Corrosion Science 43 (2001) 1111±1131

www.elsevier.com/locate/corsci

Cathodic protection a€orded by an intermittent

current applied to reinforced concrete
G.K. Glass *, A.M. Hassanein, N.R. Buenfeld
Department of Civil and Environmental Engineering, Imperial College of Science, Technology and Medicine,
Imperial College Road, London SW7 2BU, UK
Received 27 January 2000; accepted 4 September 2000

Abstract

In this work, intermittent cathodic protection was applied to chloride contaminated re-
inforced concrete exposed to simulated tidal zone conditions. It was observed that an inte-
grated protection current of just 6 mA/m2 induced the passivation of steel exhibiting an initial
corrosion rate of 60 mA/m2 in conditions characterised by weakly polarised cathodic reaction
kinetics. This provides the ®rst direct laboratory evidence that protection may be achieved
with a cathodic current that is small compared to the corrosion rate. In this case the protective
e€ects of a negative potential shift may be ignored; it is the changes in the environment at the
cathode that induce passivation and provide the basis for cathodic protection. Such changes
occur slowly and do not give the instantaneous protection o€ered by a large negative potential
shift. A large potential shift combined with a reducing environment may be generated in
saturated conditions characterised by strongly polarised cathodic reaction kinetics. Both
passivating and reducing environments at the steel will persist following current interruption.
The dominance of these persistent e€ects suggests that the integrated value of the current
required for protection will be insensitive to current variations. Positive trends in open circuit
potentials or sustained negative potentials are indicative of passivating and reducing con-
ditions respectively, although an intermittent current complicates non-destructive perfor-
mance assessment. Ó 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Cathodic protection; Chloride; Concrete; Corrosion; Criteria; Intermittent current; Steel
passivity; Tidal zone

*
Corresponding author. Tel.: +44-20-7594-5956; fax: +44-20-7225-2716.
E-mail address: g.glass@ic.ac.uk (G.K. Glass).

0010-938X/01/$ - see front matter Ó 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 0 - 9 3 8 X ( 0 0 ) 0 0 1 3 3 - 5
1112 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131

1. Introduction

In previous work it was noted that, in addition to a negative potential shift, a

current also induces a change in the local environment at the cathode that renders it
less aggressive to steel [1]. This may arise from the removal of chloride and oxygen,
as well as the production of hydroxyl ions and other species that might inhibit
corrosion [2]. The current induced change in the chloride and hydroxyl content at a
cathode in a concrete environment has been observed under laboratory conditions
[3] and such protective e€ects have at least in part contributed to the successful use of
relatively small current densities in the application of cathodic protection to atmo-
spherically exposed reinforced concrete [4]. It was noted that the changes in the
environment at the cathode will persist following current interruption [5] and that an
intermittent current will generate a similar steady state environment at the cathode
to that generated by a continuous current with the same integrated value [6]. Thus
cathodic protection may be applied intermittently [5,7,8]. This is particularly useful
when one of the components of the system, such as a seawater electrolyte connecting
the anode to the concrete in the tidal zone or the sunlight required by a system using
solar power, is not always present [9,10].
In this work intermittent cathodic protection at relatively low integrated current
densities was applied to reinforced concrete specimens exposed to simulated tidal
zone conditions. The aim was to assess the relative importance of the protective
e€ects of a negative potential shift and reduction in the aggressive nature of the
environment at the steel, evaluate the impact of these e€ects on the current required
for protection, and examine the e€ect of the intermittent application of the current
on methods of monitoring the achievement of protection.

2. Experimental methods

Reinforced concrete cylinders, 60 and 100 mm in diameter and 250 mm long, each
containing a centrally located 20 mm diameter mild steel bar (exposed length 180
mm), a zinc/zinc chloride reference electrode and an inert counter electrode, were
manufactured using ordinary Portland cement (OPC), a blend of OPC and 35%
pulverised fuel ash (PFA) or a blend of OPC and 70% ground granulated blast-
furnace slag (GGBS). The cement content of the specimens was 400 kg/m3 and the
free water/cement ratio (w/c) was 0.4 or 0.5. Initial chloride ion contents of 0%, 1%,
2% or 3% by weight of cement were imposed by adding sodium chloride to the mix
water.
After curing for 1 month the specimens were exposed in two tanks to arti®cial
seawater for 0.5 h in every 12 h (at midday and midnight) and to circulating air for
the remainder of each 12 h cycle to simulate a tidal zone environment. One tank
(referred to as the wet tank) was partially sealed to sustain a high relative humidity
after the water was drained. Dry laboratory air was forced through the second tank
(referred to as the dry tank). A controlled current pulse of 30 min duration was
applied from a distributed anode located in the seawater to the specimens while the
 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131 1113

