedeferri, 1996).
Today CP is considered as one of the possible effective options
for the repair of structures, buildings and facades suffering
carbonation-induced corrosion. Similarly to ER, it allows the
original concrete to be preserved, but being a continuous tech-
nique, it has to be applied throughout the residual service life
of the structure in order to keep corrosion rate under control.
This, however, requires constant monitoring in time.
The current is traditionally applied with impressed cur-
rent distributed inert anodes, as metallic meshes embedded
in mortar or conductive coatings, although other anodic con-
figurations are possible and the use of sacrificial anodes is
increasing (Page & Sergi, 2000). Impressed systems allow
the applied current to be adjusted in case of under protection
or over protection; sacrificial anodes are self-regulating since
the current they supply is determined by the driving voltage
and the electrical resistance between steel and anode. In the
case of impressed systems, attention should be paid to avoid
direct contact between steel and anode; in the case of sacrifi-
cial systems, the anode is directly connected to the steel and
this often allows the need of connecting cables to be avoided.
Both in impressed current and sacrificial CP systems, the
anode can be distributed, i.e., applied on the whole concrete
surface, or localised, i.e., applied in small areas of the surface
or inserted in cavities in the concrete.
It was shown that repassivation of steel may be favoured
by the application of an initial high initial current density
that promotes faster realkalisation of concrete. For instance,
with laboratory tests it was shown that current densities of
70100 mA/m2 applied for a few weeks to steel in carbonated
concrete may be effective in promoting steel repassivation,
while several months were required with a current density
of 10 mA/m2. Once repassivation of steel is achieved, this
is subsequently maintained with lower current densities of
510 mA/m2 (Bertolini, Pastore, Pedeferri, & Redaelli, 2003).
Therefore, in the design of CP for carbonated concrete struc-
tures, the benefit of an initial start-up current may be taken
into consideration.

Figure 12 Average potential of steel in reference areas (A) and realkalised areas (B). Dotted lines indicate artificial wettings and their dura-
tion, while grey area indicates ER treatment (Bertolini et al., 2010).

