Construction and Building Materials, Vol. 9, No. 2, pp.

97-103, 1995
Copyright 0 1995 Elsevier Science Ltd
09504618(95)ooo02-x Printed in Great Britain. All rights reserved
09504618195 $10.00+0.00

Electrochemical behaviour of steel in plain and

blended cement concretes in sulphate and/or
chloride environments

Nezar R. Jarrah, Omar Saeed Baghabra Al-Amoudi, Mohammed Maslehuddin”,

Oluwatoyin A. Ashiru and Abdulaziz lbrahim Al-Mana

King Fahd University of Petroleum and Miner-a/s, Dhahran 31261, Saudi Arabia

Received 2 March 1994; revised 22 October 1994; accepted 21 November 1994

The electrochemical behaviour of reinforcing steel in plain and blended cement concrete speci-
mens placed in sulphate, chloride and sulphate-chloride environments was investigated. The effect
of cement composition and the exposure condition on the corrosion behaviour of reinforcing steel
was evaluated by measuring corrosion potentials at periodic intervals and conducting potentio-
dynamic 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 environ-
ment. The time to initiation of reinforcement corrosion, however, was higher in blended cements
than plain cements in all chloride and chloride-sulphate environments. The concomitant presence
of suphate and chloride salts did not significantly influence the time to corrosion initiation. The
corrosion rate, however, was significantly influenced by the quantum of sulphate ions associated
with the chloride salts. The superior performance of silica fume blended cement, in terms of longer
time to corrosion initiation and lower corrosion rate, indicates its potential in enhancing the useful
service life of reinforced concrete structures placed in the chloride-sulphate environments.

Keywords: electrochemical behaviour; steel; concrete

In reinforced concrete, steel provides the much needed
tensile property, while concrete essentially takes care of
the compressive stresses. Furthermore, concrete
provides both physical and chemical protection to the
reinforcing steel. The physical protection is provided by
its dense structure which retards the ingress of aggres-
sive species, such as oxygen, moisture and chloride ions
to the steel-concrete interface. The chemical protection
is provided by the high alkalinity of the pore solution
due to which a submicroscopically thin protective film
of y-ferric oxide is formed on the steel surface.
In spite of the inherent protection provided to the
steel by concrete, failures of concrete structures result-
ing from reinforcement corrosion are not uncommon.
The breakdown of the passive layer is attributed to two
principal factors, namely (i) reduction in the pH of the
surrounding concrete due to carbonation and (ii) pene-
tration of aggressive ions like chlorides to the
steel-concrete interface. Reinforcement corrosion due
to penetration of carbon dioxide may result in uniform
corrosion and is predominant in industrial areas. The
chloride-induced reinforcement corrosion is basically
attributed to chlorides which are introduced into the
*Correspondence to M. Maslehuddin, KFUPM Box 442, Dhahran
31261, Saudi Arabia
concrete through an accelerator, contaminated aggre-
gates and/or mixing water. Alternatively, they may
penetrate the hardened concrete from the external envi-
ronment. Deterioration of reinforced concrete bridge
decks due to the use of de-icer salts in the temperate
climates of the US and Europe is well documented.
Corrosion of reinforcement due to chloride salts is also
a predominant durability problem in the coastal areas
of the Arabian Gulf.
The marine structures, both on-shore and off-shore,
however, are subjected to both chloride-induced rein-
forcement corrosion and sulphate attack. The role of
sulphate ions, when chlorides and sulphates are
conjointly present, on corrosion of reinforcing steel is
often a point of controversy. Holden et al.’ indicated
that the concomitant presence of chlorides and
sulphates increases the risk of corrosion significantly.
Al-Tayyib et al.* reported a seven-fold increase in corro-
sion activity on mild steel exposed to sulphate-contain-
ing calcium hydroxide solutions over those containing
chloride salts. Cheng et ~1.~ investigated the effects of
chloride and sulphate ions on the electrochemical prop-
erties of reinforcing steel using an AC impedance tech-
nique. Their results indicated that the presence of
sulphate ions could modify the surface characteristics of
reinforcing steel. Studies conducted by Al-Amoudi and

Construction and Building Materials 1995 Volume 9 Number 2 97

Electrochemical behaviour of steel: N. R. Jarrah et al.