tanks were ¯ooded. While the current was applied some specimens were only par-
tially submerged, 80%, 65% or 50% of the specimen being below the water level. A
list of the specimens in each tank used in this work, together with the magnitude of
the applied current pulses (expressed as a current per unit area of exposed steel) are
given in Tables 1 and 2. The most common current pulse applied (100 mA/m2 )
equates to an integrated current density of just 4.2 mA/m2 . Further experimental
details (specimen layout, detailed concrete mix design, 28 day cube strengths, oxide
composition of materials and composition of the arti®cial sea water) have been
previously reported [11].
The steel potential relative to the cast in reference electrode, tank relative hu-
midity, tank temperature and polarisation resistance of the steel were recorded at
regular intervals using data loggers. All embedded reference electrodes were cali-
brated against a saturated calomel reference electrode (SCE) located in the seawater
when the tanks were ¯ooded, and the measured potentials are reported on this scale.
The tank temperature and relative humidity were determined using thermocouples
and relative humidity probes that had been calibrated using the temperature de-
pression observed on a wet bulb thermometer. The e€ects of the cathodic current
pulse were allowed to decay for a minimum of 8 h before the polarisation resistance
was obtained. This was determined by applying a small potentiostatic perturbation
(typically 8 mV) for a period of 30 s and subtracting the e€ect of the electrolyte
resistance determined on subsequently interrupting the current [12]. Also recorded
was the weight change of selected specimens in the dry tank over one tidal cycle. At
the end of the test period the specimens were subjected to destructive visual exam-
ination.

Table 1
Initial corrosion potential (Ecorr ), polarisation resistance (Rp ) and corrosion rate (Icorr ) data for specimens
in the dry tank (w=c ˆ 0:4 and cover ˆ 40 mm unless otherwise stated)
Specimens Current pulse Ecorr (mV vs. Rp (X m2 ) Icorr (mA/m2 )
(mA/m2 ) SCE)
OPC, 0% Cl 0 106 170 0.15
OPC, 0% Cl 100 80 77 0.34
OPC, 1% Cl 100 270 4.6 5.6
OPC, 2% Cl 0 468 0.68 38
OPC, 2% Cl 40 413 0.84 31
OPC, 2% Cl 100 343 0.53 49
OPC, 2% Cl 150 398 0.46 57
OPC, 2% Cl 1000 338 1.3 21
OPC, 3% Cl 100 500 0.87 30
OPC, 2% Cl , 20 mm cover 0 436 0.46 57
OPC, 2% Cl , 20 mm cover 100 470 0.40 65
PFA, 2% Cl 0 397 4.7 5.5
PFA, 2% Cl 100 426 1.8 14
GGBS, 2% Cl 0 268 7.9 3.3
GGBS, 2% Cl 100 258 8.1 3.2
1114 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131

Table 2
Initial corrosion potential (Ecorr ), polarisation resistance (Rp ) and corrosion rate (Icorr ) data for specimens
in the wet tank (w/c ˆ 0:4 and cover ˆ 40 mm unless otherwise stated)
Specimens Current pulse Ecorr (mV vs. Rp (X m2 ) Icorr (mA/m2 )
(mA/m2 ) SCE)
OPC, 0% Cl 0 93 130 0.20
OPC, 0% Cl 100 64 140 0.18
OPC, 1% Cl 100 283 3.5 7.5
OPC, 2% Cl 0 373 1.1 24
OPC, 2% Cl 40 408 2.8 9.4
OPC, 2% Cl 100 335 1.6 17
OPC, 2% Cl 150 304 1.2 22
OPC, 2% Cl 1000 343 0.33 80
OPC, 3% Cl 100 460 1.9 14
OPC, 2% Cl , w/c 0.5 0 314 1.1 24
OPC, 2% Cl , w/c 0.5 100 304 1.0 27
PFA, 2% Cl 0 383 1.6 16
PFA, 2% Cl 100 410 1.7 15
GGBS, 2% Cl 0 196 10 2.5
GGBS, 2% Cl 100 178 6.7 3.9
OPC, 2% Cl (80% submerged) 100 388 0.51 51
OPC, 2% Cl (65% submerged) 100 331 0.47 55
OPC, 2% Cl (50% submerged) 100 314 0.34 77

3. Experimental results

3.1. Environment

The relative humidity and temperature inside the two exposure tanks are plotted
as a function of time in Fig. 1. A relative humidity greater than 90% was sustained at
all times in the wet tank even after the water was drained. The relative humidity in

Fig. 1. (a) Relative humidity and (b) temperature in the dry and wet tanks.
 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131 1115

the dry tank typically varied between 50% and 70%. Temperature variations were
dominated by changes in the temperature of the laboratory housing the tanks.
However the temperature was slightly higher in the wet tank where evaporation was
reduced.
The relative weight change of a 100 mm diameter specimen as the result of
evaporation during the dry cycle in the dry tank, expressed as a percentage of the
concrete weight, is given in Fig. 2. This equates to a reduction in the evaporable
water content of the specimen of approximately 7% assuming an evaporable water
content of 18% by weight of cement for the 0.4 w/c concrete. No signi®cant specimen
weight change could be determined in the wet tank.