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 E. Redaelli et al.: Electrochemical techniques in carbonated concrete
Since CP relies on the application of a continuous cur-
rent, the protection from corrosion needs to be properly
monitored in time to check the correct functioning of the
system. The need for a monitoring system differentiates
CP from temporary techniques. Although several methods
have been proposed in the literature (Bennet & Broomfield,
1997; Glass, Hassanein, & Buenfeld, 1997; Rizzo, 1988),
monitoring of reinforcement under CP is usually based on
measurement of absolute potential or potential decay (ISO
DIS 12696, 2009), the latter being more reliable since the
absolute potential depends on many factors in concrete.
Steel potential has to be measured with on-off techniques
to avoid ohmic contribution. According to the potential
decay criterion, it is usually assumed that steel under CP
can be considered protected from corrosion if the poten-
tial decay measured after interruption of the current is
higher than 100 mV in a period of 4 or 24 h. This is the
100-mV criterion, which is a semi-empirical criterion for
atmospherically exposed structures. It relies on the increase
of steel potential after depolarisation that is expected after
steel repassivation, which is not merely connected with the
potential decrease due to the applied current, but also with
the chemical changes induced by the current at the steel
surface, typically the local increase of concrete alkalin-
ity and the migration of chlorides (if present) towards the
anode (Glass & Chadwick, 1994).
Whilst many publications investigate the effectiveness of
CP in chloride-contaminated concrete structures, much less
investigations have been devoted to CP in carbonated con-
crete. Among these, an experimental research studied the
effect of concrete composition, environmental conditions
and pre-corrosion of steel on the effects of CP applied with
a current density of 10 mA/m2 preceded by a start-up value
of 100 mA/m2 for three weeks (Redaelli & Bertolini, 2011b).
The results obtained indicate that the realkalised thickness of
concrete around the steel after the start-up period is of the
order of few millimetres, and with such small values no effect
of water/cement ratio, cement type or chloride content has
been detected. However, the presence of this layer of alkaline
concrete, detected with phenolphthalein indicator, is (again)
not correlated to corrosion conditions of steel that were inves-
tigated with 4 h depolarisation tests and indicated that only
specimens made with chloride-free concrete have 4-h decays
higher than 100 mV. Afterwards, during the continuous appli-
cation of 10 mA/m2, the 4-h decay progressively increases,
however for a given concrete composition pre-corroded rein-
forcement always has lower 4-h decays compared to non-
pre-corroded specimens, in particular in the wet environment.
As for ER, also for CP the protection of steel from corro-
sion is reached with more difficulty if steel is pre-corroded,
and so the sooner it is applied, the more effective it will be.
However, unlike in ER treatment, in CP the lack of protection
indicated by 4-h decays lower than 100 mV can be overcome
(in impressed current systems) increasing the applied cur-
rent in order to reach more stable conditions of protection or
reducing the time necessary to protect the steel. This should
always be carefully considered in the design phase if hydro-
gen evolution has to be avoided.
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187
3.1. Case study on CP with localised anodes
An alternative to ordinary CP applied with distributed anodic
system, which causes the complete alteration of the concrete
surface, is the use of localised anodes. Localised anodes can
have the shape of small cylinders to be inserted inside con-
crete or thin stripes or wires to be placed on the concrete sur-
face. In principle, localised anodes can be used either with
impressed current or as sacrificial anodes; however, sacrifi-
cial anodes are more suitable for the use as localised anodes
since, being directly connected with steel reinforcement, they
do not require external cables for connection to power supply
and/or monitoring system. The use of localised anodes has
been introduced as a preventative measure in patch-repaired
concrete (Page & Sergi, 2000); later on, it was also suggested
to use localised anodes in hybrid systems, i.e., initially
with impressed current and then as sacrificial anodes (Glass,
Roberts, & Davison, 2008). These applications, however,
were mainly concerned with concrete suffering chloride-
induced corrosion and limited area to be protected. Advantages
of sacrificial anodes have also been shown for the prevention
of corrosion initiation in the splash zone of marine structures
(Bertolini, Gastaldi, Pedeferri, & Redaelli, 2002; Bertolini &
Redaelli, 2009).
Carbonated concrete, in spite of being a less aggressive
environment towards steel, is characterised by higher electri-
cal resistivity and it is usually exposed to atmospheric condi-
tions, and problems connected with current distribution typical
of localised anodes are thus emphasised: reinforcement closer
to the anode will receive higher currents, thus undergoing a
higher risk of problems connected with the application of a
high cathodic current density (e.g., hydrogen embrittlement
in the presence of high strength steels), whilst reinforcement
far from the anode will receive low or no current, thus lack-
ing protection from corrosion. As a consequence, the use of
localised sacrificial anodes should always be preceded by
a careful study of current and potential distribution, either
experimental or by means of numerical simulations, with the
aim of determining the number of anodes and their position
so that the cathodic current supplied will be able to reach all
the steel reinforcement that need protection, avoiding regions
of overprotection.
For instance, a study carried out through numerical simula-
tions of current distribution in carbonated concrete showed
that, in the presence of elements with slender geometry, the
number of anodes that are necessary to protect all the rein-
forcement may partly reduce the advantages connected with
localised anodes. Figure 13 shows, as an example, the polari-
sation and current density along the height of the reinforce-
ment of a concrete element containing longitudinal steel bars
in the front and in the rear part, with three sacrificial anodes
placed in the front part. It was assumed that concrete was car-
bonated in the front part (in contact with the atmosphere) and
alkaline in the rear part (embedded in masonry), and proper
conditions describing the behaviour of steel were specified as
a function of humidity and alkalinity/carbonation of concrete
(Redaelli, Lollini, & Bertolini, 2011). It can be seen that only
parts of rebar close to the localised sacrificial anodes receive
188 E. Redaelli et al.: Electrochemical techniques in carbonated concrete

