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Materials and Corrosion 54, 163±175 (2003) Repassivation of steel in concrete 163

Repassivation of steel in carbonated concrete


induced by cathodic protection
Durch kathodischen Schutz induzierte Repassivierung von Stahl in
karbonatisiertem Beton
L. Bertolini*, P. Pedeferri, E. Redaelli
and T. Pastore

The paper discusses the peculiarities of cathodic protection ap- Die vorliegende Arbeit diskutiert die im Zusammenhang mit der
plied to steel in carbonated concrete, which are strictly connected to Produktion von AlkalitaÈt an der StahloberflaÈche verbundenen
the production of alkalinity at the steel surface. Results of a research Merkmale des kathodischen Schutzes, der fuÈr Bewehrungsstahl
on the application of cathodic protection to specimens with steel in karbonatisiertem Beton eingesetzt wurde. Die Ergebnisse einer
bars in carbonated concrete are discussed. A thin layer of concrete Untersuchung zur Anwendung des kathodischen Schutzes fuÈr Pro-
was realkalized within a period of 4 ± 5 months by applying a cur- ben mit StahlstaÈben in karbonatisiertem Beton werden diskutiert.
rent density of 10 mA/m2 and steel could repassivate even in the Eine duÈnne Betonschicht wurde innerhalb von 4 ± 5 Monaten durch
presence of small contents of chlorides. A lower current density Anwendung einer Stromdichte von 10 mA/m2 realkalisiert und der
of 5 mA/m2 could only maintain steel passive when the concrete Stahl repassivierte sogar bei Anwesenheit geringer Gehalte an
in the vicinity of the steel had been previously realkalized through Chloriden. Eine niedrigere Stromdichte von 5 mA/m2 konnte am
the application of a start-up current density of 70 mA/m2 for one Stahl eine Passivierung nur dann aufrechterhalten, wenn der Beton
month. Protection mechanisms are investigated and design of in der NaÈhe des Stahles vorher durch die Anwendung einer An-
cathodic protection of steel in carbonated concrete is outlined. fangsstromdichte von 70 mA/m2 fuÈr einen Monat realkalisiert wur-
The possibility of obtaining protection on deeper rebars is also con- de. Die Schutzmechanismen sind untersucht worden und das De-
sidered. sign des kathodischen Schutzes fuÈr Stahl in karbonatisiertem Beton
wird skizziert. Die MoÈglichkeit, den Schutz auch fuÈr tiefer liegende
Bewehrung zu erreichen, wird ebenfalls beruÈcksichtigt.

1 Introduction concrete increases if the concrete is contaminated by chlorides


even in a small amount, e.g. lower than the value of 0.4% by
Protection of reinforcement in concrete, which is due to weight of cement that is normally assumed as a safe threshold
passivity of steel brought about by the high pH (around 13) for chloride induced corrosion in alkaline concrete [3]. Small
of the liquid in the pores of the cement paste, can be annihi- amounts of chlorides can often be found in structures built
lated by carbonation [1]. The carbonation reaction of cement before the Eighties, because of the use of chloride contami-
paste with carbon dioxide in the atmosphere lowers the pH of nated admixtures or aggregates.
the pore solution to values around 9, which are inadequate to Conventional repair, consisting in the removal of the car-
guarantee the stability of the passive film. Consequently, bonated concrete and its replacement with new alkaline mor-
when carbonation reaches the steel reinforcement, this can tar, is normally used to repair structures damaged by carbona-
corrode provided oxygen and water are available. Corrosion tion induced corrosion. If properly made, the conventional re-
rate of steel in carbonated concrete largely depends on the hu- pair can often be a cost-effective means for restoring protec-
midity content of the concrete. Corrosion rate is negligible in tion to the reinforcement [4, 5]. Nevertheless, to prevent fu-
dry concrete, e.g. lower than 1 lm/year, while in moist or wet ture damage throughout the residual service life of the struc-
concrete it can be high and soon leads to cracking or delami- ture, large quantities of concrete often need to be removed
nation of the concrete cover [2]. Corrosion rate in carbonated even if concrete is still structurally sound. In fact, if concrete
is carbonated and corrosion rate of embedded steel is not neg-
ligible, such as in moist concrete especially if contaminated by
chloride, cracking of the concrete cover can take place in a
relatively short period.
Removal of carbonated but structurally sound concrete is an
* L. Bertolini, P. Pedeferri, E. Redaelli undesirable operation because it gives a significant contribu-
Dipartimento di Chimica, Materiali e Ingegneria Chimica
ªG. Nattaº, Politecnico di Milano, tion to the cost of the repair and it leads to the replacement of a
Piazza Leonardo da Vinci 32, material that still contributes to the strength of the structure.
20133 Milano (Italy) Furthermore, the removal itself can cause problems both to the
T. Pastore structure under repair and to the structures in the vicinity of it,
Dipartimento di Ingegneria, UniversitaÁ degli Studi di Bergamo, for instance due to interruption of service, production of dust,
Bergamo (Italy) or generation of noise.

