lilUTT E R W OR T H

E!NEMANN
0950-0618(95)00002-X
Construction and Building Matertals, Vol. 9, No. 2, pp. 97-103, 1995
Copyright © 1995 Elsevier Scíence Ltd
Printed in Great Britain. Ali rights reserved
Commented [cco1]: Comportamiento electroquímico del
acero en hormigones de cemento lisos y mezclados en
0950--0618/95 $10.00+0.00 entornos de sulfato y / o cloruro.
Commented [cco2]: Se investigó el comportamiento
electroquímico del acero de refuerzo en muestras de concreto
de cemento liso y mezclado en ambientes de sulfato, cloruro
y cloruro de sulfato. El efecto de la composición del cemento
Electrochemical behavior of steel in plain and y las condiciones de exposición sobre el comportamiento a la
blended cement concretes in sulphate and/or corrosión del acero de refuerzo se evaluó midiendo los
potenciales de corrosión a intervalos periódicos y realizando
chloride environments escaneos potenciodinámicos después de dos años y medio de
exposición. Los datos del potencial de corrosión indicaron
corrosión pasiva en muestras de concreto de cemento liso y
mezclado colocado en el ambiente de sulfato puro. Sin
Nezar R. Jarrah, Omar Saeed Baghabra AI-Amoudi, Mohammed Maslehuddin*, embargo, el tiempo hasta la iniciación de la corrosión de
Oluwatoyin A. Ashiru and Abdulaziz lbrahim Al-Mana refuerzo fue mayor en los cementos mezclados que en los
cementos simples en todos los ambientes de cloruro y sulfato
King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia de cloruro. La presencia concomitante de sales de sulfato y
cloruro no influyó significativamente en el tiempo de
iniciación a la corrosión. La velocidad de corrosión, sin
Received 2 March 1994; revised 22 October 1994; accepted 21 November 1994
embargo, se vio significativamente influenciada por la
cantidad de iones sulfato asociados con las sales de cloruro.
The electrochemical behavior of reinforcing steel in plain and blended cement concrete specimens El rendimiento superior del cemento mezclado con humo de
placed in sulphate, chloride and sulphate-chloride environments was investigated. The effect of
sílice, en términos de mayor tiempo de iniciación a la
cement composition and the exposure condition on the corrosion behavior of reinforcing steel was
corrosión y menor índice de corrosión, indica su potencial
evaluated by measuring corrosion potentials at periodic intervals and conducting potentiodynamic
para mejorar la vida útil de las estructuras de hormigón
scans after two and half years of exposure. The corrosion potential data indicated passive corrosion
in plain and blended cement concrete specimens placed in the pure sulphate environment. The armado colocadas en los ambientes de cloruro-sulfato.
time to initiation of reinforcement corrosion, however, was higher in blended cements than plain Commented [cco6]: Alternativamente, pueden penetrar el
cements in all chloride and chloride-sulphate environments. The concomitant presence of sulphate concreto endurecido desde el entorno externo. El deterioro
and chloride salts did not significantly influence the time to corrosion initiation. The corrosion de las cubiertas de puentes de hormigón armado debido al
rate, however, was significantly influenced by the quantum of sulphate ions associated with the uso de sales anticongelantes en los climas templados de EE.
chloride salts. The superior performance of silica fume blended cement, in terms of longer time to UU. Y Europa está bien documentado. La corrosión del
corrosion initiation and lower corrosion rate, indicates its potential in enhancing the useful service
refuerzo debido a las sales de cloruro también es un
life of reinforced concrete structures placed in the chloride-sulphate environments.
problema de durabilidad predominante en las áreas costeras
del Golfo Arábigo.