Table 1 Chemical composition of cements and blending materials imens were covered with wet burlap for 24 h prior to
Constituent (wt. %) Fly Blast furnace Silica Type V Type I demoulding.
ash slag cement fume cement cement Test solutions. After demoulding, the specimens were
cured in potable water for a further period of 14 days
Silicon dioxide 52.3 27.7 92.5 22.0 20.5
Aluminium oxide 25.2 12.8 0.4 4.1 5.6 and then placed in the four test solutions. The compo-
Ferric oxide 4.6 1.2 0.4 4.2 3.8 sition of the test solutions is detailed below:
Calcium oxide 10.0 44.0 0.5 64.1 64.4
Magnesium oxide 2.2 8.8 0.9 2.2 2.1
Sulphur trioxide 0.6 3.1 0.5 2.0 2.1 Solution 1: 15.7% Cll (pure chloride environment)
Loss on ignition 0.4 0.9 2.6 0.8 0.7 Solution 2: 2.1% SO, - (pure sulphate environment)
Potassium oxide 0.3 0.3 Solution 3: 0.55% SO, -+ 15.7% Cl- (low sulphate-
Sodium oxide 0.2 0.2
54.6 56.7 chloride environment)
C,S
c,s 21.9 16.1 Solution 4: 2.1% SO, + 15.7% Cll (high sulphate-
_ _ 3.5 8.5
CA chloride environment)
C,AF 12.9 11.6

Test solutions 3 and 4 represent the concentration of

Maslehuddin4 showed that reinforcement corrosion
increases due to the conjoint presence of chloride and
sulphate salts as compared to those exposed to chloride
salts.
While the studies cited above provide an indication of
the role of sulphate ions on reinforcement corrosion,
there is a need to investigate the electrochemical behav-
iour of steel in concrete, particularly in blended cements
which are commonly used these days to utilize the tech-
nological benefits accrued from their use.
This investigation was carried out to study the effect
of chloride and/or sulphate ions on the electrochemical
behaviour of steel in plain and blended cement
concretes. Two types of plain cements, namely ASTM C
150 Type V (C,A: 3.5%) and Type I (C,A: 8.5%) were
used. The blended cements investigated utilized replace-
ments of fly ash, silica fume and blast furnace slag.
Materials and techniques
Materials
The fly ash blended cement contained 20% fly ash, used
as a replacement of cement, while silica fume blended
cement contained 10% silica fume. The blast furnace
slag cement concrete specimens contained 60% granu-
lated blast furnace slag and 40% Type I cement. A
cementitious material content of 350 kg/m3 and water to
cementitious material ratio of 0.5 were kept invariant in
all the concrete mixes. The coarse aggregate was 19 mm
maximum size crushed limestone, of bulk specific
gravity 2.42 and average absorption of 3.77%. A coarse
to fine aggregate ratio of 1.6 by weight was kept invari-
ant in all concrete mixes. Table I shows the chemical
composition of the cements and blending materials used
in this investigation.
Techniques
Reinforced concrete specimens. Concrete cylinders, 75
X 150 mm with a centrally embedded 12 mm 0 rein-
forcing bar, were used. The bars were cleaned thor-
oughly using silicon carbide paper and degreased before
casting. They were also coated with epoxy coating at
the concrete-air interface and the embedded end to
eliminate the crevice effect. The concrete ingredients
were mixed in a revolving mixer. After casting, the spec-
chloride and sulphate ions commonly found in the
coastal and continental sabkha brines in the Arabian
Gulf, respectively5. Test solutions 1 and 2 represent the
maximum chloride and sulphate concentrations in these
solutions.
Sodium chloride was used to provide the chloride
ions, while sodium sulphate and magnesium sulphate
were used to provide the sulphate ions. The latter two
salts were proportioned to provide 50% of the sulphate
concentration from each of them. The specimens were
partially immersed in the solution contained in glass
fibre tanks. These tanks were covered with polyethylene
sheets to minimize evaporation and the concentration
was adjusted each month.
Reinforcement corrosion. The reinforcement corrosion
was monitored by measuring the corrosion potentials at
regular intervals using a high impedance voltmeter and
recording the potentials with respect to a saturated
calomel electrode (SCE).
The electrochemical behaviour of steel in the concrete
specimens was evaluated by conducting potentio-
dynamic scans after about two and half years of expo-
sure to the four test environments. A microprocessor-
based potentiostatigalvanostat was used for polarizing
the steel. A stainless steel frame placed outside the
specimen was used as a counter electrode, while a satur-
ated calomel electrode was used as a reference electrode.
Figure 1 is a schematic representation of the test set-up.
A scan rate of 0.2 mVls was used. A positive feedback
technique was used to compensate for the Ohmic drop
(IR) between the reference electrode and the reinforc-
ing bar.
Results
Corrosion potentials
The corrosion potentials of steel in concrete specimens
made with plain and blended cements and exposed to
the four test environments are plotted against time of
exposure in Figures 2 to 5. Each point in these figures is
an average of three readings taken on triplicate speci-
mens representing similar concrete constituents and
exposure conditions. These corrosion potential-time
curves were used to evaluate the time to initiation of
corrosion based on the ASTM C 876 criterion of -350