F 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 0947-5117/03/0303-0163$17.50‡.50/0


164 Bertolini, Pedeferri, Redaelli and Pastore Materials and Corrosion 54, 163±175 (2003)

Some electrochemical methods have been developed that


can restore the protection to the reinforcement in carbonated
or chloride contaminated concrete, without requiring the re-
moval of the structurally sound concrete [6, 7]. For instance
electrochemical realkalization consists in the application of a
cathodic current of the order of 1 A/m2 to the reinforcement by
means of an external temporary anode embedded in an alka-
line electrolyte. It is aimed at restoring alkalinity around the
bars in carbonated concrete and thus restoring passivity on the
steel [8].
It was observed that realkalization of concrete can also be
produced by much lower current densities, of the order of Fig. 1. Geometry of the specimens (dimensions in mm)
10 mA/m2, typical of cathodic protection (CP) [9]. The appli- Abb. 1. Geometrie der Proben (Abmessungen in mm)
cation of CP to reinforced concrete is based on the experience
gained since the early 1970s on structures contaminated by
chlorides (principally decks of highway bridges) [10]. In
that case, protection of steel is mainly due to the lowering
of steel potential (due to cathodic polarization), which can
stop localized corrosion of steel in contact with chloride con-
taminated concrete. The alkalinity produced by the cathodic
reaction that takes place at the surface of the steel is a second-
ary beneficial effect [11 ± 13]. In the application of cathodic
protection to steel in carbonated concrete, it was shown
that, although the cathodic current leads to a modest lowering
of the steel potential, it can produce enough alkalinity to bring
the pH of the concrete in contact with the steel from values
around 9 to values higher than 12, that are enough to repassi-
vate the steel [14, 15].
Cathodic protection has been applied to several structures,
mainly buildings, suffering of carbonation induced corrosion,
especially in the presence of small amounts of chloride in the
concrete [16, 17]. Nevertheless, peculiarities of CP applied to
steel in carbonated concrete and its protection effects have
never been investigated in details. Fig. 2. Schematic representation of the arrangement of specimens
during tests: (a) tests with a single layer of bars, (b) two-layer speci-
This paper reports the results of a long term laboratory re- mens
search on reinforced concrete slabs subjected to cathodic pro-
Abb. 2. Schematische Darstellung der Probenarrangements waÈh-
tection. The realkalization produced by the application of dif- rend der PruÈfung: (a) Versuche mit einlagiger Bewehrung, (b) Ver-
ferent cathodic current densities to the reinforcement in car- suche mit zweilagiger Bewehrung
bonated concrete are discussed. Methods for monitoring and
design CP in carbonated concrete are investigated.

Nine of the specimens without chlorides and the nine with


chlorides were subjected to accelerated carbonation. Fifteen
2 Experimental procedure days after casting they were exposed to an atmosphere with
5% carbon dioxide and 60% relative humidity. After two
Tests were carried out on 27 specimens with the geometry months of exposure, when the full thickness of the specimens
shown in Fig. 1. Each specimen had three steel bars that were was carbonated, an activated titanium mesh was applied on
electrically connected. The total steel surface exposed to con- one surface, embedded in a 15 mm thick cementitious overlay.
crete in each specimen was 0.05 m2. Concrete was mixed with Subsequently each set of specimens (alkaline, carbonated, and
260 kg/m3 of Portland cement, 0.65 water to cement ratio, and carbonated with chlorides) was exposed outside, in vertical
2000 kg/m3 crushed limestone aggregate. The average com- position, as shown in Fig. 2a. One slab of each set was left
pressive strength after 28 days of moist curing was 40 in free corrosion condition. The others were subjected to
MPa. 0.4% chlorides by weight of cement were added to cathodic protection, by applying a cathodic current of
the concrete of nine specimens, as calcium chloride in the 0.5 mA to groups of 1, 2, and 5 parallel specimens, so that
mix water. The specimens were moist cured at 95% relative current densities respectively of 10, 5, and 2 mA/m2 (of steel
humidity (R.H.) for two days (in the mould during the first surface) were obtained.
day) and then exposed to a 50% R.H. atmosphere. The rein- The potential of the steel bars was monitored with respect to
forcement of each specimen consisted of three bars of carbon manganese dioxide reference electrodes. Four-hour depolari-
steel, 10 mm in diameter, electrically connected through ex- sation tests were regularly carried out; the instant-off (Eoff)
ternal wires. Manganese dioxide reference electrodes were and the four-hour (E4h) potentials were measured respectively
embedded in the concrete near the central bar for monitoring within 1 ms and after 4 hours from switching the current off;
the steel potential. pH-sensitive probes made of a thin wire of the four-hour decay was then calculated as DE4h ˆ E4h ± Eoff.
activated titanium were also embedded at a distance of 1 and Potential of activated titanium electrodes embedded in the
3 mm from the steel surface in order to monitor changes in the vicinity of the steel surface was regularly measured against
pH of the pore solution. manganese dioxide reference electrodes during depolarisation
Materials and Corrosion 54, 163±175 (2003) Repassivation of steel in concrete 165

