Construction and Building Motrriuh Vol. 9. No.

3, 149-158, 1995
Copyright $ 1995 Elsewer Science Limited
Printed in Great Britam. All rights reserved
0950-0618195 $lO.OO+O.OO
0!So-O618(95)oooW-0
Performance of 15 reinforced concrete mixtures
in magnesium-sodium sulphate environments
Omar Saeed Baghabra Al-Amoudi
Department of Civil Engineering, King Fahd University of Petroleum and Minerals,
Dhahran 31261, Saudi Arabia
Received 30 August 7994; revised 18 November 1994; accepted 21 November 7994
A review of the literature indicates that research on the durability of reinforced concrete in sulphate-
rich environments has primarily been confined to studies on sulphate attack. Despite the small
number of reports on the effect of sulphate ions on corrosion of reinforcing steel in concrete, the
findings of these reports are controversial and inconclusive. Therefore, this investigation was
conducted to assess the performance of 15 reinforced concrete mixtures in a mixed magnesium-
sodium sulphate environment. These mixtures comprised a combination of three Portland
cements, three mineral admixtures and two water-to-binder ratios. Deterioration of concrete due to
sulphate attack and corrosion of reinforcing steel was evaluated by assessing the weight loss of
concrete and measuring corrosion potentials and polarization resistance at periodic intervals. The
results of this investigation indicated that plain cement concretes, irrespective of their &A content,
performed fairly well in terms of sulphate resistance; however, they failed to protect the rebars from
corrosion. Blended cement concretes, particularly those made with fly ash and blast-furnace slag,
exhibited an advanced degree of deterioration due to both sulphate attack and reinforcement corro-
sion. Despite its inferior performance in terms of sulphate resistance, silica fume cement concrete
displayed the best performance with regard to corrosion protection. A reduction in the water-to-
binder ratio was generally detrimental in terms of sulphate attack in plain and blended cement
concretes.
Keywords: durability; reinforced concrete; sulphate
Research on the durability of structural components in
sulphate-bearing environments has long been concerned
with deterioration of concrete due to sulphate attack.
Studies on this type of attack are normally conducted
by exposing cement paste, mortar or concrete specimens
to primarily sodium, magnesium and calcium sulphate
solutions*,. Due to the limited solubility of calcium
sulphate in water at normal temperatures (approxi-
mately 1400 mg/l SO, ), higher concentrations of
sulphate ions in groundwaters, therefore, are generally
due to the presence of magnesium sulphate and sodium
sulphate. When both of these salts are abundant, as is
the case in the arid, saline sabkha soils long the Arabian
Gulf coast4, the use of mixed sodium and magnesium
sulphate solutions to study the durability of hardened
concrete is recommendedi~~iO.
The mechanisms of sodium sulphate (NS) and
magnesium sulphate (MS) attack on hardened cement
pastes are summarized in the following reactions*-3:
CH + NS + 2H + CSH, + NH
CH + MS + 2H + CSH, + MH
C,AH,3 + 3CSH, + 14H + C,AS,H,, + CH
*C=CaO. N=Na20, M=MgO, f&SO,, S=SiO,, H=H,O
(1)
(2)
(3)
C,ASH,, + 2CSH, + 16H + C,AS,H,,
(4)
C,A + 3CSH, + 26H + C,AS,H,,
(5)
C&HZ + xMS + (3x + 0.5~ - z) H + xCSH,
+ xMH + O.SyS,H
(6)
4MH + SH, + M,SH,,, + (n - 4.5)H
(7)
In mixed sulphate environments, as in the present inves-
tigation, the mode of sulphate attack is predominantly
controlled by MS due to the generation of MH (brucite)
in Equation (2) above I3 MH, being insoluble (its solu- .
bility is 0.01 g/l compared to 1.37 g/l for CH) and its
saturated solution having a pH of about 10.5, causes
the destabilization of both ettringite (C,AS,H,,) and
calcium silicate hydrate (C-S-H)8,i4,5. Therefore the
formation of secondary ettringite is significantly
hindered in such environments. Accordingly, the mani-
festation of this type of sulphate attack is typically char-
acterized by a deterioration akin to eating away of the
hydrated cement paste and progressively reducing it to
a cohesionless granular mass leaving the aggregate
proud and exposed and associated with loss of
strengthi6J7. This type of sulphate attack is attributed
mainly to the formation of gypsum.