Keywords: electrochemical behavior; steel; concrete
Commented [cco3]: En el concreto reforzado, el acero
proporciona la propiedad de tracción que tanto se necesita,
In reinforced concrete, steel provides the much needed Alternatively, they may penetrate the hardened concrete mientras que el concreto esencialmente se ocupa de las
tensile property, while concrete essentially takes care of from the external environment. Deterioration of tensiones de compresión. Además, el hormigón proporciona
the compressive stresses. Furthermore, concrete reinforced concrete bridge decks due to the use of de- protección física y química al acero de refuerzo. La
provides both physical and chemical protection to the icer salts in the temperate climates of the US and Europe protección física es proporcionada por su estructura densa
que retarda la entrada de especies agresivas, como el
reinforcing steel. The physical protection is provided by is well documented. Corrosion of reinforcement due to oxígeno, la humedad y los iones cloruro a la interfaz acero-
its dense structure which retards the ingress of aggressive chloride salts is also a predominant durability problem hormigón. La protección química es proporcionada por la
species, such as oxygen, moisture and chloride ions to the in the coastal areas of the Arabian Gulf. alta alcalinidad de la solución de poro debido a la cual se
steel-concrete interface. The chemical protection is The marine structures, both on-shore and off-shore, forma una película protectora submicroscópicamente delgada
provided by the high alkalinity of the pore solution due however, are subjected to both chloride-induced de óxido de hierro sobre la superficie del acero.
to which a submicroscopically thin protective film of reinforcement corrosion and sulphate attack. The role of Commented [cco4]: A pesar de la protección inherente
y-ferric oxide is formed on the steel surface. sulphate ions, when chlorides and sulphates are proporcionada al acero por el hormigón, las fallas de las
In spite of the inherent protection provided to the conjointly present, on corrosion of reinforcing steel is estructuras de hormigón resultantes de la corrosión del
steel by concrete, failures of concrete structures resulting often a point of controversy. Holden et al.1 indicated refuerzo no son infrecuentes. La descomposición de la capa
from reinforcement corrosion are not uncommon. The pasiva se atribuye a dos factores principales, a saber (i) la
that the concomitant presence of chlorides and reducción del pH del hormigón circundante debido a la
breakdown of the passive layer is attributed to two sulphates increases the risk of corrosion significantly. Al- carbonatación y (ii) la penetración de iones agresivos como
principal factors, namely (i) reduction in the pH of the Tayyib et al.2 reported a seven-fold increase in corrosion los cloruros en la interfaz acero-hormigón. La corrosión del
surrounding concrete due to carbonation and (ii) activity on mild steel exposed to sulphate-containing refuerzo debido a la penetración de dióxido de carbono
penetration of aggressive ions like chlorides to puede dar como resultado una corrosión uniforme y es
calcium hydroxide solutions over those containing predominante en áreas industriales.
the steel-concrete interface. Reinforcement corrosion
chloride salts. Cheng et al. 3 investigated the effects of
due to penetration of carbon dioxide may result in Commented [cco5]: La corrosión de refuerzo inducida
chloride and sulphate ions on the electrochemical
uniform corrosion and is predominant in industrial por cloruro se atribuye básicamente a los cloruros que se
areas. The chloride-induced reinforcement corrosion is properties of reinforcing steel using an AC impedance introducen en el hormigón a través de un acelerador,
basically attributed to chlorides which are introduced technique. Their results indicated that the presence agregados contaminados y / o agua de mezcla.
into the concrete through an accelerator, contaminated of sulphate ions could modify the surface characteristics of
Commented [cco7]: Las estructuras marinas, tanto en
aggregates and/or mixing water. reinforcing steel. Studies conducted by Al-Amoudi and tierra como en alta mar, sin embargo, están sujetas a
Maslehuddin4 showed that reinforcement corrosion corrosión de refuerzo inducida por cloruro y a ataque de
*Correspondence to M. Maslehuddin, KFUPM Box 442, Dhahran increases due to the conjoint presence of chloride and sulfato. El papel de los iones sulfato, cuando los cloruros y
31261, Saudi Arabia sulfatos están presentes conjuntamente, en la corrosión del
sulphate salts as compared to those exposed to chloride salts.
acero de refuerzo es a menudo un punto de controversia.