tests (i.e. when current was switched off), in order to monitor


pH changes in the concrete near the steel surface. The actual
realkalization of concrete was also measured by phenolphtha-
lein tests on samples cored from the tested specimens.
After 18 months, tests were interrupted in the slabs with the
lowest current density of 2 mA/m2 and some of these speci-
mens were subjected to further tests. Two carbonated speci-
mens (one free of chlorides and one with chlorides) were sub-
jected to a current density of 70 mA/m2 for 28 days, in order to
evaluate the influence of a high current density at start up (this
current density was equivalent to 100 mA/m2 on the anode,
i.e. the maximum design current density for activated titanium
anodes); the current density on the rebars was then reduced to
10 mA/m2. In a further carbonated specimen, after the appli-
cation of 70 mA/m2 for 28 days, the current density was de-
creased to 5 mA/m2.
To evaluate the throwing power of cathodic protection in a
slab with two layers of reinforcement, couples of specimens Fig. 4. Average value and standard deviation of the potential of ac-
were joined with a layer of mortar (Fig. 2b) and all the rebars tivated titanium electrodes placed at 1 mm (MMO-1 mm) and
were electrically connected. A current of 1 mA was applied 3 mm (MMO-3 mm) from the steel surface in the control specimens
through one of the anodic meshes, so that nominal current Abb. 4. Mittelwert und Standardabweichung des Potentials der ak-
density on the rebars was 10 mA/m2. The current distribution tivierten Titanelektroden, die 1 mm (MMO-1 mm) und 3 mm
was evaluated by measuring the current circulating in each (MMO-3 mm) entfernt von der StahloberflaÈche in den Kontrollpro-
layer of bars, by means of 10 X shunt resistances. A multi- ben platziert waren
layer specimen was also subjected to a start up current density
of 35 mA/m2 for 60 days, before the application of 10 mA/m2.
After five years the tests were interrupted for 1 month in all
the specimens and the polarization resistance of rebars was 3.1 Control specimens
measured with potentiostatic tests at  10 mV versus the
free corrosion potential. Afterwards cathodic protection The free corrosion potential of steel was around 200 mV
was applied again and four-hour decay was measured after in alkaline concrete, while it decreased in the range 600 mV
one week. to 300 mV in carbonated concrete without chlorides and
700 to 500 mV in carbonated concrete with 0.4% chlorides
by weight of cement (Fig. 3). Significant changes in time were
3 Results observed especially on active steel in carbonated concrete
without chlorides, due to seasonal and humidity variations.
Results of monitoring of potential in the control specimens The polarization resistance of the steel bars measured during
and in the specimens protected with different current densities the first month of exposure was 50, 6 and 3 X  m2 in alkaline,
are shown in Fig. 3 ± 8. The potential values are measured carbonated and carbonated with chlorides concrete, respec-
against internal manganese dioxide reference electrodes. tively. The potentials of the activated titanium electrodes
were rather constant. Fig. 4 shows that they had average va-
lues below 100 mV in alkaline concrete and 0 ± 70 mV in
carbonated concrete.

3.2 CP in alkaline concrete

Fig. 5 shows the potential of steel bars in alkaline concrete


protected with 2, 5 and 10 mA/m2 cathodic current densities.
The instant off potentials (Eoff) ranged between 450 and
900 mV depending on the current density. The potentials
measured four hours after switching the current off (E4h)
were around 250/ 350 mV. Four-hour decay (E4h ± Eoff)
was constantly higher than 200 mV, even with the lowest cur-
rent density of 2 mA/m2. The potential of the activated tita-
nium electrodes placed both at 1 mm (MMO-1 mm) and
3 mm (MMO-1 mm) from the steel surface, remained around
100 mV in all the specimens.

Fig. 3. Free corrosion potential of steel in alkaline concrete, car-


bonated concrete and carbonated concrete with 0.4% chlorides 3.3 CP in carbonated concrete
by weight of cement
Abb. 3. Freies Korrosionspotential des Stahles in alkalischem Be- Fig. 6 shows the results of the tests on steel in carbonated
ton, karbonatisiertem Beton und karbonatisiertem Beton mit 0,4% concrete and carbonated concrete with 0.4% of chloride by
Chloriden (bez. auf Zement) weight of cement. Seasonal fluctuations of Eoff were observed
166 Bertolini, Pedeferri, Redaelli and Pastore Materials and Corrosion 54, 163±175 (2003)

Fig. 5. Potential measurements in alkaline concrete protected with 2, 5 and 10 mA/


m2: ( *) Eoff, (*) E4h, (‡) MMO-1 mm, () MMO-3 mm
Abb. 5. Potentialmessungen in alkalischem Beton, der mit 2, 5 und 10 mA/m2 ge-
schuÈtzt war: ( *) Eoff, (*) E4h, (‡) MMO-1 mm, () MMO-3 mm