98 Construction and Building Materials 1995 Volume 9 Number 2

 Electrochemical behaviour of steel: N. R. Jarrah et al.

: 0.55% !504 +
15.70% Cl

.o
0
;TIC ANK

Threshold Potential

I I I I
01 I I
b75mm_I &AL, BRIDGE 0 100 200 300 LOO 500 600 ‘0
Period of Immersion, Days
Figure 1 Schematic representation of the electrochemical test set-up
Figure 3 Corrosion potentials on steel in plain and blended cement
concrete specimens exposed to a low sulphate-chloride environment
- + - Type 1 Cement
900 - - -z- - Type Y Cement
900 - --+--Type I Cement
- -O- - Flv Ash Cement
......Q--... 5l1ca Fume Cement
- -%-Type Y Cement Test Environment :15.7% Cl
-+-- Blast Slag Cement @ 800 - + -Fly Ash Cement
-.,.-.o.--..- Stka Fume Cement
‘” 700
<
1 600
G_
6 500
z
a 100

o~_~
2
‘: 300
5

2 200
a ,_. .Ja”‘”
ET==-
100 ‘..&3_.~.__.~.Q 6
...... ...
-ww
T&t Enyironmen! : 2.1% ?I4 + 15.7;~ CL
1
0 100 200 300 400 500 600 700
0 I I I L I I
Period of Immersion. Days 0 100 200 300 400 500 600 100

Figure 2
Corrosion potentials on steel in plain and blended cement Period of Immersion, Days
concrete specimens exposed to a high sulphate-chloride environment
Figure 4 Corrosion potentials on steel in plain and blended cement
concrete specimens exposed to a pure chloride environment

mV CSE, i.e. -270 mV SCE. The corrosion initiation

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

Construction and Building Materials 1995 Volume 9 Number 2 99

Electrochemical behaviour of steel: N. R. Jarrah et al.

700 . 0 BOO
I-
Test Environment : 2.10% SO4
~~BFS
w 600 -4 0 600 TEST ENVIRONMENT 2.1% SO,+15 7% Cl
y FA
=:
> 500 - :;;
t *mu- rype I cement
+ Type V Cement -;I; )I:
SF -
- LOO - a- -Fly Ash Cement
0
:
: 81hra Fume Cement
m
A Blast Slag Cement
j$ 300 - Threshold Potential

TYPE I

0
0 600
0 100 200 300 100 500 600 700 800

Period of Immersion. Days

Figure 5 Corrosion potentials on steel in plain and blended cement

concrete specimens exposed to a pure sulphate environment

Table 2 Time to initiation of corrosion in plain and blended

cements Figure 6 Potentiodynamic plot for steel in plain and blended cement
concrete specimens exposed to a high sulphate-chloride environment
Time to reinforcement corrosion initiation (days) in
Cement Table 3 Electrochemical data for steel in plain and blended cement
Pure Low-sulphate High-sulphate Pure concrete specimens placed in a high sulphate-chloride environment
chloride chloride chloride sulphate
Cement type RP Corrosion rate
Type 1 175 108 162 Passive (kR.cm*) (mpy)
Type V 107 80 106 Passive
Fly ash 220 152 210 Passive Type 1 4.9 4.113
Silica fume 631 548 552 Passive Type V 4.4 5.632
Type I + fly ash 6.4 3.002
*Indicates passivity Type I + B.F. slag 17.1 1.367
Type I + silica fume 29.7 0.902