3.2. Dry tank electrochemical measurements

The specimens exposed in the dry tank associated with various protection currents
are listed in Table 1. Also included are their initial potentials and polarisation re-
sistance values determined prior to applying intermittent cathodic protection. The
corrosion potentials varied between 80 and 500 mV (SCE). The polarisation
resistance values have been converted to corrosion rates using anodic and cathodic
Tafel slopes of 120 mV. This method of corrosion rate determination has been
shown to be accurate to within a factor of 2 under normal conditions [13,14]. The
initial corrosion rates varied between 0.15 and 65 mA/m2 .
The corrosion potentials and corrosion rates were dependent on the initial
chloride content with more positive potentials and lower corrosion rates being ob-
served at chloride contents below 2%. The use of GGBS and PFA also tended to
decrease the corrosion rate. However signi®cant variations were evident in replicate
specimens. For example OPC specimens containing 2% chloride exhibited initial
corrosion potentials between 343 and 470 mV (SCE) and corrosion rates between
23 and 65 mA/m2 . The relationship between the initial corrosion potential and

Fig. 2. Weight change in specimen expressed relative to weight of concrete resulting from the loss of
evaporable water during the dry cycle in the dry tank.
1116 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131

Fig. 3. Initial corrosion rate±corrosion potential relationship observed.

corrosion rate is plotted in Fig. 3. To a ®rst approximation, a linear decrease in

potential is accompanied by an exponential increase in the corrosion rate.
The cyclic potential variations occurring over a 16 h period that included the
application of two current pulses are given in Fig. 4. A large negative potential shift,
which depended on the magnitude of the current pulse, was observed while the
current was applied. In the current free period the potentials recovered rapidly to
more positive values.
The open circuit potential measured 8 h after the application of a current pulse is
plotted as a function of time of exposure in the dry tank for specimens containing 2%
chloride that had been treated with a range of current pulses in Fig. 5. Trends in the
measured potentials became evident as the duration of the experiment increased.

Fig. 4. Typical cyclic variations in steel potentials induced by various current pulses.
 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131 1117

Fig. 5. Potentials in the dry tank determined 8 h after the application of a current pulse.

After 13 months the potentials of all specimens treated with current pulses of 100
mA/m2 or less had decreased to between 400 and 550 mV, while the potentials of
specimens treated with current pulses of 150 and 1000 mA/m2 rose by more than 200
mV to values more positive than 150 mV.
The corresponding e€ects on the polarisation resistance values determined 8 h
after a current pulse are plotted in Fig. 6. For specimens receiving 0.15 and 1 A/m2
current pulses, the measured polarisation resistance increased over the 13 month
period of the experiments to values above 2 X m2 . By contrast, the polarisation re-
sistance of the specimens treated with pulses of 100 mA/m2 or less exhibited a net
decrease in the polarisation resistance.

Fig. 6. Polarisation resistance values in the dry tank determined at least 8 h after the application of a
current pulse.
1118 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131

Fig. 7. E€ect of chloride content on the potentials in the dry tank determined 8 h after the application of a
current pulse.

The e€ects of the initial chloride content on the open circuit steel potentials
measured eight hours after the 100 mA/m2 current pulses are plotted in Fig. 7. The
potential of the specimen containing no chloride decreased to a value of 150 mV
(SCE), which was approximately 50 mV below the untreated control containing no
chloride. The potential of the specimen containing 1% chloride rose by more than
100 mV to values more positive than 150 mV. The polarisation resistance of this
specimen increased by a factor of 5 over the same period. The potentials of speci-
mens containing 2% and 3% chloride were more negative and values close to 500
mV were achieved by the end of the test.
The e€ect of concrete type (GGBS, PFA and OPC) on the open circuit potential is
given in Fig. 8. A current pulse of 100 mA/m2 applied for 0.5 h in every 12 appeared
to have little e€ect, the most positive ®nal potential arising from the PFA control and
the most negative arising from the OPC control. As indicated in Table 1, the
polarisation resistance values of the embedded steel in the GGBS and PFA speci-
mens were much higher than that of the OPC specimens. However no signi®cant
di€erences between the control and electrochemically treated PFA and GGBS
specimens were observed over the duration of the experiment.

3.3. Wet tank electrochemical measurements

The specimens exposed in the wet tank associated with various protection cur-
rents are listed together with their initial potentials, polarisation resistance values
and corrosion rates in Table 2. The initial corrosion potentials and rates were again
dependent on the chloride content and cement type prior to electrochemical treat-
ment. The corrosion potential±corrosion rate data are included in Fig. 3. The
average slope of the initial potential±log corrosion rate relationship for the speci-
mens in both tanks was 126 mV.
 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131 1119

Fig. 8. E€ect of concrete type on the potentials in the dry tank determined 8 h after the application of a
current pulse.