in all the specimens; lower values of potential were measured specimen contaminated by chloride (Fig. 6f) also showed
in winter time. In the specimens protected with 2 mA/m2 the increase in E4h after five months of application of
(Fig. 6a and 6b), Eoff and E4h fluctuated around 550/ 10 mA/m2, although only minor changes in time were ob-
600 mV. The four-hour decay was always negligible (less served in the potential of activated titanium electrodes.
than 50 mV in carbonated concrete and 20 mV in carbonated
concrete with chlorides). The potential of the activated tita-
nium electrodes was higher than 0 mV throughout the testing 3.4 CP with start-up current density
period. These tests were interrupted after 18 months.
In the specimens protected with 5 and 10 mA/m2, Eoff ran- Fig. 7 shows the results obtained by applying a current den-
ged between 600 and 900 mV. In the carbonated slab pro- sity of 70 mA/m2 for 1 month, followed by current densities of
tected with 5 mA/m2 (Fig. 6c), E4h remained close to Eoff even 5 or 10 mA/m2. These tests were carried out on the specimens
after five years of testing, and thus the four-hour decay was previously tested at 2 mA/m2 for 18 months. During the ap-
low (rarely higher than 60 mV). In the specimen with carbo- plication of 70 mA/m2, the instant off potential reached very
nated concrete contaminated by chlorides (Fig. 6d), E4h was negative values in all the specimens (about 1.2 V). Subse-
slightly higher, and four-hour decay occasionally exceeded quently, when the current density was reduced to 10 mA/m2 or
100 mV. Potential of activated titanium electrodes placed at 5 mA/m2 Eoff reached 800/ 600 mV, and the four-hour de-
1 mm from steel surface (MMO-1 mm) only showed a slight cay was higher than 200 mV.
decrease from the initial value of about 0 mV, and after more In all the specimens, after the start up period, the potential
than five years of tests it was around 100 mV. The potential of the activated titanium electrode placed at 1 mm from steel
of the electrodes placed at 3 mm (MMO-3 mm) remained surface was steadily within 100 and 200 mV. The potential
higher than 0 mV. of electrodes placed at 3 mm were 100 ± 200 mV higher.
In the carbonated specimen protected with 10 mA/m2
(Fig. 6e), E4h was initially lower than 600 mV and close
to Eoff, but after five months of testing it shifted to higher va- 3.5 Two-layer specimens
lues, in the range from 600 to 400 mV. Correspondingly,
four-hour decay reached values higher than 200 mV, which Fig. 8a ± b show the steel potential and current density
were maintained for more than four years. Lower decays measured on the carbonated specimens with two layers of re-
were only measured during two short periods after 14 and inforcement protected with a nominal current density of
44 months. 10 mA/m2. The first layer of bars picked up most of the cur-
After four-five months of testing, the potential of the acti- rent; the effective current density ranged from 12 to 15 mA/m2
vated titanium electrode nearest to the steel surface also de- on the upper bars and 5 ± 8 mA/m2 on the second layer. A low-
creased and reached values constantly lower than 200 mV er instant off potential was reached in the rebars of the first
(Fig. 6e). The potential of the electrode placed at 3 mm also layer, where the four-hour decay reached values up to
decreased, but remained approximately 100 mV higher. The 100 mV after several months of testing. In the second layer
Materials and Corrosion 54, 163±175 (2003) Repassivation of steel in concrete 167

Fig. 6. Potential measurements in carbonated


concrete (a, c, e) and carbonated concrete with
0.4% chlorides by weight of cement (b, d, f)
protected with 2, 5 and 10 mA/m2: ( *) Eoff,
(*) E4h, (‡) MMO-1 mm, () MMO-3 mm
Abb. 6. Potentialmessungen in karbonatisier-
tem Beton (a, c, e) und karbonatisiertem Be-
ton mit 0,4% Chloriden (bez. auf Zement) (b,
d, f), der mit 2, 5 und 10 mA/m2 geschuÈtzt
war: ( *) Eoff, (*) E4h, (‡) MMO-1 mm, ()
MMO-3 mm

of rebars E4h only was some tens of mV higher than Eoff. In the 3.6 Phenolphthalein tests
specimen with carbonated concrete contaminated by chlor-
ides, the four-hour decay reached values of the order of Concrete cores were taken from the slabs and subjected to
200 mV in the upper bars (Fig. 8c); after three years it also phenolphthalein tests to detect realkalization around the re-
increased in the second layer (Fig. 8d). bars. Fig. 9 shows two cores from the specimen with carbo-
Fig. 8e ± f show results of the two-layer specimen with a nated concrete that was protected at 10 mA/m2. It can be ob-
start up current density of 35 mA/m2 (equal to 100 mA/m2 served that a realkalized layer could be detected around the
on the anode). During the start up, the actual current density steel bar, where concrete had the pink colour of phenolphtha-
was about 50 mA/m2 on the first layer of rebars and 20 mA/m2 lein in alkaline environments, even though it was somewhat
on the second layer. After two months, the nominal current weaker than the colour that is normally found in alkaline con-
density was decreased to 10 mA/m2; actual values were crete. On the specimen of Fig. 9, the thickness of realkaliza-
15 ± 17 mA/m2 on the first layer and 3 ± 5 mA/m2 on the sec- tion after 25 months was 8 mm on the side facing the anode
ond one. The four-hour decay was steadily of the order of and only 1 mm in the opposite side; at the end of tests (62
200 mV on the upper bars after the start up; potential of months) the thickness reached respectively 14 and 3 mm.
both activated titanium electrodes reached a value around Table 1 summarizes the results of phenolphthalein tests, and
200 mV. In the second layer of rebars the four-hour decay shows that realkalization was observed in all of the specimens.
was negligible, only during the first months after the start up it In fact, some realkalization was also observed around the re-
approached 100 mV. bar protected with 5 mA/m2 or in the second layer of rebars in
multilayer specimens. In the presence of chlorides the realk-
alized layer had a somewhat more uniform thickness.
168 Bertolini, Pedeferri, Redaelli and Pastore Materials and Corrosion 54, 163±175 (2003)

Fig. 7. Potential measurements in carbonated concrete (a, b) and carbonated concrete


with 0.4% chlorides by weight of cement (c) protected with 70 mA/m2 for one month
and then with 5 or 10 mA/m2: ( *) Eoff, (*) E4h, (‡) MMO-1 mm, () MMO-3 mm
Abb. 7. Potentialmessungen in karbonatisiertem Beton (a, b) und karbonatisiertem
Beton mit 0,4% Chloriden (bez. auf Zement) (c), der fuÈr 1 Monat mit 70 mA/m2 und
anschlieûend mit 5 oder 10 mA/m2 geschuÈtzt war: ( *) Eoff, (*) E4h, (‡) MMO-1 mm,
() MMO-3 mm