Holden et al.1 indicaron que la presencia concomitante de
Construction and Building Materíals 1995 Volume 9 Number 2 97 cloruros y sulfatos aumenta significativamente el riesgo de
corrosión. Al-Tayyib et al.2 reportaron un aumento de siete
veces en la actividad de corrosión en acero dulce expuesto a
soluciones de hidróxido de calcio que contienen sulfato ...
 Electrochemical behaviour of steel: N. R. Jarrah et al. Electrochemical behaviour of steel: N. R. Jarrah et al.

Commented [cco12]: Soluciones de prueba. Después del

Table l Chemical composition of cernents and blending materials Test solutions. After demoulding, the specimens were cured desmoldeo, las muestras se curaron en agua potable durante
in potable water for a further period of 1 4 days and un período adicional de 14 días y luego se colocaron en las
Constituent (wt. %) Fly Blast furnace Silica Type V Type I
ash slag cement fume cement cernen! then placed in the four test solutions. The composition cuatro soluciones de prueba. La composición de las
soluciones de prueba se detalla a continuación:
of the test solutions is detailed below:
Silicon dioxide 52.3 27.7 92.5 22.0 20.5
Aluminium oxide 25.2 12.8 0.4 4.1 5.6
Commented [cco13]: Las soluciones de prueba 3 y 4
Ferric oxide 4.6 12 0.4 4.2 3.8 Solution 1: 15. 7% Cl (pure chloride environment) representan la concentración de iones de cloruro y sulfato
Calcium oxide JO.O 44.0 0.5 64.l 64.4 Solution 2: 2.1 % SO¡ -- (pure sulphate environment) que se encuentran comúnmente en las salmueras de sabkha
Magnesium oxide 2.2 8.8 0.9 2.2 2.1 costeras y continentales en el Golfo Arábigo,
Sulphur trioxide 0.6 3.1 0.5 2.0 2.1 Solution 3: 0.55% SO¡-+ 15.7% CI- (low sulphate- respectivamente '. Las soluciones de prueba 1 y 2
Loss on ignition 0.4 0.9 2.6 0.8 0.7 chloride environment) representan las concentraciones máximas de cloruro y sulfato
Potassium oxide 0.3 0.3 Solution 4: 2.21% SO¡-+ 15.7% CI- (high sulphate-
Sodiurn oxide 0.2 0.2 en estas soluciones.
C3S 54.6 56.7 chloride environment)
Commented [cco8]: Si bien los estudios citados
C3A 3.5 8.5 anteriormente proporcionan una indicación del papel de los
C4AF 12.9 11.6 Test solutions 3 and 4 represent the concentration of iones sulfato en la corrosión por refuerzo, es necesario
chloride and sulphate ions commonly found in the investigar el comportamiento electroquímico del acero en el
While the studies cited above provide an indication of coastal and continental sabkha brines in the Arabian concreto, particularmente en cementos mezclados que se
Gulf, respectively'. Test solutions 1 and 2 represent the usan comúnmente hoy en día para utilizar los beneficios
the role of sulphate ions on reinforcement corrosion, tecnológicos acumulados de sus utilizar.
there is a need to investigate the electrochemical behavior maximum chloride and sulphate concentrations in these
of steel in concrete, particularly in blended cements which solutions. Commented [cco14]: Se usó cloruro de sodio para
Sodium chloride was used to provide the chloride proporcionar los iones cloruro, mientras que se usaron
are commonly used these days to utilize the technological sulfato de sodio y sulfato de magnesio para proporcionar los
ions, while sodium sulphate and magnesium sulphate
benefits accrued from their use. iones sulfato. Las dos últimas sales se dosificaron para
were used to provide the sulphate ions. The latter two
This investigation was carried out to study the effect proporcionar el 50% de la concentración de sulfato de cada
of chloride and/or sulphate ions on the electrochemical salts were proportioned to provide 50% of the sulphate
una de ellas. Las muestras se sumergieron parcialmente en la
behavior of steel in plain and blended cement concentration from each of them. The specimens were solución contenida en los tanques de fibra de vidrio. Estos
concretes. Two types of plain cements, namely ASTM C partially immersed in the solution contained in glass tanques se cubrieron con láminas de polietileno para
150 Type V (C3 A: 3.5%) and Type 1 (C3A: 8.5%) were
fibre tanks. These tanks were covered with polyethylene minimizar la evaporación y la concentración se ajustó cada
sheets to minimize evaporation and the concentration mes.