Figure 13 Reinforced concrete element subject to CP with localised sacrificial anodes (A), distributions of cathodic polarisation (B) and of
current density (C) obtained by FEM numerical simulations.

enough current to be protected (in this case, protection was
evaluated with a modified decay criterion), while parts far
from the anode do not receive enough current. With similar
simulations it was estimated that full protection of steel in
carbonated concrete during wetting periods can be achieved
by placing anodes at a distance of 0.5 m from each other.
Although current distribution is likely to be the major
problem connected with the application of CP with loca-
lised sacrificial anodes in carbonated concrete, another factor
that should be considered is the consumption of the anode
material due the anodic reaction of metal dissolution. These
anodes are usually made of zinc embedded in an activating
medium. The smaller is the anode, the higher is the current
density supplied and therefore, according to Faradays law,
the higher is the rate of consumption of zinc. This factor may
limit the time duration of the anodic system, however it is
difficult to estimate in advance since it depends on all the fac-
tors influencing the current, such as the number of anodes and
their position and the trend of environmental conditions (that
determines the electrical resistivity of concrete). Also in this
regard, experimental trials or numerical simulations are nec-
essary to make an estimation of the current, and therefore, of
the anode duration, in particular if on-site monitoring is not
feasible.
4. Concluding remarks
The repair of reinforced concrete buildings, facades or monu-
ments that have a high cultural, historical and architectural
value requires the original materials to be preserved as much
as possible and reduce the alteration of the surface and, as
a consequence, the use of electrochemical techniques is
increasing. In the case of carbonation-induced corrosion, two
techniques can be used: electrochemical realkalisation and
cathodic protection.
In the case of the temporary technique of electrochemi-
cal realkalisation, the realkalisation of concrete detected
with phenolphthalein test is mainly affected by the circulated
charge density, however also concrete porosity, cement type,
and the presence of chloride may play a role. The mechanisms
involved in realkalisation due to electrolyte penetration, as
well as the physical changes induced in the concrete, have
not been clarified yet. Also the parameters that may affect the
corrosion conditions of steel after the treatment need further
investigation, in order to assess the complete reliability of the
technique and the possible ways to determine it, in particular
in the presence of high level of steel corrosion prior to the
application of the treatment.
In the case of cathodic protection, which is based on the
application of a continuous current, steel pre-corrosion as
well as the presence of chlorides also have an effect on the
fulfilment of protection on steel, in particular in wet environ-
ments. However, in this case a lack or reduced protection can
be overcome by a proper increase in the applied current, pro-
vided no risk of hydrogen embrittlement occurs.
Works reported in the literature show that under specific
conditions the electrochemical techniques of ER and CP are
effective in controlling the corrosion rate of steel in carbonated
concrete, preserving meanwhile concrete. Nevertheless, as dis-
cussed in the paper, there are still several open questions which
need further research in order to provide input data regarding
the selection of the technique and the most appropriate moment
to apply it (especially in the case of temporary treatment).

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 E. Redaelli et al.: Electrochemical techniques in carbonated concrete
Furthermore, there is still opportunity for improvement in the
application of electrochemical methods. For instance, the appli-
cation of cathodic protection with localised and sacrificial anodes
has been introduced recently with the aim of reducing the inva-
siveness of the technique and the alteration of the surface. When
considering such intervention, it should be considered that the
durability of the anode is expected to be lower compared to inert
anodic systems due to anode consumption. The study of current
distribution, either by means of trial tests or numerical simula-
tions, may allow to determine the anode configuration (in terms
of number and position of anodes) that optimises protection to
steel and also to estimate anode consumption.
Acknowledgements
The authors would like to dedicate this paper to the memory of Pietro
Pedeferri acknowledging his great contribution to the development
of electrochemical techniques in reinforced concrete.
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