3.7 Final measurements ments of the potential of these electrodes suggest that the re-
alkalization reached a distance of at least 1 mm from the steel
Table 2 shows the potential and the polarization resistance surface after four-five months of application of a current den-
measured during the interruption of cathodic protection for sity of 10 mA/m2. Fig. 6e shows that the potential of the elec-
one month. The slabs were regularly wetted. After one month trode placed at 1 mm from the steel (MMO-1 mm) shifted
the potential of bars that where subjected to cathodic protec- from about 100 mV vs MnO2, i.e. a value typical of carbo-
tion remained higher than the potential of control bars in car- nated concrete (Fig. 4b), to about 100 mV vs MnO2 or low-
bonated concrete ( 450 mV vs MnO2), although it did not er, i.e. values typical of alkaline concrete. Fig. 6e also shows a
reach the potential of the passive bars in the non-carbonated contemporaneous change in the steel potential measured at the
control specimen ( 195 mV vs MnO2). Surprisingly, polari- end of four-hour depolarization tests (E4h). In fact, while the
zation resistances of bars subjected to cathodic protection instant-off potential only showed seasonal variations during
were almost one order of magnitude lower than that of the the initial period, after five months E4h quickly raised from
passive bar in alkaline and chloride free concrete (which values lower than 600 mV vs MnO2 to values of about
was about 60 X  m2). The low values of polarization resis- 300/ 400 mV vs MnO2, i.e. it approached the value of
tance were measured between 24 hours to one month after E4h in the specimen with passive steel in alkaline concrete sub-
the current was switched off. jected to the same current density (Fig. 5c). As a consequence,
Subsequently each specimen was again subjected to catho- the four-hour depolarisation also increased and reached steady
dic protection. Table 3 shows the four-hour decay measured values around 200 mV.
after one week of application of the current and compares it This variation can be attributed to the repassivation of steel
with the last value measured before interruption of the catho- induced by the realkalization of the surrounding concrete.
dic protection. It is clearly evident that, in spite of the inter- Fig. 10 illustrates the electrochemical behaviour of steel in
ruption of one month in the protection current, the four-hour contact with alkaline and carbonated concrete, when it is sub-
decay was still of the same order of that measured before the jected to the circulation of a cathodic current density (iCP).
interruption in all the specimens. Steel has active-passive behaviour in alkaline concrete
(Fig. 10a), and active behaviour in carbonated concrete
(Fig. 10b). Corrosion rate, icorr, and corrosion potential, Ecorr
4 Discussion are given by the intersection of the curves of the anodic pro-
cess and the cathodic process of oxygen reduction. In alkaline
The phenolphthalein tests of Fig. 9 show that the applica- concrete the corrosion rate is under passivity control (icorr,p).
tion of a current density of 10 mA/m2 to a steel bar embedded The corrosion rate of active steel in carbonated concrete
in carbonated concrete can lead to the realkalization of a few (icorr,a) depends on the resistivity of concrete: the higher the
millimetres of carbonated concrete around the steel. Fig. 9a resistivity, the lower the corrosion rate. It has been suggested
also shows the location of the pH-sensitive activated titanium that an increase in concrete resistivity can be described as an
electrodes utilized for monitoring the realkalization. Measure- increase in the slope of the anodic curve [3].
Materials and Corrosion 54, 163±175 (2003) Repassivation of steel in concrete 169

Fig. 8. Potential and current measurements


on two-layer specimens with steel in carbo-
nated concrete (a, b) and carbonated concrete
with 0.4% chlorides by weight of cement (c, d,
e, f): ( *) Eoff, (*) E4h, (‡) MMO-1 mm, ()
MMO-3 mm, (^) current density
Abb. 8. Potential- und Strommessungen an
den zweilagigen Proben in karbonatisiertem
Beton (a, b) und karbonatisiertem Beton mit
0,4% Chloriden (bez. auf Zement) (c, d, e,
f): ( *) Eoff, (*) E4h, (‡) MMO-1 mm, ()
MMO-3 mm, (^) Stromdichte

When an external cathodic current density (iCP) is applied, a larization takes place. After the interruption of the current, the
lower potential of steel is reached and the rate of the anodic potential of steel tends to return towards the free corrosion
process ia is depressed to a value at which: potential, which is much higher for passive steel. Fig. 11a,
for instance shows results of four-hour depolarization tests
ia ˆ ic iCP carried out after about 1 month of application of 10 mA/m2
on steel in alkaline and carbonated concrete. In alkaline con-
where ic is the rate of the cathodic process at ECP potential. crete the potential of passive steel increased from 700 mV to
Fig. 10 shows that a higher polarization occurs on a passive 300 mV during the test, showing a four-hour decay of about
reinforcement in alkaline concrete compared to an active re- 400 mV. In carbonated concrete the potential showed a neg-
inforcement in carbonated concrete (iCP is the same in the ligible increase. Fig. 11b shows the depolarization tests car-
logarithmic scale of Fig. 10a ± b). As a consequence, in ried out on the same specimens after 12 months, i.e. after re-
both cases steel may reach a similar potential (ECP,p  alkalization took place in the carbonated specimen. This de-
ECP,a), as it can be observed by comparing Fig. 5c and 6e dur- polarization test was continued for 24 hours. It can be ob-
ing the first months of testing. Therefore, significant changes served that the potential of steel in the carbonated specimen
in the instant-off potential should not be expected even if re- shows a decay with a trend similar to that of steel in alkaline
alkalization took place in carbonated concrete and led to the concrete, although a lower potential is reached after four
repassivation of steel. hours. This behaviour of the rebars supports the hypothesis
Conversely, differences between passive and active steel that the cathodic current of 10 mA/m2 applied for about 5
can be observed when the current is switched off and depo- months to steel in carbonated concrete could actually lead
170 Bertolini, Pedeferri, Redaelli and Pastore Materials and Corrosion 54, 163±175 (2003)