Construction and Building Materials 1995 Volume 9 Number 3 149
Performance of reinforced concrete mixtures: 0. S. 6. Al-Amoudi
Nowadays, there are many instances whereby rein-
forced concrete structures are being exposed directly to
sulphate-bearing soils and groundwaters. Such situa-
tions have brought attention to the role of sulphate ions
in the corrosion of reinforcing steel. There are a few
studies reporting the influence of sulphate ions on rein-
forcing steel in actual cement paste, mortar or concrete,
rather than exposing the rebars to saturated calcium
hydroxide solutions. Stratful* reported the individual
effect of both sodium sulphate and sodium chloride
solutions on reinforcement corrosion in concrete speci-
mens. He concluded that, within the test duration of
214 days, corrosion of reinforcing steel in concrete was
observed only in the concrete specimens placed in the
chloride solution and no corrosion was evidenced in the
specimens placed in the sodium sulphate environment.
An investigation carried out at King Fahd IJniversity of
Petroleum and Minerals (KFUPM) reported the effect
of sulphate ions, as well as the concomitant effect of
chlorides and sulphates, on steel embedded in cement
paste specimens for a period of about 500 days. Apart
from the role of sulphate ions in the chloride-induced
reinforcement corrosion, minimal corrosion was
observed in steel embedded in the specimens placed in
the pure sulphate solution. Another investigation
carried out at KFUPMZn on reinforced concrete speci-
mens prepared with different water-to-cement (w/c)
ratios and immersed in a 5% MgSO, solution indicated
that the sulphate ions were able to initiate reinforce-
ment corrosion within about 4.50 days of exposure. The
authors attributed such corrosion to the reduction in
the alkalinity of the hydrated cement paste surrounding
the rebars.
Table I Details of the concrete mixtures
Mix Cement Blending material
number
type (replacement)
I I
7
;
V
I Fly ash (20%)
4 I Silica fume (I 0%)
5 1 BFS (60%)
6 II
7 I
s V Fly ash (20%)
9 V Silica fume (IO/;,)
I 0 V
II I BFS (60%)
12 I Fly ash (20%)
13 V Fly ash (20%)
14 I Silica fume (IO%,)
15 V Silica fume (loo/)
Water-to-cementitious materials ratio
h Blast-furnace slag
w/cm
0.50
0.50
0.50
0.50
0.50
0.50
0.35
0.50
0.50
0.35
0.35
0.35
0.35
0.35
0.35
comprehensive investigation on the performance of
reinforced concrete made with 15 different concrete
mixtures in a mixed-sulphate environment. Such a
quantity of data may help in elucidating these contro-
versial issues. Furthermore, rational recommendations
for durable concrete mixtures to provide both corrosion
and sulphate resistance may be endorsed.
Experimental programme
Materials
The above review reveals that the influence of
sulphate ions on corrosion of reinforcing steel in
concrete is controversial and inconclusive. Furthermore,
the use of high quality concrete made with low w/c ratio
and incorporating mineral admixtures such as fly ash,
silica fume and blast-furnace slag are, at present,
increasingly used to improve the performance of
concrete. However, no data is available on the corro-
sion of rebars in such blended cement concretes when
exposed to sulphate-bearing environments. Therefore.
this research programme was conducted to assess the
performance of 15 reinforced concrete mixtures, which
comprised a combination of three Portland cements,
three blended cements and two water-to-cementitious
materials ratios, in a mixed-sulphate solution for 44
months. The details of the concrete mixtures used in
this investigation are presented in Table 1.