Fig. 9 shows the e€ect of the protection current on the open circuit potential of the
steel in OPC specimens containing 2% chloride in the wet tank. The unexpected
increase in values observed between 30 and 50 days was the consequence of the tank
not being ¯ooded for a two week period. The open circuit potentials in all specimens
that received current shifted to more negative values and the potential of the em-
bedded steel in specimens that received pulses of 100 mA/m2 was eventually sus-
tained at values close to 1000 mV (SCE). In the absence of any applied current, a
corrosion potential of between 400 and 500 mV was sustained. Similar current
induced changes in potential were observed in specimens made using GGBS or PFA,
a w/c of 0.5 as opposed to 0.4 and contaminated with di€erent initial chloride
contents.

Fig. 9. Potentials in the wet tank determined 8 h after the application of a current pulse.
1120 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131

Fig. 10. E€ect of level of immersion on the steel potential in the wet tank determined 8 h after the ap-
plication of a 100 mA/m2 current pulse.

The e€ect of the current on the steel potential in specimens that were only par-
tially submerged is given in Fig. 10. The same current pulses (100 mA/m2 ) were
applied irrespective of the percentage of the specimen above the water level when the
tanks were ¯ooded. Relatively positive potentials were maintained for the duration
of the test when the concrete extended above the water that was used to distribute the
current.
The polarisation resistance data obtained on OPC specimens containing 2%
chloride in the wet tank subject to various current densities are given in Fig. 11.
These values appeared to be strongly dependent on the magnitude of the current
pulse with the lowest values being associated with the highest currents.

Fig. 11. Polarisation resistance values in the wet tank determined at least 8 h after the application of a
current pulse.
 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131 1121

3.4. Visual examination

Periodic visual examination indicated that many of the specimens in the dry tank
cracked during the test, while specimens in the wet tank remained intact. The ap-
plication of current to specimens in the dry tank increased the time to corrosion
induced cracking. In the case of the OPC specimens with 40 mm of cover containing
2% chloride, the control cracked less than 2 months after casting (1 month after
exposure in the tank). This was increased to 7 months when 100 mA/m2 current
pulses were applied, while specimens that received 150 and 1000 mA/m2 current
pulses did not crack (Fig. 12). An increase in the magnitude of the current pulses
applied also resulted in a signi®cant reduction in the quantity of corrosion product
observed on breaking the specimens open. Other specimens in the dry tank that did
not exhibit corrosion induced cracking were those with a lower initial chloride
content (0% or 1% by weight of cement).
Reducing the concrete cover to 20 mm or increasing the initial chloride content to
3% increased the level of deterioration observed irrespective of whether the speci-
mens were treated (100 mA/m2 current pulses) or untreated. The corrosion induced
cracking observed in the GGBS and PFA specimens was much ®ner than that in
equivalent OPC specimens and signi®cantly less deterioration occurred. The di€er-
ences between treated (100 mA/m2 current pulses) and untreated GGBS and PFA
specimens were also less apparent.
As noted above, none of the specimens in the wet tank exhibited corrosion in-
duced cracking. Destructive examination at the end of the test revealed that the
corrosion product in treated specimens was black in colour as opposed to the more
usual orange product (Fig. 13). Furthermore the quantity of corrosion product
appeared to be strongly dependent on the initial corrosion rate determined prior to
applying the electrochemical treatment (cf. Figs. 13 and 14).
An examination of the specimens that were only partially submerged when the
wet tank was ¯ooded and the protection current was applied (100 mA/m2 current
pulse) revealed an orange corrosion product with some black product also being
present in specimens that were 80% submerged (Fig. 14). No signi®cant e€ect of the
level of immersion on the quantity of corrosion product was observed. However,
more corrosion resulted than in the case of fully submerged specimens, although this
would be expected as the initial corrosion rates were higher (cf. Table 2).

4. Discussion

4.1. Induced passivity

It is well known that the critical parameters maintaining passive steel in concrete
are an alkaline environment, the absence of signi®cant aggressive ion contamination
and relatively unrestricted cathodic reaction kinetics [15,16]. The signi®cant initial
corrosion rates of the steel observed in this work resulted from chloride induced
passive ®lm breakdown. The relationship in Fig. 3 is characteristic of weakly
1122 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131
 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131 1123