used. The blended cements investigated utilized
replacements of fly ash, silica fume and blast furnace slag. was adjusted each month. Commented [cco9]: Esta investigación se llevó a cabo
Reinforcement corrosion. The reinforcement corrosion para estudiar el efecto de los iones cloruro y / o sulfato en el
Materials and techniques was monitored by measuring the corrosion potentials at comportamiento electroquímico del acero en hormigones de
regular intervals using a high impedance voltmeter and cemento lisos y mixtos. Se utilizaron dos tipos de cementos
Materials recording the potentials with respect to a saturated simples, a saber, ASTM C 150 Tipo V (C3A: 3.5%) y Tipo 1
The fly ash blended cement contained 20% fly ash, used (C3A: 8.5%). Los cementos mixtos investigados utilizaron
calomel electrode (SCE).
as a replacement of cement, while silica fume blended reemplazos de cenizas volantes, humo de sílice y escoria de
The electrochemical behavior of steel in the concrete alto horno.
cement contained 10% silica fume. The blast furnace specimens was evaluated by conducting
slag cement concrete specimens contained 60% potentiodynamic scans after about two and half years of Commented [cco15]: Corrosión de refuerzo. La corrosión
granulated blast furnace slag and 40% Type I cement. A exposure to the four test environments. A del refuerzo se controló midiendo los potenciales de
cementitious material content of 350 kg/m3 and water to corrosión a intervalos regulares usando un voltímetro de alta
microprocessorbased potentiostat/galvanostat was used impedancia y registrando los potenciales con respecto a un
cementitious material ratio of 0.5 were kept invariant in for polarizing the steel. A stainless steel frame placed electrodo de calomelano saturado (SCE).
all the concrete mixes. The coarse aggregate was 19 mm outside the specimen was used as a counter electrode,
maximum size crushed limestone, of bulk specific while a saturated calomel electrode was used as a reference Commented [cco10]: El cemento mezclado con cenizas
gravity 2.42 and average absorption of 3. 77%. A coarse volantes contenía un 20% de cenizas volantes, usadas como
electrode. Figure 1 is a schematic representation of the reemplazo del cemento, mientras que el cemento mezclado
to fine aggregate ratio of 1.6 by weight was kept invariant test set-up. A scan rate of 0.2 mV/s was used. A positive con humo de sílice contenía un 10% de humo de sílice. Las
in all concrete mixes. Table 1 shows the chemical feedback technique was used to compensate for the muestras de hormigón de cemento de escoria de alto horno
composition of the cements and blending materials used Ohmic drop (IR) between the reference electrode and contenían un 60% de escoria granulada de alto horno y un
in this investigation. the reinforcing bar. 40% de cemento tipo I. Un contenido de material cementoso
de 350 kg / m3 y una relación de agua a material de cemento
Results de 0,5 se mantuvieron invariables en todas las mezclas de ...
Techniques
Corrosion potentials Commented [cco16]: El comportamiento electroquímico
Reinforced concrete specimens. Concrete cylinders, 75
The corrosion potentials of steel in concrete specimens del acero en las muestras de hormigón se evaluó realizando
X 150 mm with a centrally embedded 12 mm 0
reinforcing bar, were used. The bars were cleaned made with plain and blended cements and exposed to escaneos potenciodinámicos después de aproximadamente
the four test environments are plotted against time of dos años y medio de exposición a los cuatro entornos de
thoroughly using silicon carbide paper and degreased prueba. Se usó un potenciostato / galvanostato basado en
before casting. They were also coated with epoxy coating exposure in Figures 2 to 5. Each point in these figures is
microprocesador para polarizar el acero. Se usó un marco de...