Significance of this research
Many publications have raised controversial points,
which were once accepted as facts, such as the role of
C A
1
Z5, cement content, water-to-cement (w/c) or to-
cementitious (w/cm) materials ratio2 ?x, and the role of
high profile pozzolonic materials, particularly of silica
fume and blast-furnace slag 5.7.y.12 14~2(1.2y ?I, on sulphate
attack. This paper, therefore, reports the results of a
Three ASTM C 150 Portland cements (Type I, Type II
and Type V) were used in preparing plain cement
concrete specimens ASTM C 6 18 Class F fly ash (FA)
was used as a 20% replacement by weight of Type
I/Type V cement to prepare FA blended cements. In the
silica fume (SF) cement concrete specimens, SF was
used as a 10% replacement by weight of Type I/Type V
cement. In addition, one blast-furnace slag (BFS)
cement, containing 60~ BFS and 40% Type I cement,
was also used. Table 2 shows the chemical composition
of the cements and blending materials. A cementitious
materials content of 356 kg m i (600 lb yd ) was used
in all concrete specimens. The coarse aggregate was 19
mm maximum size crushed limestone, of bulk specific
gravity 2.42, and absorption 3.77X, while the fine
aggregate was dune sand with a specific gravity of 2.64
and an absorption of 0.23%~ A coarse-to-fine aggregate
ratio of 2.0 by weight was kept invariant in all con-
crete mixtures. Two effective water-to-cementitious
materials (w/cm) ratios of 0.50 and 0.35 were used. In
the mixtures made with a w/cm of 0.35, a naphthalene
sulphonate-based superplasticizer was used at a dosage
of 2% by weight of cement.
Cusiing qfspecirnens
Concrete cylinders, 75 mm in diameter and 150 mm in
height, with a centrally embedded 12 mm diameter rein-
forcing bar, were used to study the effect of the mixed-
sulphate environment on the physico-chemical
150 Construction and Building Materials 1995 Volume 9 Number 3
Performance of reinforced concrete mixtures: 0. S. 8. Al-Amoudi
Table 2 Chemical composition of the cements and blending materials
Constituent
Fly
(wt. %I) ash
BSF Silica
Type V Type 11 Type f
fume cement cement cement
Silicon dioxide
Aluminium oxide
Ferric oxide
Calcium oxide
Magnesium oxide
Sulphur trioxide
Loss on ignition
Potassium oxide
Sodium oxide
C,S
C,S
C,A
C,AF
52.3 27.1 92.5 22.0
25.2 12.8 0.4 4.1
4.6 1.2 0.4 4.2
10.0 44.0 0.5 64.1
2.2 8.8 0.9 2.2
0.6 3.1 0.5 2.0
0.4 0.9 2.6 0.8
0.3
_
_ 0.2
54.6
_ 21.9
_ _
_ 3.5
12.9
21.3 20.5
5.5 5.6
5.2 3.8
63.2 64.4
I.0 2.1
2.5 2.1
0.8 0.7
0.3 0.3
0.2 0.2
43.5 56.1
28.3 16.1
5.8 8.5
15.8 11.6
characteristics of concrete and the electro-chemical
behaviour of its reinforcement. The steel bars were
coated with an epoxy paint at the concrete-air interface
and at their ends which were embedded in concrete to
prevent crevice corrosion. The reinforcing bars were
cleaned thoroughly using silicon carbide paper and
degreased before casting in concrete. The concrete
ingredients were mixed in a revolving mixer for about
four to five minutes. More time was given for the silica
fume cement concrete mixtures to ensure full dispersion.
After casting, the specimens were covered with wet
burlap for 24 h prior to demoulding. Thereafter, they
were cured in potable water for a further period of 14
days. The specimens were then air-dried for one day in
the laboratory (21 + 2C) and their initial weights ( Wi)
recorded, following which they were exposed to the test
solution.
Test solution
The concentration of the test solution was 2.1% SO, .