Fig. 9. Phenolphthalein test on concrete cores


taken from the carbonated slab protected with
10 mA/m2 after (a) 25 months and (b) 62
months
Abb. 9. PhenolphthaleinpruÈfung an Bohrker-
nen aus der karbonatisierten Platte, die mit
10 mA/m2 geschuÈtzt war: (a) nach 25 Mona-
ten und (b) nach 62 Monaten

Fig. 10. Schematic representation of the elec-


trochemical conditions of: (a) passive steel in
alkaline concrete and (b) active steel in carbo-
nated concrete, in free corrosion conditions
and under cathodic polarization
Abb. 10. Schematische Darstellung der elek-
trochemischen Bedingungen von: (a) passi-
vem Stahl in alkalischem Beton und (b)
aktivem Stahl in karbonatisiertem Beton,
bei freien Korrosionsbedingungen und bei ka-
thodischer Polarisation

to repassivation of the corroding steel, as a consequence of the distinction was made between results in carbonated concrete
realkalization of the concrete near to its surface. without chlorides and with 0.4% chloride by weight of ce-
ment). The frequency distributions of values measured on pas-
sive steel in alkaline concrete fit gaussian distributions with
4.1 Realkalization of concrete average values increasing from 250 to 450 mV as the applied
current density increases from 2 to 10 mA/m2. Different is the
Fig. 12 plots the thickness of the realkalized layer around case of measurements in carbonated concrete. In fact, the fre-
the bars protected with different cathodic current densities, as quency distribution changes from a normal distribution in the
a function of charge circulated per unit area. Since realkaliza- specimen subjected to 2 mA/m2 (Fig. 13a) to a two-peak dis-
tion was not uniform around the bars (Fig. 9), the averages of tribution in the specimens subjected to 10 mA/m2 (Fig. 13c).
the thickness of the layer detected around the steel with phe- The second peak in specimens at 10 mA/m2 (white symbols)
nolphthalein tests (reported in Table 1) have been considered. is a consequence of measurements taken after realkalization
It can be observed that, even though the results have a signifi- took place and it coincides with the frequency distribution
cant scatter, the average realkalizations around the bars pro- measured on specimens which were initially realkalised
tected with different current densities and for different times with a start-up current density of 70 mA/m2 (grey symbols).
tend to overlap along an approximately linear relationship The existence of two separate gaussian distributions can be
with the circulated charge. Results are also in agreement hypothesized: the one with lower mean value (about
with those reported in reference [18] which were obtained 90 mV) represents steel in carbonated concrete while the
by applying higher current densities (100 and 1000 mA/m2) one with a higher mean value (about 230 mV) represents steel
to steel in carbonated mortar (white symbols in Fig. 12). in realkalized concrete. Two separate statistical distributions
This suggests that the average extension of the realkalization can also be observed on steel in carbonated concrete subjected
around the steel can be essentially considered a function of the to a current density of 5 mA/m2, even though the second one is
charge circulated owing to the cathodic current that flows to only evident after the start up current was applied (grey sym-
steel surface. No significant influence of the applied current bols).
density could be observed in the range of 5 ± 70 mA/m2. Values of four-hour decay are normally used to assess the
effectiveness of cathodic protection of steel in reinforced con-
4.2 Repassivation of steel crete structures exposed to the atmosphere and 100 mV decay
is usually assumed as characteristic of protection conditions
Fig. 13 analyzes the values of four-hour decay measured on [11 ± 13]. Although this criterion was developed empirically,
steel in specimens with alkaline and carbonated concrete (no it has also been suggested that the achievement of decay of
Materials and Corrosion 54, 163±175 (2003) Repassivation of steel in concrete 171

Table 1. Thickness of realkalization around the steel bar measured by phenolphthalein test
Tabelle 1. Dicke der Realkalisierung um den Stahl; mittels Phenolphthaleintest bestimmt

Start up current Current Chloride Layer Time* Thickness of realkalization


density density (vs cement) (months)
(mA/m2) (mA/m2) a b c d
(mm) (mm) (mm) (mm)

± 10 ± 1 25 8 4 4 1
1 62 14 10 10 3
± 10 0.4% 1 25 6 3 4 3
1 62 11 5 5 4
± 5 ± 1 39 6 3 6 0.5
62 8 1.5 2.5 0.5
± 5 0.4% 1 39 1 1 2 1
62 4 2 3.5 1
± 14‡ ± 1 21 6 4 4 4
44 10.5 6 6 12
± 6‡ ± 2 21 3.5 1 2 2
44 2.5 3 4 4
‡
± 14 0.4% 1 20 5 6 4 4
44 9.5 7 7 7.5
± 6‡ 0.4% 2 20 2 2 2 2
44 3.5 2.5 4 3
70 (1 month) 10 ± 1 22 6 3 3 1
46 9 3 5.5 1.5
70 (1 month) 10 0.4% 1 22 3 0.5 2 1
46 7 5 5.5 1
70 (1 month) 5 ± 1 26 4 1 3 0.5
46 4 3 3 1
50‡ (2 months) 16‡ 0.4% 1 2 2 2 1 0.5
26 8 7 7 7
‡ ‡
20 (2 months) 4 0.4% 2 2 0 0 0 0
26 2 3 2 3
* Time since cathodic protection was applied
‡
Average value of current density measured on each layer of two-layer specimens
172 Bertolini, Pedeferri, Redaelli and Pastore Materials and Corrosion 54, 163±175 (2003)

