98 DOI: 10.1002/maco.200804155
Effect of corrosion inhibitors on the initiation of
chloride-induced corrosion on reinforced
concrete structures
Dedicated to Professor Dr. Bernd Isecke on the occasion of his 60th birthday
Corrosion of carbon steel rebars is the main cause of failure of
reinforced concrete structures. To prevent and delay the occurrence
of corrosion, a high quality concrete with a proper cover and a good
mixture proportion should be designed. Additional prevention
methods are used if severe environmental conditions occur, or
when structures require very long service life. Corrosion inhibitors
seem to be attractive because of their low cost and easy handling,
1 Introduction
Corrosion inhibitors are one of the prevention methods
used to avoid rebar corrosion when reinforced concrete
structures are exposed to severe environmental conditions, or
in the case of structures requiring very long service life.
Corrosion of carbon steel rebar is caused by carbonation of
concrete (the reaction of atmospheric CO2 with cement
paste that lowers pH and causes rebar general corrosion) or
by the presence of chlorides at the carbon steel surface in
concentrations higher than a critical threshold, generally
considered to be in the range of 0.4–1% by cement weight for
structures exposed to the atmosphere [1].
Inhibitors seem to be attractive because of their low cost
and easy handling, compared with other preventive methods.
From a practical point of view, inhibitors can be divided into
two groups [2]: admixed inhibitors, added to fresh concrete
as an additive, and migrating inhibitors, applied on hardened
concrete surface and able to penetrate into it (usually used in
repair systems). While admixed inhibitors are commercially
available since 1970s, migrating corrosion inhibitors for
concrete structures were proposed in the last 15–20 years [2].
Inhibitors can also be divided into inorganic or organic,
according to their chemical composition: inorganic com-
pounds are based on nitrites, especially used as additives
[3–7], or on sodium mono-fluoro-phosphate, used only as
migrating inhibitors [2,8,9]. Organic inhibitors are based on
mixtures of alkanolamines, amines and amino acids, or based
on emulsion of unsaturated fatty acid ester. They may be
used both as admixed and migrating inhibitors [2,10–17].

M. Ormellese, F. Bolzoni, L. Lazzari, P. Pedeferri
Department Chemistry, Materials and Chemical Engineering,
Politecnico di Milano, Via Mancinelli 7, 20131 Milano (Italy)
E-mail: marco.ormellese@polimi.it
www.wiley-vch.de/home/wuk ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Materials and Corrosion 2008, 59, No.
M. Ormellese*, F. Bolzoni, L. Lazzari and
P. Pedeferri
compared to other preventive methods. This paper analyses results
of a 10-year investigation on the effectiveness of four commercial
inhibitors and two pure organic compounds in preventing chloride-
induced corrosion. Tested inhibitors seem to be able to increase
time-to-corrosion: their effects on chloride penetration rate and on
critical chloride threshold are discussed.
Other non-commercial inhibitors, both inorganic and organic
have been studied: even if some substances show good
inhibitive properties in solution tests, concerns are with their
negative influence on concrete properties, mainly on the
setting time, workability and compressive strength [2].
Nitrite-based inhibitors (NITs) are considered the most
effective products available in the market. They have been
studied since the 1960s and their effectiveness have
been demonstrated by field applications. Nitrites act as a
passivator due to its oxidising properties, and its inhibitive


effectiveness is related to the [NO
2 ]/[Cl ] molar ratio that
should be higher than 0.5–0.6 to prevent corrosion [2–7].
Concerns are with their toxicity, solubility and possible
increase of corrosion rate in case of low dosage or in the
presence of cracks. Controversial results were obtained in
severe conditions (presence of cracks in concrete cover,
seawater) [18]. Under similar conditions, some commercial
organic products showed low inhibition efficiency too
[19,20].
Commercial organic inhibitors are available from 1980s.
As reported in the state of the art report by Elsener [2], there
is no agreement among the scientific community in defining
the effectiveness of these inhibitors; conflicting results are
frequently reported [2,10–17]. Moreover, the chemical
composition of the organic commercial inhibitors and the
concentration of the inhibitive substances are not clearly
known. No indication is given about the inhibitor dosage to
prevent corrosion in relation to the chloride content, and no
literature data provide values of critical chloride threshold in
the presence of organic inhibitors.
During the last 10 years, two different laboratory tests on
commercial corrosion inhibitors have been carried out.
Tested products were available on market in 1997 and in
2000; also two pure organic compounds (sodium benzoate
and di-methyl-ethanol-amine, DMEA) have been analysed.
Materials and Corrosion 2008, 59, No. 2 Effect of corrosion inhibitors 99