at the concrete-air interface and the embedded end to an average of three readings taken on triplicate
eliminate the crevice effect. The concrete ingredients specimens representing similar concrete constituents and Commented [cco11]: Especímenes de hormigón armado
exposure conditions. These corrosion potential-time Se usaron cilindros de hormigón, 75 X 150 mm con una
were mixed in a revolving mixer. After casting, the
curves were used to evaluate the time to initiation of barra de refuerzo de 12 mm 0 incrustada centralmente. Las
specimens were covered with wet burlap for 24 h prior barras se limpiaron minuciosamente con papel de carburo de
to demoulding. corrosion based on the ASTM C 876 criterion of -350
silicio y se desengrasaron antes del moldeado. También se
mV CSE, i.e. -270 mV SCE. recubrieron con revestimiento de epoxi en la interfaz de ...

98 Construction and Building Materials 1995 Volume 9 Number 2

 Electrochemical behaviour of steel: N. R. Jarrah et al.
The corrosion initiation times based on the potential-time
records for concrete specimens exposed to the four
environments are summarized in Table 2. Initiation of
reinforcement corrosion was indicated in Type I and Type
V cement concrete specimens placed in the high
sulphate-chloride environment after 162 and 106 days,
respectively (Figure 2). Initiation of
reinforcementcorrosion was indicated in fly ash blended
cement concrete specimens after 210 days of
exposure, The corrosion potential-time curve for steel
in silica fume blended cement concrete specimens crossed
the -270 mV SCE threshold line after about 552 days of
exposure. The corrosion potentials of steel in blast furnace
slag cement concrete specimens were lower than -270 mV
SCE even before placement in the test environment. The
high corrosion potentials in the BFS cement concrete speci-
mens may be attributed to the reducing effects of
sulphur species, namely s- -, S203, etc., derived from the
slag6 . These sulphur species in the BFS cement create a more
98 Construction and Building Materials 1995 Volume 9 Number 2
Electrochemical behaviour of steel: N. R. Jarrah et al.
reducing environment than in the other Portaland and
blendedcements. Due to this reducing environ- ment, the
potentials may be low. The corrosion rate, however,
remains low.
The time to initiation of reinforcement corrosion in
Type I and Type V cement concrete specimens exposed
to the low sulphate-chloride environment was 108 and
80 days (Figure 3). The time to initiation of corrosion of
steel in fly ash and silica fume blended cement concrete
specimens was 152 and 548 days, respectively. The
corrosion potentials of steel in blast furnace slag cement
concrete specimens were more negative than -270 mV
SCE.
The corrosion potential-time curves for specimens
placed in the pure chloride environment are presented
in Figure 4. Initiation of reinforcement corrosion in
Type I and Type V cement concrete specimens was indi-
cated after 175 and 107 days, respectively, and in fly ash
and silica fume cement concretes after 220 and 631 days
of exposure. The potential-time curve for steel in the
blast furnace slag cement concrete specimens indicated
Electrochemical behaviour of steel: N. R. Jarrah et al. Electrochemical behaviour of steel: N. R. Jarrah et al.

a trend similar to that observed in the two sulphate-

chloride environments.
The corrosion potential-time curves for specimens
placed in the pure sulphate environment indicated no
corrosion initiation even after about two years of expo-
sure (Figure 5).
In summary, the data in Table 2 indicate that the
performance, in terms of time to initiation of
reinforcement corrosion, of silica fume cement concrete
was significantly superior to fly ash and plain cement
concretes. However, the performance of fly ash cement
concrete was better than plain cements. In plain
cements, Type I cement performed better than Type V
cement in ali chloride and chloride-sulphate
environments. Further, these data also indciated that
sulphate ions alone do not initiate reinforcement
corrosion and that the time to initiation of reinforcement
corrosion
was not significantly affected by the concentration of
the sulphate ions associated with chloride ions.