This SO, should not be confused with the 2.1%
MgSO, reported in the literature29,31, the SO,- used in
the latter two reports being only 1.7%. Sodium sulphate
and magnesium sulphate was used to provide the
sulphate ions. These two salts were proportioned to
provide 50% of the sulphate concentration from each of
them.
The specimens were immersed to their mid-height in
the test solution, which was periodically agitated gently
using a plastic water pump. The concentration of the
solution was adjusted on a monthly basis during the
first year and thereafter three to four times every year.
The solution was kept in a glass fibre tank and covered
with a polythene sheet to minimize evaporation.
Weight loss
The physical deterioration due to sulphate attack was
evaluated in terms of the reduction/increase in weight of
the reinforced concrete specimens after 7, 13, 21 and 44
months, At the scheduled time, the specimens were
retrieved, air-dried for one day in the laboratory envi-
ronment, cleaned and weighed. The weight loss of the
concrete materials (WL) was determined using the
following relationship
Construction and Building Materials 1995 Volume 9 Number 3
151
where Wi = average initial weight of three specimens (g)
and W, = average weight of three specimens after an
exposure period of t months (g).
Reinforcement corrosion
The corrosion in reinforcing steel was monitored by
measuring the corrosion potentials and polarization
resistance at regular intervals. The corrosion potentials
were measured using a high impedance voltmeter and
recording the potentials with respect to a saturated
calomel electrode (SCE). The linear polarization resis-
tance technique was used to measure the polarization
resistance (R,), which was determined by conducting a
linear polarization scan in the range of + 10 mV of the
corrosion potential. A microprocessor-based potentio-
stat/galvanostat was used for polarizing the steel. A
stainless steel frame placed outside the specimen was
used as a counter-electrode, while a saturated calomel
electrode was used as a reference electrode. Figure 1
shows the experimental set-up for the polarization resis-
tance measurements. A scan rate of 0.1 mV s-l was
used. A positive feedback technique was used to
compensate for the Ohmic drop (ZR) between the refer-
ence electrode and the reinforcing bar32,33.
Results
Concrete weight loss
The data on weight loss of the various concrete
mixtures exposed to the test solution is plotted against
the exposure period in Figure 2. These results exhibited
initially a marginally negative weight loss (Figure 2)
attributable to the filling up of the pores by the expan-
sive reaction products, thereby densifying the hardened
mortar matrix and increasing the weight and
strength2,34. Subsequently, the disruption of the
hydrated cementitious matrix by these expansive reac-
tion products resulted in a decrease in the weight of
specimens, thus increasing the weight loss.
Performance of reinforced concrete mixtures: 0. S. B. Al-Amoudi
' 25mnv pm_l
Figure 1 Schematic diagram for the set-up used to measure the polar-
ization resistance
The data in Figure 2(u) indicates that the weight loss
increased after 7 months for Mixes #4 and 5 (SF +
Type I cement and BFS cement at w/cm = 0.5, respec-
tively) and after 21 months for the other mixes. The
maximum weight loss of 37.4%, after 44 months of
exposure, was observed in Mix #5 (BFS cement at 0.5
w/cm) followed by a weight loss of 23.1% in Mix #3
(FA + Type I cement at w/cm = 0.5) and the minimum
weight loss (about 1%) was measured in both Mixes #l
and 2 (Type I and V cements at w/c = 0.5). For Mix #4,
the loss in weight was observed to fall midway at about
9%. Similarly, Figure 2(b) shows the weight loss in
Mixes #6 through #lo. This figure indicates that Mix
#9 (SF + Type V cement at w/cm = 0.5) exhibited the
maximum weight loss of 14.8%, followed by Mixes #8,
7 and 10. The minimum loss in weight of 3.1% was
observed in Mix #6 (Type II cement at w/c = 0.5). It is
to be noted that the values of weight loss in Figure 2(a)
were relatively more than those observed in Figure 2
(b). The data in Figure 2(c) indicates that the weight
loss in all concrete mixtures varied from 11 .O% to 18.5%
after an exposure period of 44 months. The weight loss
in Mix #ll (BFS cement at w/cm = 0.35), however,
exhibited a maximum weight loss of 44K
Corrosion potentids
The corrosion potentials on steel in the various concrete
specimens are presented in Figure 3. These potentiall
time curves were used to evaluate the time to initiation
of rebar corrosion based on the ASTM C 876 criterion
of -350 mV CSE (copper coppersulphate electrode)jj,
corresponding to -270 mV SCE (saturated calomel elec-
trode). Figure 3(a) indicates that the rebars embedded
in all concrete mixtures, except in Mix #5, exhibited less
negative potentials than the threshold -270 mV SCE.