polarised cathodic reaction kinetics, with the changes in the anodic reaction kinetics
accompanying passive ®lm breakdown producing the changes in corrosion rate and
corrosion potential [11,17].
Weakly polarised cathodic reaction kinetics are common in atmospherically ex-
posed concrete structures. The data in Figs. 4 and 5 would suggest that such kinetics
were sustained by the conditions in the dry tank. Even after the application of large
cathodic current pulses, the steel potential rapidly rose to the positive values asso-
ciated with aerated conditions. These conditions would be maintained by the sig-
ni®cant loss of evaporable water in the dry period (Fig. 2). Passivity may be restored
by cathodic protection under such conditions [5].
Strong evidence that passivity was induced in specimens that received 150 and
1000 mA/m2 current pulses is provided by the absence of corrosion induced cracking
(Fig. 12) and the positive shift in open circuit potentials (Fig. 5). Indeed the
potentials rose by more than 200 mV indicating that the corrosion rate may have
decreased by up to two orders of magnitude. The potentials measured 8 h after the
specimens had been cathodically polarised eventually reached values between 100
and 150 mV (SCE), values that were associated with negligible corrosion rates (less
than 1 mA/m2 ) in this work (cf. Fig. 3). It may also be noted that these potentials
only provide a conservative estimate of more positive fully depolarised corrosion
potentials (cf. the potentials of treated and untreated chloride free specimens in
Fig. 7).
The conventional mechanism whereby cathodic protection induces passivity is via
a negative potential shift into the passive region [18]. Such a mechanism is only
e€ective when the applied current density is at least as large as the corrosion rate, i.e.
for 30 min in every 12 h while the current pulse was applied. The rapid rise in po-
tential following the short current pulse (Fig. 4) suggests that, if the potential shift
mechanism were the principle protective e€ect, the specimen would only be protected
for a small percentage of its life. Thus this mechanism could not account for the
reduction in deterioration observed.
Corrosion initiation on passive metals would normally be accompanied by a local
decrease in pH and increase in chloride concentration at the sites of passive ®lm
breakdown. As noted above, a cathodic current may also re-establish passivity by
reversing these e€ects. This would increase the range of potentials over which the
passive ®lm is stable; the pitting potential will be more positive if the pH is stabilised
at high values and the chloride content is reduced at the steel [1,3,5]. The positive
shift in the open circuit potentials suggests that these protective e€ects are more
dominant than those arising from a current induced negative potential shift.

Fig. 12. Final condition of specimens that received current pulses of 0, 40, 100, 150 and 1000 mA/m2 (left
to right) in the dry tank.
Fig. 13. Corrosion in the control (left) and treated specimen (100 mA/m2 ) (right) after exposure in the wet
tank. The initial corrosion rates were 24 and 27 mA/m2 , respectively.
Fig. 14. Corrosion in specimens that were 80% (left) and 65% (right) submerged when the wet tank was
¯ooded. The initial corrosion rates were 51 and 55 mA/m2 , respectively.
1124 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131

The importance of the current induced changes in the local environment that
promote steel passivity, is highlighted by comparing the integrated protection cur-
rent densities with the initial corrosion rates. In one case (the specimen receiving a
150 mA/m2 for 30 min every 12 h) steel passivity was induced by an integrated
current density of 6 mA/m2 when the initial corrosion rate was approximately 60
mA/m2 (Table 1). This low integrated current density would not be expected to have
any signi®cant impact if protection arose from an induced negative potential shift.
The e€ect of a change in the local environment at the steel that may restore
passivity is illustrated in Fig. 15. In this example it is assumed that the cathodic
reaction kinetics are described by the trend line through the corrosion potential±
corrosion rate relationship in Fig. 3 and an increase in anodic polarisation resulted in
a 200 mV positive shift in the open circuit potential of steel that was initially cor-
roding at 30 mA/m2 . It may be noted that this reduced the open circuit corrosion rate
to negligible value of 0.8 mA/m2 . By contrast, the application of 40 mA/m2 (the
integrated value of the 1000 mA/m2 current pulses) to steel that is corroding at 30
mA/m2 would only induce a 30 mV negative potential shift and reduce the rate of
anodic dissolution to 15 mA/m2 . Larger negative potential shifts are induced with
less current at lower open circuit corrosion rates (less than 10 mA/m2 will induce 150
mV at a corrosion rate of 0.8 mA/m2 ). However once again the reduction in the
anodic dissolution rate induced by a negative potential shift is relatively small
compared to the very signi®cant e€ect of an increase in anodic polarisation resulting
from a change in environment at the steel.
It has previously been noted that corrosion rates greater than the applied current
density may well have been arrested in the practical application of cathodic pro-

Fig. 15. E€ect of an increase in anodic polarisation that would result in a 200 mV positive shift in the open
circuit steel potential. The cathodic reaction kinetics are assumed to be given by the corrosion potential±
rate relationship plotted in Fig. 3.
 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131 1125