The potentiodynamic plots for steel embedded in environment are shown in Table 3. These data indicate
plain and blended cement concrete specimens exposed higher corrosion activity in plain cement concrete
to the high sulphate-chloride environment are shown in specimens than that in blended cement concrete
Figure 6. The polarization current density was observed specimens. Minimum corrosion activity, as measured by
to be higher in plain cements than in blended cements. the corrosion rate, was indicated in silica fume blended
Higher corrosion activity was measured in Type V cement concrete specimens followed by blast furnace
cement (C3 A: 3.5%) than that in Type I cement (C3 A: slag and fly ash blended cement concrete specimens.
8.5%). The potential-current curve for steel in silica The potentiodynamic plots for steel in concrete
fume blended cement concrete specimens tended to be specimens placed in the low sulphate-chloride
more cathodic as compared to the corresponding curves environment are plotted in Figure 7. These curves
for other blended cement concrete specimens. indicated a trend similar to that in Figure 6. However,
The electrochemical data for steel in plain and the following
blended cements placed in the high sulphate-chloride

4 Construction and Building Materials 1995 Volume 9 Number

Construction 2
and Building Materials 1995 Volume 9 Number 2 4
 Electrochemical behaviour of steel: N. R. Jarrah et al.
features differentiate the behavior of reinforcing steel
placed in this solution from those placed in the high
sulphate-chloride environment:
(i) a passive region was indicated for steel in silica
fume cement concrete specimens, in the range of
-650 to -200 mV SCE;
(íi) the anodic portions of the potential-current
density plots for the blast furnace slag and silica
fume cement concrete specimens tended to merge
together, indicating no superior performance of
the silica fume as compared to blast furnace slag
in this environment;
(iii) the possibility of pitting corrosion is discernible
for steel in Type V cement concrete specimens
beyond -300 mV SCE.
The electrochemical data for steel in plain and
blended cement concrete specimens placed in a low
sulphate-chloride environment are shown in Table 4.
These data indicated a trend more or less similar to that
exhibited in Table 3. However, comparison of data in
TabÍes 3 and 4 indicated higher corrosion activity in
specimens placed in the high sulphate-chloride
environment than in specimens placed in the Iow
sulphate- chloride environment.
The potentiodynamic curves for steel in plain and
blended cement concrete specimens placed in the pure
chloride environment are shown in Figure 8. Uniform
corrosion was observed on steel in all the cements
except Type I cement in which pitting corrosion occurs
5 Construction and Building Materials 1995 Volume 9 Number
Construction
and Building Materials 1995 Volume 9 Number 2
Electrochemical behaviour of steel: N. R. Jarrah et al.
at a potential of -50 mV SCE. Silica fume and fly ash
cement concretes indicated superior performance in
inhibiting reinforcement corrosion compared to plain
cements. The performance of blast furnace slag cement
concrete was marginally better than that of plain
cement concretes. The potential-current density plot for
Type V cement concrete tended to be more anodic
compared to Type I cement concrete.
The electrochemical data for steel in plain and
blended cement concrete specimens exposed to the pure
chloride environment are shown in Table 5. These data
also indicated a superior performance by silica fume
cement concrete in inhibiting reinforcement corrosion.
The potential-current density curves for steel in
concrete specimens placed in the pure sulphate solution
are plotted in Figure 9. These curves indicated uniform
corrosion in all the specimens exposed to this
environment. The silica fume cement concrete specimens
indi- cated superior performance in this environment as
well. The current-potential curve for steel in blast
furnace slag cement concrete tends to shift towards a
more anodic region as compared to plain cement
concrete specimens.
The electrochemical data for steel in concrete
specimens placed in this solution are presented in Table
6. These data índicate minimal corrosion activity on steel
in silica fume cement concrete specimens placed in this
environment. The corrosion rate of steel in both plain
and blended cement concrete specimens placed in this
environment was much lower than in the corresponding
specimens placed in either chloride or sulphate-chloride
environments.
2
5
 Electrochemical behaviour of steel: N. R. Jarrah et al.