On the basis of obtained experimental results (described

in previous papers [21,22]), the efficiency of inhibitors on
initiation time in the case of chloride-induced corrosion is
discussed in this paper: the effects on both chloride
penetration rate and critical chloride threshold are con-
sidered.

2 Experimental

Three series of concrete specimens were casted: series A

and B with commercial corrosion inhibitors (three organics
and one nitrite-based product) and series C with two pure
organic compounds. Specimens were subjected to acceler-
ated chlorides penetration, i.e. ponding cycles 3 weeks long:
in the first week the upper surface of the concrete samples
was wetted with a 3.5% sodium chloride solution, then
for the next 2 weeks, samples were dried in laboratory. Tests
on series A last 3 years, while tests on series B and C were
5 year long.
Fig. 1. Details of specimen for concrete tests (series A)

2.1 Concrete specimens of series A

Concrete specimens (160  250  70 mm3) were casted
with 300 kg/m3 of cement CEM II A/L 42,5R (European
standard CEN ENV 197/1 [23]), a water/cement ratio (W/C)
equal to 0.5 and calcareous aggregates (10 mm maximum
size) from Zandobbio (BG, Italy) (Table 1). Concrete
samples were cured for 7 days at 20 8C and 95% relative
humidity.
A carbon steel rebar was placed in each concrete
specimen: 10 mm in diameter and 270 mm length. The
ends of each rebar were covered by thermoretractil sheath, so
that only a length of 170 mm was exposed to the concrete
(Fig. 1). Concrete cover was 20 mm. Two AISI 304 stainless
steel rebars (10 mm in diameter) and an AISI 304 stainless
steel wire (1 mm diameter) were placed in concrete
specimens for corrosion rate measurements.
Commercial corrosion inhibitors (available on market
in 1997) were added to concrete mixture according to
producers recommendations. Three organic products and one
nitrite-based product were considered. Dosages are reported
in Table 1. For comparison purposes, specimens without
inhibitors were casted.
For each condition, cubic concrete specimens (100 mm in
side) were casted for compressive strength measurements,
performed after 28 days of curing: commercial inhibitors do
not influence the mechanical properties (Table 1).
2.2 Concrete specimens of series B
Concrete specimens (200  250  50 mm3) were casted
with 367 kg/m3 of cement CEM II A/L 42,5R (European
standard CEN ENV 197/1 [23]), W/C ratio equal to 0.6, and
1.770 km/m3 of limestone aggregates (12 mm maximum
diameter). An acrylic super-plasticizer (0.6% by cement
weight) was added to concrete mixture. After 2 days of
curing in the mould, the concrete was cured until 28 days in a
wet environment (95% RH).
Two carbon steel rebars (10 mm in diameter and 290 mm
length) were placed in each concrete specimen (Fig. 2). The
ends of each rebar were coated, so that only a length of
210 mm was exposed to the concrete. Concrete cover was
20 mm. A thin wire of mixed metal oxide activated titanium
(MMO) was fixed near each rebar to be used as reference
electrode and three AISI 304 stainless steel wires (2 mm in
diameter) were embedded in the specimens and used as
counter-electrode for corrosion rate measurements.

Table 1. Concrete mixture proportion, properties and inhibitors dosages

Series A Series B Series C

Cement content kg/m3 300 367 367

Water/cement ratio 0.5 0.6 0.6
Aggregate content kg/m3 2000 1770 1770
Plasticizer kg/m3 4.5 2.2 2.2
Slump mm 160 190 190
Curing time (95% RH) Days 7 28 28
Compressive strengtha) MPa 46–47 40–43 41–42
OCIA-1 (liquid–amino-alcohols) L/m3 10 10
OCIA-2 (liquid–alkanolamines) L/m3 1.6 1.6
OCIA-3 (liquid–amine-esters) L/m3 5 5
NIT (30% solution of calcium nitrite) kg/m3 7.5 10
DMEA (liquid) L/m3 3.6
Sodium benzoate (powder) kg/m3 3.6
a)
Mean value of concrete without chlorides, with or without inhibitor.