Fig. 11. Potential decay during depolariza-


tion tests carried on specimens with (*) alka-
line concrete and ( *) carbonated concrete
protected with 10 mA/m2, after (a) 1 month
and (b) 1 year
Abb. 11. Potentialabnahme waÈhrend der De-
polarisation an Proben mit (*) alkalischem
Beton und ( *) karbonatisierten Proben, die
mit 10 mA/m2 geschuÈtzt waren; nach (a) 1
Monat und (b) nach 1 Jahr

charge was higher than 200 A  h/m2. In the mean time, speci-
mens which were subjected to the start-up current of 70 mA/
m2 for a month and then were protected with 5 mA/m2, al-
ready had a four-hour decay remarkably higher than
100 mV at the end of the start-up period, when a charge of
less than 50 Ah/m2 was circulated. Therefore, for a higher
current density a lower charge was sufficient to lead to con-
ditions of high values of depolarization. Furthermore, for a
given current, higher values of depolarization seem to be
more easily reached in specimens in carbonated concrete con-
taminated with chlorides than in specimens with chloride-free
carbonated concrete. Therefore it is clear that repassivation
cannot be simply associated either with the circulated charge
or with a specific average thickness of the realkalized layer.
The amount of alkalinity required to achieve repassivation
may depend on the amount of corrosion that the steel has un-
dergone before cathodic protection was applied. This could
explain why at 14 mA/m2 high values of decay were only
reached for charge values much higher than those which
Fig. 12. Relationship between the average values of thickness of
the realkalised layer detected around the steel with phenolphthalein led to high depolarization on specimens with current density
tests (Table 1) and the charge density on specimens subjected to of 10 mA/m2. In fact these results were obtained from two-
different current densities layer specimens of Fig. 8a ± d, which were subjected to this
Abb. 12. Beziehung zwischen dem Mittelwert der Dicke der real- protection current 18 months later than specimens at lower
kalisierten Schicht um den Bewehrungsstahl, die mittels der Phe- current densities (during that period they were subjected to
nolphthaleinpruÈfung (Tabelle 1) ermittelt wurden, und der 2 mA/m2 and protection was not achieved).
Ladungsdichte an den Proben, die verschiedenen Stromdichten aus- The current distribution around the bar can also play an im-
gesetzt waren portant role. Fig. 9 shows that the part of the rebar that does
not face towards the anode is subjected to a lower thickness of
realkalization because of an uneven current distribution. It can
100 mV should actually imply that a near passive state has then be hypothesized that the four-hour decay measurement
been induced on the protected steel [19]. The two different can only detect a nearly complete repassivation of the rebar.
distributions in Fig. 13b and 13c can thus be assumed as re- It has been shown that coupling with areas of still active steel
presentative respectively of active and repassivated steel. Re- can depress the depolarization of passive areas [20], and thus
gardless of the applied current density, decay values lower the four-hour decay is expected to increase remarkably only
than 100 mV actually follow the distribution of active steel, when most of the surface of the rebar has been repassivated. It
while decays higher than about 150 mV follow the curve can also be expected that, if a more uniform thickness of the
of repassivated steel. Only values in the range of 100 ± realkalized layer can be produced by a more even current dis-
150 mV are indeterminate. It should however be observed tribution, repassivation can be achieved earlier. This could
that the frequency curves measured on realkalised concrete also explain the high values of depolarization reached in
are significantly shifted towards lower decay values with re- the presence of chlorides; in fact, chlorides by lowering the
spect to the frequency distributions of passive steel in alkaline resistivity of concrete improved the current distribution and
concrete. thus led to a more uniform thickness of the realkalized layer
The specimens protected with 10 mA/m2 showed four-hour (Table 1).
decay values higher than 150 mV, i.e. conditions of repassiva- The influence of small non-repassivated areas on the depo-
tion, above 30 A  h/m2 (that is after about 4 months, as pre- larization behaviour of the rebars could also explain the
viously discussed). In specimens protected with a current den- slower depolarization of steel in carbonated concrete after re-
sity of 5 mA/m2, however, the four-hour decay was normally alkalization occurred compared with that of passive steel in
lower than 100 mV even after four years, when the circulated the non carbonated concrete (Fig. 11), as well as the lower
Materials and Corrosion 54, 163±175 (2003) Repassivation of steel in concrete 173

Table 2. Corrosion potential (mV vs MnO2) and polarization resistance (X  m2) measured at the end of tests
Tabelle 2. Am Ende der PruÈfung gemessenes Korrosionspotential (mV gegen MnO2) und Polarisationswiderstand (X  m2)