a trend similar to that observed in the two sulphate-

chloride environments. 0 800
BFS7
The corrosion potential-time curves for specimens o 6oo _ TEST ENVlRONMENT:0.55%SOL+15.7%CI
placed in the pure sulphate environment indicated no
corrosion initiation even after about two years of expo- 0 400 -
sure (Figure 5).
g 0 200 -
In summary, the data in Table 2 indicate that the -
performance, in terms of time to initiation of reinforce- ’ 0 000 -
ment corrosion, of silica fume cement concrete was <
significantly superior to fly ash and plain cement F -0 200 -
iz
concretes. However, the performance of fly ash cement
$ -0 400 I-
concrete was better than plain cements. In plain
cements, Type I cement performed better than Type V -0 600 -
cement in all chloride and chloride-sulphate environ-
-0 800 -
ments. Further, these data also indciated that sulphate
ions alone do not initiate reinforcement corrosion and 1 000 1R I I
_)
I
, c
10" 10' 10' 10' lo* 10' 106
that the time to initiation of reinforcement corrosion
CURRENT DENSITY, nA/cm'
was not significantly affected by the concentration of
the sulphate ions associated with chloride ions. Figure 7 Potentiodynamic plot for steel in plain and blended cement
concrete specimens exposed to a low sulphate-chloride environment
The potentiodynamic plots for steel embedded in
plain and blended cement concrete specimens exposed
to the high sulphate-chloride environment are shown in environment are shown in Table 3. These data indicate
Figure 6. The polarization current density was observed higher corrosion activity in plain cement concrete
to be higher in plain cements than in blended cements. specimens than that in blended cement concrete speci-
Higher corrosion activity was measured in Type V mens. Minimum corrosion activity, as measured by the
cement (C,A: 3.5%) than that in Type I cement (C,A: corrosion rate, was indicated in silica fume blended
8.5%). The potential-current curve for steel in silica cement concrete specimens followed by blast furnace
fume blended cement concrete specimens tended to be slag and fly ash blended cement concrete specimens.
more cathodic as compared to the corresponding curves The potentiodynamic plots for steel in concrete spec-
for other blended cement concrete specimens. imens placed in the low sulphate-chloride environment
The electrochemical data for steel in plain and are plotted in Figure 7. These curves indicated a trend
blended cements placed in the high sulphate-chloride similar to that in Figure 6. However, the following

100 Construction and Building Materials 1995 Volume 9 Number 2

 Electrochemical behaviour of steel: N. R. Jan-ah et al.

Table 4 Electrochemical data for steel in plain and blended cement Table 5 Electrochemical data for steel in plain and blended cement
concrete specimens placed in a low sulphate-chloride environment concrete specimens placed in a pure chloride environment

Cement type Corrosion rate Cement type Corrosion rate

(mpy) fmpy)

Type I 4.8 3.338 Type 1 14.3 1.612

Type V 3.5 5.032 Type V 12.1 1.738
Type I + fly ash 9.8 2.291 Type I + fly ash 12.6 1.533
Type I + B.F. slag 19.3 1.134 Type I + B.F. slag 32.1 0.759
Type I + silica fume 27.7 0.582 Type I + silica fume 62.7 0.338

0 800 0.800
I TEST ENVIRONMENT : 2.10% SO‘ , .TYPE P

0.600 -

0.400 -

\ I’
-0.600 - /
-._-..---a-~~._\_
_/”
-0.800
‘-A
-1000 I I 1 1 I
t ‘\
-1.000’ I
I I I t

100 10' 102 103 106 105 106 10° lo’ lo* lo3 104 10S 106
CURRENT DENSITY, “A/cm2 CURRENT DENSKY. nA/cm2
Figure 8 Potentiodynamic plot for steel in plain and blended cement Figure 9 Potentiodynamic plot for steel in plain and blended cement
concrete specimens exposed to a pure chloride environment concrete specimens exposed to a pure sulphate environment

at a potential of -50 mV SCE. Silica fume and fly ash

features differentiate the behaviour of reinforcing steel
placed in this solution from those placed in the high
sulphate-chloride environment:
(9 a passive region was indicated for steel in silica
fume cement concrete specimens, in the range of
-650 to -200 mV SCE;
(ii) 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
Tab&s 3 and 4 indicated higher corrosion activity in
specimens placed in the high sulphate-chloride environ-
ment than in specimens placed in the low 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
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 environ-
ment. 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 speci-
mens placed in this solution are presented in Table 6.
These data indicate 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.