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100 Ormellese, Bolzoni, Lazzari, and Pedeferri
Fig. 2. Details of specimen for concrete tests (series B and C)
The same four commercial corrosion inhibitors (but
available on market in 2000) were added to the concrete
mixture in the recommended dosages, as reported in Table 1.
For comparison purposes, specimens without inhibitors were
casted. It is important to underline that the tested corrosion
inhibitors of these two series may have different chemical
composition since they were bought in 1997 and 2000,
respectively.
For each condition, three cubic specimens (100 mm in
side) were casted in order to check compressive strength
(mean values are reported in Table 1). Also in this case
inhibitors do not influence concrete mechanical properties.
2.3 Concrete specimens of series C
Concrete samples with the same mixture proportion of
series B were casted with two pure organic compounds,
sodium benzoate and DMEA: they are claimed to be active
constituents of some organic commercial corrosion inhibi-
tors [2], for example they are present in OCIA-1 and
OCIA-2. The two substances were added in dosages 1% with
respect to cement weight that correspond to 3.6 kg/m3. That
is a higher dosage with respect to the supposed recommended
one. Powder of sodium benzoate and liquid DMEA were
firstly dissolved in water and then added to the mixture as an
additive.
2.4 Corrosion monitoring
Free corrosion potential was measured with respect to a
saturated calomel reference electrode (SCE) placed on the
external surface of the concrete samples [24]. Corrosion
rate was measured using the linear polarization resistance
technique (LPR) [25,26]: a potential scan rate of 10 mV/
minute from
10 to þ10 mV with respect to the free
corrosion potential was applied. Mean corrosion rate was
Materials and Corrosion 2008, 59, No. 2
calculated by means of Stern–Geary equation:
icorr ðmm=yÞ ¼ 1:17  icorr ðmA=m2 Þ ¼ 1:17  C=Rp (1)
where Rp is the measured polarization resistance (Vm2) and
constant C is assumed equal to 26 mV for actively corroding
rebars, and 52 mV for passive rebars [26]. Since corrosion
penetration lower than 1–2 mm/y can be considered negligible
[27,28], polarization resistance of about 10–20 Vm2 is the
threshold value below which corrosion is significant.
2.5 Chloride penetration
Chloride profiles were determined on concrete cores
(30 mm in diameter) drilled from the reinforced concrete
specimens. Cores were cut into 10 mm slices. Each slice was
crushed and then dissolved into nitric acid. Total chloride
content was analysed by potentiometric titration with 0.01 N
silver nitrate.
Titrations were performed on the three series as follows:
two times on series A (at the 4th and 37th ponding cycle);
five times on series B (at the 14th, 30th, 47th, 65th and 86th
ponding cycles); four times on series C (at the 14th, 29th,
47th and 57th ponding cycles).
3 Results
Aim of the paper is the evaluation of the effect of corrosion
inhibitors on chloride penetration rate and on critical
chloride threshold for the initiation of chloride-induced
corrosion in concrete. A detailed description of corrosion
monitoring results (free corrosion potential and polarization
resistance) on concrete samples of series A and B is reported
in previous papers [21,22]. Here, only potential and chloride
profiles measurements are presented and discussed.
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Materials and Corrosion 2008, 59, No. 2 Effect of corrosion inhibitors 101

content at the rebar level was measured in

all the reinforced specimens: the lower
values were detected in concrete with
organic inhibitors (1.5–2% by cement
weight), while in reference concrete
chloride content was 3.2%.
3.2 Tests on concrete specimens of
series B

Concrete specimens of series B were

exposed to 87 ponding cycles, each 3
weeks long. Free corrosion potential
trends are shown in Fig. 6. Initial rebar
free corrosion potential was about
100
mV SCE, i.e. rebars were in passive
Fig. 3. Free corrosion potential of rebars in specimen subjected to chloride penetration
condition. Also in this case, the sudden
(series A)
decrease of potential to values lower than