DISCUSSION
Th e time to initiation and propagation of reinforcement
corrosion are the two components of the service life
model presented by Tuutti? and Browne8. The initiation
period represents the time for the diffusion of aggressive
substances through concrete to the steel-concrete interface
to cause activation of the corrosion process. The
propagation time represents the time before loss of
serviceability or damage prevents the structure from being
used for its intended function. The data developed in this
investigation are discussed in the light of this model.
The data on time to initiation of reinforcement corrosion,
presented in Table 2, indicated a superior performance
by the blended cements, particularly silica fume cement
in inhibiting reinforcement corrosion. The time to
initiation of reinforcement corrosion in plain cement
concrete specimens placed in a pure chloride
environment was in the range of 107 to 175 days, while
for the specimens placed in sulphate-chloride
environments it was in the range of 80 to 160 days. The
time to initiation of reinforcement corrosion in fly ash
and silica fume cement concrete specimens ranged from
220 to 631 and from 152 to 552 days in the chloride and
sulphate-chloride environments, respectively.
The data in Table 2, however, do not indicate a
systematic trend with regard to the role of sulphate ions on
the time to initiation of reinforcement corrosion. The
insignificant role of sulphate ions on time to initiation of
reinforcement corrosion may be attributed to the fact that
chloride ions diffuse much faster than sulphate ions into
hardened cement matrix9 and hence totally domínate the
initiation of reinforcement corrosion. Rio and Turriziani'?
observed that the chloride penetration depth was about
twice as muchas that for S04--. This is consistent with the
diffusivity data of Barnes and Roy11 who found in
salt-containing mixtures (containing fly sh and/or slag)
consistently lower diffusion rates by a factor of 2 to 5 for SO,-
than Na’ and other cations. Based on an extensive literature
review, Oberholster” reported that the diffusion of chloride is
generally 10 to 100 times faster than that of sulphates. The
greater penetration of chlorides compared to sulphates was
also observed by Stratful13, who indicated that concrete
retained 14 times more chlorides than sulphates.
The effect of sulphate concentration on reinforcement
corrosion in sulphate-chloride environments is plotted in
Figure 10. As shown in this figure, the corrosion activity
increases with the concentration of sulphate ions
associated with chloride salts.
6 Construction and Building Materials 1995 Volume 9 Number
Construction 2
and Building Materials 1995 Volume 9 Number 2
Electrochemical behaviour of steel: N. R. Jarrah et al.
This trend is in line with the earlier results on the effect of
sulphate-chloride environments on reinforcement corrosion in
paste specimens made with Type I cement4.
A comparison of corrosion rate data, Figure IO, with that on
time to initiation of corrosion (Table 2) indicates that while
sulphate ions do not contribute to the initiation of
reinforcement corrosion, their presence at the steel-concrete
interface, once corrosion is initiated, increases the corrosion
activity. This increase in the corrosion activity due to the
conjoint presence of chloride and sulphate salts as compared
to that due to the presence of only chloride ions may be
attributed to the decrease in the electrical resistivity which aids
in the flow of the corrosion current from the anodic to the
cathodic site and vice versa.
The superior performance of blended cements, particularly
silica fume blended cement, over plain cements in sulphate,
chloride and sulphate-chloride environments, indicates the
technologica1 benefits that can be accrued due to their use. The
higher time to initiation of reinforcement corrosion in blended
cements, particularly in silica fume cement concrete
specimens, may be attributed to the dense and impermeable
structure of these cements compared to plain cements. Mineral
admixtures react with calcium hydroxide (CH) liberated by
the hydration of the tricalcium silicate (C,S) and dicalcium
silicate (C,S) in the Portland cement forming secondary
calcium silicate hydrate14J5. The secondary C-S-H phase,
although less dense than the primary C-S- H formed in the
plain cements, nevertheless effectively fills up the large
voids in the hydrated Portland- pozzolan cement
concretes. Li and Roy16 indicated that the diffusion of
aggressive agents, chloride ions in particular, is affected
not only by the pore structure of the materials but also by
the diffusion mechanism. According to them, a reduction
in chloride transport rate also occurs dueto the change in
chemical composi- tion beyond that caused by physical
factors. It is assumed that because of the pozzolanic reaction
a significant amount of gel is produced during hydration
in the pozzolanic materials; the critical point is that the
gel-type hydrates are located to block the pores instead
of just forming a layer on the solid pore surfaces. The
6
 Electrochemical behaviour of steel: N. R. Jarrah et al.