tection to reinforced concrete [4,19]. This is indicated by the successful use of con-
tinuous protection current densities less than 20 mA/m2 (the upper limit of the
recommended design current density [20]) when steel corrosion rates may be as high
as 100 mA/m2 [21]. Furthermore the open circuit steel potentials at locations initially
exhibiting the most negative values (indicative of the greatest corrosion risk and
highest corrosion rates) have been shifted to signi®cantly more positive values fol-
lowing a period of cathodic protection (cf. Fig. 15). Examples include rises in the
most negative initial potentials of at least 150 mV on the Tay Road Bridge (Scotland)
[22], 180 mV on the Blackpool Police Station (England) [5] and 350 mV on the Hood
Canal Bridge (Washington) [8,23]. These increases are in line with the 200 mV re-
ported above when passivation of actively corroding steel was induced (cf. Fig. 5).
The present experimental data provides the ®rst direct evidence that high corrosion
rates can be arrested with low average current densities.
Thus the current induced change in the local environment at the steel may provide
a basis for the use of relatively small currents in cathodic protection. The e€ects of a
negative potential shift are negligible. Such a basis is particularly relevant when the
cathodic reaction kinetics are weakly polarised. In these conditions, the achievement
of a signi®cant potential shift would require a protection current that is substantially
greater than the corrosion rate [18]. Indeed published data on steel in concrete has
indicated that the current density required to achieve 100 mV of potential shift
would typically be ®ve times the open circuit steel corrosion rate [11]. If this current
requirement was not reduced by the changes induced in the environment at the steel,
cathodic protection of reinforced concrete may have been impractical in many cases.

4.2. Reducing conditions

Sustained negative potentials (below 800 mV SCE) were induced by relatively

small current pulses in the wet tank (Fig. 9). This suggests that the availability of
oxygen was restricted by its slow di€usion through the saturated pore system of
concrete and could not produce any signi®cant recovery in the potential during the
current-o€ period [15]. Under these conditions the products of cathodic reduction
will build up at the steel to generate a reducing environment. The black corrosion
product observed (Fig. 13) is indicative of such an environment. Indeed the absence
of the orange product that would have formed prior to exposure and treatment in the
wet tank suggests that some reduction of these higher oxidation state corrosion
products has occurred. The sustained negative potentials indicate that the corrosion
risk is negligible and the conventional basis for cathodic protection applies in this
case [24].
The integrated current density must be greater than the limiting current for
oxygen reduction to achieve a reducing environment. Thus, the limiting current in
specimens in the wet tank would have been less than 2 mA/m2 , the integrated current
density of the 40 mA/m2 current pulse (cf. Fig. 9). This value is dependent on factors
such as the degree of saturation of the concrete. Saturation of the concrete was
maintained at a high value by the high relative humidity and periodic submersion in
the arti®cial seawater in the wet tank. It may be noted that a current pulse of 100
1126 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131

mA/m2 did not achieve sustained reducing conditions, as indicated by the more
positive open circuit potentials and orange corrosion product, when the concrete
specimens were only partially submerged on ®lling the tanks with water (cf. Fig. 10).
The initial corrosion rates of specimens in the dry and wet tanks were very similar
(Fig. 3). These relatively high rates could only be sustained for a short period by the
residual oxygen content of the specimen when oxygen access was subsequently re-
stricted in the wet tank. In the longer term the corrosion in treated specimens would
be rapidly arrested by the sustained negative potential shift achieved. The anodic
dissolution of iron in untreated specimens may be supported by the cathodic re-
duction of previously formed iron(III) compounds. This will result in less expansive
products and reduce the risk of disruption of the concrete cover. Indeed even the
untreated specimens exposed in the wet tank showed no sign of corrosion induced
cracking.

4.3. Intermittent cathodic protection

The protective e€ects of the current that generate either reducing conditions or a
passivating environment will persist following the interruption of the current. It is
these persistent changes in the local environment at the steel, which include the re-
moval of oxygen and chloride ions as well as an increase in pH to a sustained high
value [1,25] that provide the basis for the application of intermittent cathodic pro-
tection [5,9]. The experimental data presented above shows that intermittent
cathodic protection proved to be e€ective for some current pulses (cf. Fig. 12).
A key di€erence between the protective e€ects of a negative potential shift and
inducing an inhibitive environment is that a negative potential shift may achieve
instantaneous protection, while the more persistent changes in the local environment
induced at the steel occur more slowly. Nevertheless the achievement of protection
must be suciently fast to prevent disruption of the concrete cover. The initial
protection current density will therefore depend on both the initial corrosion rate
and the rate of current induced improvement in the local environment at the steel. In
the present work an integrated current density of 4.2 mA/m2 applied as a 100 mA/m2
current pulse for 30 min in every 12 h to a specimen containing 2% chloride exposed
in the dry tank more than trebled the time to the onset of corrosion induced cracking
of the cover but failed to prevent it (cf. Fig. 12).
Factors such as the specimen geometry and level of chloride contamination will
determine the initial current density required to induce passivating conditions when
the cathodic reaction kinetics are weakly polarised. For example, the corrosion in-
duced deterioration observed increased when the concrete cover was reduced from
40 to 20 mm or the chloride content was increased from 2% to 3%. Indeed current
pulses of 100 mA/m2 were sucient to restore passivity in a specimen containing 1%
chloride, while 150 mA/m2 current pulses were required when 2% chloride was in-
itially present (cf. Figs. 5 and 7). Current pulses of 100 mA/m2 also failed to prevent
corrosion induced cracking in aerated concrete containing 2% chloride when cement
replacement materials (GGBS and PFA) were used despite much lower initial cor-
rosion rates in these materials (cf. Table 1). It is postulated that this may, in part,
 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131 1127