300 mV SCE indicates the occurrence of
corrosion. At the end of the test (after
3.1 Tests on concrete specimens of series A 2000 days) only one rebar embedded in concrete with
inhibitor OCIA-1 remained in passive condition (free
Forty-seven ponding cycles have been performed on corrosion potential close to
100 mV SCE and corrosion
concrete samples of series A. Initial rebar free corrosion rate lower than 2 mm/y).
potential was close to
100 mV SCE (Fig. 3), i.e. rebars Time-to-corrosion is reported in Fig. 7: in the reference
were in passive condition (polarization resistance was close specimens, corrosion occurred on the four rebars in between
to 100 Vm2 [22]). The sudden decrease of potential to values the 10th and 38th ponding cycle. Similar values were
lower than
300 mV SCE indicates the occurrence of measured in the presence of inhibitor OCIA-2. The best
corrosion. At the end of the test, after 1100 days, corrosion effect was offered by inhibitor OCIA-1: one of the four
occurred on all the reinforcements: low free corrosion rebars remained passive, while the others showed corrosion
potential and high corrosion rate were measured. Figure 4 after 57 ponding cycles. Corrosion on rebars embedded in
summarizes the number of the cycle at which corrosion concrete with inhibitor OCIA-3 occurred around the 65th
occurred for each rebar: commercial organic inhibitors seem ponding cycle. The presence of nitrite showed a behaviour
to be able to delay corrosion initiation with respect to the slightly better than that observed in concrete with OCIA-2.
reference concrete samples; organic inhibitor OCIA–1 has Five total chloride profiles have been measured during the
the best effect, even better than the nitrite-based product. 5 year long test. Figure 8 shows results obtained at the 14th,
At the 37th ponding cycle (after 820 days) a core has been 47th and 86th ponding cycles. No significant difference in
taken for each specimen and total chlorides profile was chloride penetration was detected after 14 ponding cycles.
determined. Commercial corrosion inhibitors reduced the Chloride content increased with time: after 47 ponding
penetration of chlorides (Fig. 5): at the rebar level (20 mm) cycles, at the rebar level (20 mm), the highest chloride
chlorides content is close to 2.1% by cement weight for content was measured in the reference concrete (0.4% by
concrete without inhibitor, while it is in the range of concrete weight), while in the presence of corrosion
1.2–1.8% in concrete with corrosion inhibitors. At the end of inhibitors the concentration was in the range 0.18–0.24%
the tests (after 47 ponding cycles, 1100 days) chlorides by concrete weight. At the end of the test (after 87 ponding
cycles) the lowest chloride profiles were measured in the
presence of organic inhibitors (OCIA-1 offers the highest
resistance to chloride penetration); the chloride profile
measured in concrete with NIT is slightly lower than the
profile for reference concrete.
3.3 Tests on concrete specimens of series C

Eighty-seven ponding cycles were carried out. Free

Fig. 4. Time-to-corrosion for specimens subjected to chloride
penetration (series A)
corrosion potential trends are reported in Fig. 9. Both
organic substances increase corrosion initiation time:
corrosion occurred after 40 ponding cycles on rebars
embedded in concrete with sodium benzoate, and after 60
ponding cycles on rebars in concrete with DMEA (Fig. 7).
Chloride profile has been measured four times during the
5 year long test. Figure 10 shows results obtained at the 14th,
47th and 57th ponding cycle. In the presence of DMEA,
chloride content at the rebar level (20 mm) increased from
0.2% by concrete weight at the 14th ponding cycle to 0.5% at
the 57th ponding cycle; in the presence of sodium benzoate
chloride content at the rebar level increased from 0.18% at
the 14th ponding cycle to 0.38% at the 57th ponding cycle.