lower amount of Ca(OH)i in the pozzolanic cement
pastes, and their higher silica and alumina contents, are of
benefit for these kinds of cementitious materials to
minimize the penetration of chloride ions. Further, the
pore channels in these cements have a high tortuosity
compared to plain cement pastes. Also, the chloride ions
may be inhibited by interaction of these secondary hydrates
formed, by the pozzolanic reactions, with other ions
as they pass through these channels.
The dense pore structure of blended cements also
impedes the flow of moisture and oxygen to the
steel--concrete interface, thereby retarding the anodic
reaction. Moreover, the electrical resistivity of blended
cements being higher than that ofplain cements17,
propagation of corrosion current will be hampered in
these cements compared to plain cements. The lower
corrosion activity in blended cements as compared to
plain cements may be attributed to these factors, namely
the dense microstructure, lower oxygen and moisture
diffusion as well as increased electrical resistivity.
Conclusions
The corrosion potential-time curves for steel in
plain and blended cement concrete specimens placed
in a pure sulphate environment, for about two years,
indicated passivity.
2 The data on time to initiation of corrosion did not
indicate a clear and systematic trend on the role of
sulphate ions in corrosion activation.
3 The potentiodynamic curves for steel in plain and
blended cements generally indicated uniform
corrosion in all exposure conditions. These plots
indicated active corrosion in plain cements
compared to blended cements.
4 Increasing the sulphate concentration from O to
2.1% in 15.7% chloride solution increased the
corrosion current density. This trend was observed
in both plain and blended cement concrete specimens.
5 The increase in corrosion activity associated with
increasing sulphate concentration may be attributed
to the decrease in the electrical resistivity of concrete
due to the presence of sulphate ions.
6 The superior performance of blended cements,
particularly silica fume blended cement, in both the
chloride and sulphate-chloride environments, is
attributable to the dense pore structure which
inhibits the diffusion of chloride, oxygen and
moisture to the steel-concrete interface. The lower
corro- sion rates in these cements are also
attributable to the higher electrical resistivity of these
cements than in the plain cements. The higher
electrical resistivity impedes the flow of electrons
from the anodic to the cathodic sites, thus retarding
the propagation of the corrosion process.
7 Construction and Building Materials 1995 Volume 9 Number
Construction
and Building Materials 1995 Volume 9 Number 2
Electrochemical behaviour of steel: N. R. Jarrah et al.
7 The longer time to initiation of reinforcement
corrosion and lower corrosion rate observed in the
silica fume cement concrete exposed to chloride and/or
sulphate environments reflects its usefulness in
enhancing the useful-service life of reinforced
concrete structures. Commented [cco23]: El tiempo más largo para el inicio
de la corrosión de refuerzo y la menor tasa de corrosión
observada en el concreto de cemento de humo de sílice
Acknowledgements expuesto a ambientes de cloruro y / o sulfato refleja su
utilidad para mejorar la vida útil del servicio de las
The authors wish to acknowledge the Research Institute estructuras de concreto reforzado.
and the Department of Civil Engineering, King Fahd
University of Petroleum and Minerals for support of
this research.
References
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15 Feldman, R.F. Pore structure formation during hydration of fly
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16 Li, S. and Roy, D.M. Investigation of relations between poros- con humo de sílice, en los ambientes de cloruro y cloruro de
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17 Gjorv, O.E. Durability of concrete containing condensed silica hormigón de acero. Las menores tasas de corrosión en estos
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mayor resistencia eléctrica impide el flujo de electrones
desde los sitios anódicos a los sitios catódicos, lo que retrasa
la propagación del proceso de corrosión.
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