result from a decrease in the rate of improvement in the local environment due to the
immobilisation of the chloride ions presenting the corrosion risk [26,27].
The achievement of reducing conditions is dominated by the limiting current for
oxygen reduction, with a low limiting current being required if intermittent cathodic
protection is to produce such conditions. However, this would normally imply that
the corrosion rate is relatively low [15]. Thus supplementary forms of corrosion
protection may not always be necessary in these conditions.
A critical factor in the design of an intermittent cathodic protection system is the
magnitude of the design current density. Design current densities of up to 20 mA/m2
are commonly used for the continuous cathodic protection of concrete [20]. Possible
factors that may increase the current requirement in an intermittent system include
the need to address the worst case in the cyclic environmental conditions induced at
the steel by the intermittent current and the absence of the protective e€ects of a
negative potential shift during the current o€ period in dry environments. However
these are countered by the relatively slow transport properties of species in concrete
that limits ¯uctuations in the environment [6], and a more signi®cant potential shift
induced while the current is applied.
The application of an intermittent current as opposed to a continuous current
with the same integrated value will also have bene®cial e€ects. For example current
distribution is a€ected by potential variations between anodic and cathodic sites on
the steel that may favour the ¯ow of current to the more positive cathodic sites [28].
The higher voltage driving the intermittent current will limit this adverse e€ect.
Furthermore anodic areas on steel in concrete are also associated with larger in-
terfacial capacitance values than areas where the passive ®lm is intact [12,29]. This
would reduce the resistance to the high frequency component of the intermittent
current at the anode. Indeed pulsed cathodic protection systems have already been
suggested as a means of improving current distribution on coated steel pipelines [30].
The above discussion suggests that the positive e€ects of an intermittent current
may counter any adverse e€ects. Furthermore the same mechanisms of protection
provide the basis for the application of both intermittent and continuous cathodic
protection to reinforced concrete. Thus, in theory, the integrated design current
densities should be similar for these two types of systems in a given set of en-
vironmental conditions. This is supported by the present work in which intermittent
protection currents with similar integrated values to those applied in continuous
current cathodic protection (less than 20 mA/m2 ) proved to be e€ective in arresting
corrosion.

4.4. Monitoring corrosion

In the present work, potential, polarisation resistance and visual data were used to
assess the protection achieved in the reinforced concrete specimens. To some extent,
the visual data provides the reference against which other data may be assessed.
The normal method of assessing cathodic protection of steel in concrete uses the
potential decay determined on interrupting the current [24]. The typical requirement
is to achieve a decay of 100 mV. However such a potential shift does not always
1128 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131

result in immediate protection [31]. This is particularly true when high current
densities (100 mA/m2 ) are required to achieve it. On the other hand, small current
densities typical of those applied in practice (of the order of 10 mA/m2 ) will be able
to induce signi®cant potential shifts after the open circuit corrosion rate has been
reduced to negligible values (cf. Fig. 15). Thus the theoretical basis for this criterion
is that it gives an indication of the restoration of open circuit steel passivity [32].
To strengthen the criterion, the potential shift should be linked to the applied
current density. This may enable open circuit corrosion rate information to be ex-
tracted using the relationship between a large potential shift, the applied current
density and the corrosion rate [19,32]. Such analysis may also be applied to the
potential decays following current pulses of short duration. However, this is only
true when the applied current pulse is less than the limiting current for oxygen re-
duction, which was not the case for most current pulses of interest in the present
work. Thus very large potential decays were sometimes induced by current pulses
that did not prevent corrosion induced cracking (Fig. 4).
The interpretation of small perturbation polarisation resistance data in terms of
corrosion rates also presented problems in some of the conditions encountered in this
work. While the initial corrosion rates determined prior to electrochemical treatment
and exposure to simulated tidal zone conditions are supported by visual (cf. Figs. 13
and 14) and gravimetric data [13,14], and some reasonable trends in the polarisation
resistance values were observed in the dry tank (cf. Figs. 5 and 6), very low polar-
isation resistance values that would normally indicate high corrosion rates, were
determined on the specimens receiving the most current in the wet tank. Indeed even
the unpolarised specimen in the wet tank produced polarisation resistance values
that would be associated with corrosion rates signi®cantly above the limiting current
for oxygen reduction for the full duration of the experiment. Similar observations
have previously been reported [21,33,34].
Errors in the estimated corrosion rate will result when neither of the half reactions
are under activation control, the open circuit potential is close to the equilibrium
potential of one of the half reactions or the oxidation of species previously reduced
by the cathodic current occurs. However it should be noted that the loss of activation
control of the half reactions would normally be expected to increase the polarisation
resistance and it is therefore unlikely that this is responsible for the low values
measured.
The wide range of potentials over which this problem occurs and the decrease in
polarisation resistance with increase in cathodic current in the wet tank (Fig. 11)
supports the hypothesis that the polarisation resistance is determined by the rate of
oxidation of previously reduced species. This e€ect may also be operative in the dry
tank as indicated by the open circuit potential 8 h after the current pulse was applied
to the treated chloride free specimen that was more negative than either its initial
potential or that of the untreated control (Fig. 7).
However the oxidation of previously reduced species cannot explain the low po-
larisation resistance values determined on the untreated specimen in the wet tank
(Fig. 11). As noted above, corrosion in this case may involve the cathodic reduction of
iron(III) compounds formed prior to placing the specimens in this tank (the reduction
 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131 1129