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102 Ormellese, Bolzoni, Lazzari, and Pedeferri
Fig. 5. Total chloride penetration profiles measured at the 38th
ponding cycle for reinforced concrete samples of series A
4 Discussion
During the last 10 years, two different laboratory tests on
commercial corrosion inhibitors have been carried out. From
1997 to 2001 commercial products available on market in
1997 were tested in concrete with W/C ratio equal to 0.5 and
curing time 7 days (series A); from 2000 to 2006 products
available on market in 2000 were tested in concrete with a
higher W/C ratio, equal to 0.6 (i.e. more porous cement
paste) but with a higher curing time, too (28 days) (series B).
In this latter case, also two pure organic compounds have
been studied (series C).
Even if concrete specimens were casted with different
W/C ratio and curing time, on the basis of the measured
compressive strength (40–46 MPa, Table 1), it is possible to
assume that the porosity of the two concrete mixtures may be
considered similar.
An effective corrosion inhibitor should influence the
service life of reinforced concrete structure: it could delay
corrosion initiation, by increasing the critical chlorides
threshold or reducing chlorides penetration rate, or, even
Fig. 6. Free corrosion potential of rebars in specimen subjected to chloride penetration
(series B)
Materials and Corrosion 2008, 59, No. 2
Fig. 7. Time-to-corrosion for specimens subjected to chloride
penetration (series B and C)
once corrosion occurred, it may reduce corrosion rate. In this
paper only the influence on time-to-corrosion has been
discussed.
4.1 Influence of inhibitors on time-to-corrosion
On the basis of the corrosion monitoring results, the
presence of both admixed commercial inhibitors and pure
compounds increases time-to-corrosion, as clearly illustrated
in Figs. 4 and 9 that report the number of the ponding cycle in
which the occurrence of corrosion was detected by the
sudden reduction of free corrosion potential (Figs. 3,6 and 9).
Rebars embedded in concrete without inhibitors show the
lowest time-to-corrosion. The more effective inhibitor is
OCIA-1: at the end of test on series B (after 86 ponding
cycle, corresponding to more than 2000 days) one rebar is
still in passive condition. Only a slight effect was noticed in
the presence of inhibitor OCIA-2. Inhibitor OCIA-3 has an
intermediate behaviour. NIT effect is scattered: time-
to-corrosion ranged from values similar to those measured
in the absence of inhibitors to values slightly lower than those
obtained in the presence of inhibitor OCIA-3. The two pure
organic substances, which are two of the main compounds
used in the organic commercial inhibitors, behave as
inhibitor OCIA-3.
The influence of inhibitors on initiation
of corrosion may be related to an increase
in the critical chloride threshold, as well
as to a reduction of chloride penetration
rate (as a reduction of chloride diffusion
coefficient). These two parameters were
estimated by interpolating the experimen-
tal chloride profiles with the analytical
solution of the second Fick’s law, valid for
non-stationary diffusion phenomena:
!
x
Cx ¼ CS 1
erf pffiffiffiffiffiffiffiffiffiffi (2)
2 Dapp t
where Cs is the surface chlorides content,
Dapp is the apparent diffusion coefficient,
Cx is the chloride content at the depth x
and t is time [1].
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Materials and Corrosion 2008, 59, No. 2 Effect of corrosion inhibitors 103

Fig. 8. Total chloride penetration profiles measured at the 14th, 47th and 86th ponding cycle for reinforced concrete samples of series B

4.2 Influence of inhibitors on chlorides penetration content was measured in concrete without inhibitor, while in
rate the presence of organic inhibitors chloride penetration is
reduced with time. A slight effect was also noticed in the
Tested commercial corrosion inhibitors reduce the presence of NIT. The two pure organic compounds behave
penetration of chlorides into concrete: considering the like organic inhibitors (Fig. 10).
measured profiles in time (Fig. 8), the higher chlorides Chlorides penetration in concrete is due to the presence
of different mechanisms: mainly diffusion
and capillary sorption. Only for compar-
ison purposes, experimental profiles may
be interpolated using an analytical solution
of the second Fick’s law (Equation (2)),
supposing that chlorides content at the
concrete surface is constant with time, and
considering an apparent chloride diffusion
coefficient that does not vary with time and
space (i.e. concrete is homogeneous). By
the interpolation, the apparent chloride
diffusion coefficients were estimated
(Table 2).
First of all, in the case of series B, it is
important to underline that apparent
diffusion coefficient decreases with time
as a result of the continuous cement
hydration that leads to a concrete porosity
Fig. 9. Free corrosion potential of rebars in specimen subjected to chloride penetration reduction, that is independent of the type of
(series C) tested inhibitors. Similar trend was