Start-up Current Chloride Time after interruption of cathodic protection


current density (vs cement)
density (mA/m2) 1 day 1 week 1 month
(mA/m2) E Rp E Rp E Rp
± (control) No Cl ‡ 159 60 195 58 175 60
alkaline
concrete
± 381 27 433 13 440 20
0.4% 417 29 466 13 457 26
± 5 ± 766 23 578 13 404 20
0.4% 575 28 326 7 250 13
± 10 ± 462 5 346 8 316 10
0.4% 441 10 327 6 273 13
‡
± 14 ± 650 4 476 5 ± ±
± 6‡ ± 417 5 305 5 ± ±
± 14‡ 0.4% 384 5 292 4 ± ±
‡
± 6 0.4% 209 10 202 8 ± ±
70 (1 month) 10 ± 398 5 341 4 288 7
10 0.4% 378 10 311 6 265 10
5 ± 363 10 331 15 283 25
50‡ (2 months) 16‡ 0.4% 500 2 356 3 ± ±
‡ ‡
20 (2 months) 4 0.4% ± ± 445 9 ± ±
‡
Average in time of current density measured on each layer of two-layer specimens

average value of the four-hour decay (Fig. 13). Coupling with steel in alkaline concrete (Table 2). These low values of po-
active areas, by depressing the depolarization of passive areas, larization resistance cannot be ascribed to re-activation of
may delay the potential changes. From these considerations it steel, since there is no reason for expecting a higher corrosion
can be assumed that a 100 ± 150 mV decay can be used as cri- rate with respect to control specimens and the four-hour decay
terion to detect repassivation of most of the surface of rebars. remained very high when the cathodic current was newly ap-
Probably, higher values of four-hour decay would mean that plied to the steel (Table 3). Although a clear explanation for
the repassivation has extended to larger areas. the low polarization resistance values could not be found, it
Furthermore, the passive film produced after realkalization should be reminded that the electrochemical behaviour of pas-
of concrete might be different from the original one, since the sive film can affect the result of polarization resistance tests
repassivation takes place under different electrochemical con- and this method can be applied only to steel under free corro-
ditions than initial passivation. In fact, the potential is lowered sion condition [21, 22].
by the cathodic polarization and the composition of pore solu- Visual observation of bars cannot be helpful either. In fact,
tion is different owing to the previous carbonation process and observation of pieces of rebars extracted with cores for ana-
the presence of corrosion products near the surface of the re- lysis of realkalisation showed that corrosion products can be
inforcement. Values of pH in the realkalized layer lower than found also on repassivated steel, owing to corrosion occurred
those in the alkaline concrete can also be hypothesized. Thus, prior to repassivation. Nevertheless, from a practical point of
even if the whole surface was repassivated, a passive film with view, the presence of small portions of the surface of steel not
different electrochemical and protective properties could ex- passive can be accepted. In fact, even if a complete repassiva-
plain the lower four-hour decay compared with originally pas- tion is not reached, small areas of steel in active condition
sive steel in alkaline concrete. would also benefit of protection provided by the small low-
It should be observed that from the results of this work it is ering of potential that has been observed even on active steel.
not possible to be conclusive. Polarization resistance measure- Tests with bars protected with higher current densities
ments carried out after the protection current was switched off showed that the repassivation is facilitated with higher current
could not provide evidence of effective repassivation. The po- densities. Therefore, the use of a start-up current should be
larization resistance of steel bars that had high decays under encouraged since it helps in producing a stable passive
cathodic protection, did not show values typical of passive film. A start-up current density of 70 mA/m2, which led to
174 Bertolini, Pedeferri, Redaelli and Pastore Materials and Corrosion 54, 163±175 (2003)

Table 3. Results of four-hour depolarization measured just before interruption of cathodic protection for one month and one week after
cathodic current had been re-applied (mV vs MnO2)
Tabelle 3. Ergebnisse der 4-stuÈndigen Depolarisation, die kurz vor der Unterbrechung des kathodischen Schutzes fuÈr einen Monat sowie
eine Woche nach Wiedereinschalten des kathodischen Stromes gemessen wurden (mV gegen MnO2)

Start-up cur- Current Chloride Before interruption of CP 1 week after re-application of CP


rent density density
(mA/m2) (mA/m2) (vs cement) Eoff E4h DE4h Eoff E4h DE4h

± 5 ± 923 861 62 958 876 82


0.4% 788 708 80 928 864 64
± 10 ± 811 567 244 896 678 218
0.4% 807 587 220 874 703 171
‡
± 14 ± 942 782 160 1054 936 118
± 6‡ ± 639 541 98 792 735 57
‡
± 14 0.4% 720 496 224 794 626 168
± 6‡ 0.4% 511 308 203 641 520 121
70 (1 month) 10 ± 742 492 250 825 582 243
10 0.4% 680 457 223 755 514 241
5 ± 665 466 199 787 587 200
50‡ (2 months) 16‡ 0.4% 782 570 212 870 646 224
‡
Average in time of current density measured on each layer of two-layer specimens

Fig. 13. Statistical analysis of four-hour decay as a function of applied current den-
sity: * steel in alkaline concrete; * steel in carbonated concrete; * steel in carbonated
concrete after the application of the start up current
Abb. 13. Statistische Analyse der Potentialabnahme nach 4 Stunden als Funktion der
eingesetzten Stromdichte: * Stahl in alkalischem Beton; * Stahl in karbonatisiertem
Beton; * Stahl in karbonatisiertem Beton nach der Anwendung eines Anlaufstromes

instant-off potentials of about 1.2 V vs MnO2, brought about 4.3 Throwing power
stable values of four-hour decay higher than 200 mV even
when the current density was decreased to 5 mA/m2 For the design of cathodic protection in carbonated concrete
(Fig. 14b). structures, it is important to assess the possibility of achieving
Materials and Corrosion 54, 163±175 (2003) Repassivation of steel in concrete 175

protection conditions also on deeper bars if they have been 7 References


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(Received: April 8, 2002) W 3636


6 Acknowledgements

This project was initially supported by ENEL-CRIS and


then by the Italian Ministry of University and Research
(MIUR).