of previously oxidised species). For example the reduction of Fe(OH)3 to Fe(OH)2

may start at potentials below the equilibrium potential of this half reaction which
range between 400 and 700 mV (SCE) as the pH changes from 6 to 12 [35]. Thus
the corrosion potential may be close to the equilibrium potential of the cathodic
reduction half reaction. A similar e€ect may also have occurred at the sustained
negative open circuit potentials induced by the cathodic current in the wet tank that
could be close to the equilibrium potential of the anodic dissolution of iron.
It was noted that, when a positive trend in open circuit potentials (Figs. 5 and 7)
or sustained negative potentials were observed (Fig. 9), corrosion induced deterio-
ration was e€ectively arrested and no disruption of the concrete cover occurred.
Thus such measured potential trends may be used to indicate protection. However,
between these two cases, representing aerated (atmospherically exposed) and oxygen
starved (submerged) conditions, there will be a transition zone. In this zone potential
decays will be slow although oxygen may still be present in sucient quantity to
prevent a sustained negative potential shift [8]. A possible example of this is given by
the partially submerged specimens in the wet tank (Fig. 10) that, despite their rel-
atively high initial corrosion rates, showed no signs of corrosion induced cracking.
While corrosion induced deterioration may be arrested under these conditions, any
overall trend in measured potentials will be limited. The absence of such trends does
not therefore necessarily indicate a lack of protection.
Other suggested methods of monitoring cathodic protection systems include the
use of the local applied current density [8,36] and the voltage drop through the
concrete cover [19,37]. These are supported by a basis for protection that does not
rely on any change in the steel potential but rather on an improvement in the local
environment at the steel induced by the current ¯owing across the interface and the
electric ®eld in the concrete cover. Indeed the voltage drop through the concrete may
be monitored both as a direct means of assessing system performance and as a means
of assessing current distribution.

5. Conclusions

Cathodic protection at integrated current densities that are small compared to the
corrosion rate will, in some cases, induce changes in the local environment at the
steel that promote steel passivity in chloride contaminated concrete. In one example
presented, an initial corrosion rate of approximately 60 mA/m2 was arrested by an
integrated current density of 6 mA/m2 . This provides the ®rst direct evidence that the
relatively low current densities applied in practice may be e€ective in arresting high
corrosion rates of steel in concrete.
An increase in anodic polarisation, resulting from the passivating conditions in-
duced at the cathode, provides a basis that renders cathodic protection more viable
when the cathodic reaction kinetics are weakly polarised. The instantaneous pro-
tective e€ects of a negative steel potential shift induced by a relatively small current
density may be neglected. By contrast a positive shift in the open circuit potential
occurs.
1130 G.K. Glass et al. / Corrosion Science 43 (2001) 1111±1131

When the cathodic reaction kinetics are strongly polarised (e.g. when oxygen
access is restricted in saturated concrete), a small cathodic current may induce a
reducing environment at the steel. The conventional basis for cathodic protection
then applies and sustained negative steel potentials indicate that the corrosion risk is
negligible.
The small integrated protection current densities required by continuous and
intermittent cathodic protection systems applied to reinforced concrete will be
similar. This is the result of the persistence of the passivating or reducing conditions
generated at the cathode that are the dominant e€ects giving protection in both of
these types of systems.
Unlike the instantaneous protection achieved by a large negative potential shift,
the onset of the protection a€orded by relatively small cathodic currents is gradual.
Nevertheless it must be achieved suciently fast to prevent disruption of the con-
crete cover. The initial current density will depend on factors such as the concrete
cover, level of chloride contamination, chloride mobility and oxygen access.
Possible methods of assessing the performance of intermittent cathodic protection
include monitoring the applied current density and voltage induced through the
concrete cover. A positive trend in open circuit potential or a sustained negative
potential also indicates that protection is being achieved although the absence of
such trends does not necessarily indicate a lack of protection.
Caution must be exercised when using potential decays induced by large current
pulses of short duration to assess the protection achieved by an intermittent current.
In addition the polarisation resistance may be in¯uenced by the rate of oxidation of
species previously reduced by the cathodic current and an open circuit potential that
is close to the equilibrium potential of a number of possible half reactions.

Acknowledgements

This work was funded at Imperial College by the Engineering and Physical Sci-
ences Research Council (grant no. GR/J 85553). The authors would also like to
thank Mr. R. Baxter for his help in setting up the experimental programme.

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