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104 Ormellese, Bolzoni, Lazzari, and Pedeferri Materials and Corrosion 2008, 59, No. 2

Fig. 10. Total chloride penetration profiles measured for reinforced concrete samples in the presence of DMEA and sodium benzoate
(series C)

observed for concrete with DMEA and sodium benzoate:
apparent diffusion coefficient decreases from 5.6  10
8 to
2.5  10
8 cm2/s, and from 7.4  10
8 to 4.8  10
8 cm2/s,
respectively.
The presence of organic inhibitors reduces the apparent
diffusion coefficient from two to four times the values
obtained for reference concrete (Table 2). Maximum
reduction occurs in specimens containing inhibitors OCIA-2
and OCIA-3, as already reported in literature [2,10,20]. Also
NIT show a slight effect on chloride penetration, since it
contains some organic compounds.
Inhibitors have a sort of ‘physical-barrier’ effect: this is
probably due to the formation of gel compounds among
organic substances and cement paste that block the pores,
reducing chlorides penetration rate. From an electrochemical
point of view, this effect cannot be considered a real
inhibiting action, since it can be obtained acting on concrete
mixture proportion, reducing W/C ratio or using pozzolanic
or blended cements [1]. Nevertheless, compact and adequate
concrete cover can have a synergic effect in combination
with inhibitors. For example, Berke and other authors
recommended the use of NIT in combination with low W/C
ratio and high concrete cover, not only to prevent leaching of
inhibitor [4].
4.3 Effect of inhibitors on critical chloride threshold
On the basis of the obtained apparent diffusion coef-
ficients, knowing the time of corrosion initiation (Figs. 4
and 7), the critical chloride content at the rebar level
(x ¼ 20 mm) has been estimated by means of second Fick’s
law analytical solution (Equation (2)). Critical chloride
values were evaluated also graphically using the measured
profiles. Results regarding the three tested series are
summarized in Fig. 11.
First of all, it must be underlined that the extrapolated data
have to be carefully analysed, since the diffusion coefficient
is not constant with time (see Table 2), as requested to use the
analytical solution of Fick’s law. Besides, values are related
to the described experimental conditions, so they should
not be considered as absolute values, but used only for
comparison purposes.
In the absence of inhibitor, estimated critical chloride
content is in the range 0.5–1.2% with respect to cement
weight: those values are in accordance with literature, at
least the minimum ones [1]. As reported by Andrade and
co-workers [29], the critical chlorides content is influenced
by a lot of parameters: pH of concrete pore solution, type of
cement, oxygen availability and temperature. Glass and
Buenfeld [30] underlined the relationship of the critical
chloride content with the cement paste porosity at the
interface rebar-concrete: the lower is the porosity, the higher
is the critical chloride content. Due to the laboratory-
controlled condition during casting of concrete samples, it is
possible to assume that a low level of porosity is achieved at
the interface rebar-concrete: this is the reason of the higher
maximum critical chloride value measured in our tests.
In the case of commercial organic inhibitors, literature
data do not allow to define a critical chloride content. As
reported in the state of the art report by Elsener [2], there is
no agreement among the scientific community in defining the

Table 2. Apparent chloride diffusion coefficients (10
8 cm2/s)

for concrete with commercial corrosion inhibitor
Series A Series B

14th 30th 47th 65th 86th

No inhibitor 12 7.2 7.4 6.8 8.4 10

OCIA-1 6.6 6.8 3.5 2.9 3.4 2.5
OCIA-2 8.6 4.7 2.9 2.3 2.0 3.5
OCIA-3 7.9 3.2 2.8 1.9 2.0 1.8
NIT 8 6.1 4.5 3.1 3.5 6.0
Fig. 11. Estimated critical chloride threshold