Construction and Building Materials 1995 Volume 9 Number 2 101

Electrochemical behaviour of steel: N. R. Jarrah et al.
Table 6 Electrochemical data for steel in plain and blended cement
concrete specimens placed in a pure sulphate environment
Cement type Corrosion rate
(lcZm2) (mpy)
Type I 23.4 0.867
Type V 126.1 0.151
Type I + fly ash 131.6 0.183
Type I + B.F. slag 24.5 0.880
Type I + silica fume 224.6 0.065
Discussion
The time to initiation and propagation of reinforcement
corrosion are the two components of the service life
model presented by Tuutti’ and Brownes. The initiation
period represents the time for the diffusion of aggressive
substances through concrete to the steel-concrete inter-
face 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 corro-
sion, presented in Table 2, indicated a superior perfor-
mance 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 environ-
ment 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 initia-
tion 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 initia-
tion 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
dominate the initiation of reinforcement corrosion. Rio
and Turriziani’O observed that the chloride penetration
depth was about twice as much as that for SO,--. This is
consistent with the diffusivity data of Barnes and Roy”
who found in salt-containing mixtures (containing fly
ash 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 IO. As shown in this figure, the corrosion
activity increases with the concentration of sulphate
ions associated with chloride salts. This trend is in line
102 Construction and Building Materials 1995 Volume 9 Number 2
6,
0 0.02 0.04 0.06 0.08 0.1 0.12 0.11,
SULFATE / CHLORIDE RATIO
Figure 10 Effect of sulphate ion concentration on reinforcement
corrosion in sulphate-chloride environments
with the earlier results on the effect of sulphate-chloride
environments on reinforcement corrosion in paste speci-
mens made with Type I cement4.
A comparison of corrosion rate data, Figure IO, with
that on time to initiation of corrosion (Table 2) indi-
cates 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 chlo-
ride 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, partic-
ularly 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 rein-
forcement corrosion in blended cements, particularly in
silica fume cement concrete specimens, may be attrib-
uted to the dense and impermeable structure of these
cements compared to plain cements. Mineral admix-
tures react with calcium hydroxide (CH) liberated by
the hydration of the tricalcium silicate (C,S) and dical-
cium 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 Royi 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 due to 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
lower amount of Ca(OH), 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 of plain cementsr7, prop-
agation of corrosion current will be hampered in these
cements compared to plain cements. The lower corro-
sion activity in blended cements as compared to plain
cements may be attributed to these factors, namely the
dense microstructure, lower oxygen and moisture diffu-
sion 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.
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.
The potentiodynamic curves for steel in plain and
blended cements generally indicated uniform corro-
sion in all exposure conditions. These plots indicated
active corrosion in plain cements compared to
blended cements,
Increasing the sulphate concentration from 0 to
2.1% in 15.7% chloride solution increased the corro-
sion current density. This trend was observed in
both plain and blended cement concrete specimens.
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.
The superior performance of blended cements,
particularly silica fume blended cement, in both the
chloride and sulphate-chloride environments,
attributable to the dense pore structure which
inhibits the diffusion of chloride, oxygen and mois-
ture 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.
Construction and Building Materials 1995 Volume 9 Number 2
Nectrochemical behaviour of steel: N. R. Jarrah et al.
7 The longer time to initiation of reinforcement corro-
sion 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.
Acknowledgements
The authors wish to acknowledge the Research Institute
and the Department of Civil Engineering, King Fahd
University of Petroleum and Minerals for support of
this research.
References
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chlorides and sulfates on concrete durability. Corrosion of
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of Chemical Industry, London, 1983, pp 143-149
2 Al-Tayyib, A.J., Somuah, SK., Boah, J.K., Lublanc, P. and Al-
Mana, AI., Laboratory study on the effect of sulfate ions on
rebar corrosion. Cem. Concr. Res. 1988, 18(5), 774-782
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