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Materials and Corrosion 2008, 59, No. 2
effectiveness of these inhibitors; conflicting results are
frequently reported.
Considering results illustrated in Fig. 11, organic
inhibitors OCIA-1 and OCIA-3 provide a significant increase
in critical chloride content: both minimum and maximum
values are doubled with respect to reference condition.
Inhibitor OCIA-2 does not offer any significant influence.
The inhibitive effect of inhibitor OCIA-1 is also confirmed
by results obtained in a parallel series of tests in which
chlorides were directly added in the mixture of the concrete
in concentration 1.2% with respect to cement weight:
all carbon steel rebars were in passive condition even after
5 years [21].
The two pure organic compounds have only a minimum
effect on the critical chloride interval. As previously
mentioned, these organics substances are two of the active
compounds used in some commercial organic corrosion
inhibitors: OCIA-1 and OCIA-2 contain both of them in
unknown concentrations. Elsener [2] underlines that only
in the presence of both sodium benzoate and DMEA a clear
inhibitive effect is demonstrated; otherwise, the two pure
compounds have a little or negligible effect. Results obtained
with series C are in agreement with literature.
Calcium NIT must be analysed separately; more literature
data are available on its inhibiting action [2–7], suggesting
that the corrosion inhibitor is effective if the molar ratio


[NO
2 ]/[Cl ] is higher than 0.5–0.6. Tests results seem to be
in accordance with literature: considering inhibitor dosage
(7.5 L/m3 for series A and 10 L/m3 for series B) and the
obtained critical chloride content (Fig. 11), the estimated


molar ratio [NO
2 ]/[Cl ] is in the range 0.42–0.51. The
reliability of the threshold molar ratio was also confirmed by
tests performed on concrete specimens casted with chloride
0.8 and 1.2% by cement weight [21]: after 5 year tests rebars
are still in passive condition, and the calculated molar ratio is
0.55 and 0.37, respectively.
5 Conclusions
During the last 10 years, two different laboratory tests on
commercial corrosion inhibitors have been carried out. Also
two pure organic compounds were tested. Reinforced
concrete samples were exposed to accelerated chloride
penetration by means of 3 week long ponding cycles: the first
week wetting the upper surface of concrete with 3.5%
sodium chloride solution; then next 2 weeks drying concrete
in laboratory.
On the basis of corrosion monitoring results and chloride
profiles measurements the following can be drawn:
– tested commercial corrosion inhibitors (available in the
market in 1997 and 2000) and the two pure organic
substances seem to be able to delay the occurrence of
corrosion; inhibitor OCIA-1 is the more effective;
– the increase of time-to-corrosion is related to both a
reduction of chloride penetration rate (as reduction of
apparent chloride diffusion coefficient) and to a certain
increase on the critical chloride threshold;
– organic commercial inhibitors reduce apparent chloride
diffusion coefficient from two to four times; from an
electrochemical point of view, this effect is not a real
inhibitive action, but a sort of ‘physical barrier’ effect;
– organic commercial inhibitors OCIA-1 and OCIA-3
provide a significant increase of the critical chloride
threshold: both minimum and maximum values are
doubled with respect to reference condition;
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Effect of corrosion inhibitors 105
– results obtained in the presence of NIT confirm literature
data: the inhibitor is effective if the molar ratio [NO

2 ]/
[Cl
] is higher than 0.5–0.6.
It is worth noticing that in any case estimated values are
scattered: so the inhibitive effect of tested inhibitors is not
fully clear, above all in experimental conditions different
from those used in this research. Nevertheless, 10 years of
testing allow to state that two commercial organic inhibitors
(OCIA-1 and OCIA-3) provide a significant increase in
time-to-corrosion, due to both an increase of the critical
chloride threshold and to a reduction of the apparent chloride
diffusion coefficient.
6 References
[1] L. Bertolini, B. Elsener, P. Pedeferri, R. Polder, Corrosion of
Steel in Concrete: Prevention, Diagnosis, Repair, Wiley,
Weinheim, 2004.
[2] B. Elsener, Corrosion Inhibitors for Steel in Concrete—State
of the Art Report, EFC Publications, Cambridge, Number
35–2001.
[3] N. S. Berke, Mater. Perform. 1989, 10, 41.
[4] N. S. Berke, T. G. Weil, presented at CANMET, Athen, Greece,
1992, pp. 899–924.
[5] I. A. Callander, F. Gianetti, presented at Annual Middle East
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(Received: October 10, 2007) W4155
(Accepted: October 28, 2007)
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