Therefore, it can be concluded that the steel in these
concrete specimens was in a passive state during the
initial 450 days of immersion. In the case of Mix #5
(BFS cement at w/cm = 0.5) however, the corrosion
potentials of steel were more negative than the -270 mV
SCE, even before placement in the test solution, indi-
cating that the ASTM C 876 criterion is not applicable
-*iix#7 +Mix#jO
Figure 2 Results of the weight l oss of concrete materials: (a) Mixes
#I to 5: (b) Mixes #6 to IO: (c) Mixes #II to I5
for evaluating the corrosion of reinforcement in these
concrete specimens. Similar observations have been
reported in the literature for reinforcing steel in
concrete made with BFS blended cements and exposed
to chloride solutions3 38. The higher negative potentials
exhibited by steel in BFS cement concretes are attrib-
uted to the reducing agents in BFS (i.e. primarily the
soluble sulphides) which tend to impede the early
formation of oxidized passive layers on steel in high
BFS cement concrete$.
Similarly, Figures 3(b) and 3(c) show that the steel
in all the concrete mixtures, except in Mix #l 1, was in
a passive state during the 450 days of immersion. Mix
#11 exhibited a peculiar trend where the corrosion
potentials were initially less negative than the ASTM C
152 Construction and Building Materials 1995 Volume 9 Number 3
0 50 100 150 200 250 3im .m 4a 4m m
Period of Immersion, Days
0 50 1w 1s iw ml 300 xu 4w 4.50 xm
Period of Immersion, Days
m-.~.Mix#ll +Mix#14
I2 .
&~_,wo_ + Mix #12 + Mix #15
3
2x0 Threshold Potentid
0
Period of Immersion, Days
Figure 3 Potential-time records for the various reinforced concrete
mixtures: (a) Mixes #I to 5; (b) Mixes #6 to 10; (c) Mixes #I 1 to 15
876 threshold potential of -270 mV and increased
significantly after an exposure period of 277 days.
Polarization resistance
Quantitative information on reinforcement corrosion
was developed by determining the polarization resis-
tance using the linear polarization resistance technique
after 14, 18, 22 and 44 months of exposure to the test
solution. The data on polarization resistance on steel in
the various mixtures is presented in Figure 4. Figure
4(a) indicates that the polarization resistance (hereafter
abbreviated as RP) on steel in Mixes #l through 4 was
initially very high; being in the range of about 3500
to 4300 k!S cm*. Thereafter, a significant drop was
Performance of reinforced concrete mixtures: 0. S. B. Al-Amoudi
observed, attaining R, values of 56.7, 76.6, 24.1 and 844
kQ cm* after 44 months of exposure in Mixes #l, 2, 3
and 4, respectively In contrast, the R, was initially very
low in Mix #5 (BFS cement at 0.5 w/cm) compared
with the other mixtures. Its R, then decreased at a slow
rate, reaching 12.8 ka cm* after 44 months of exposure.
Likewise, the data in Figure 4(b) indicates a similar
trend whereby the initially very high values of R,
decreased sharply with an increase in the exposure
period. After 44 months, the R, values on steel in Mixes
#6 through #lO were 70.7, 696, 8.92, 30.5 and 386
kQ cm*, respectively. In the same direction, Figure 4(c)
reports the R, values on steel in Mixes #l 1 to 15, and
the same trend can be observed for Mixes #12 through
15. The R, values on steel in these concrete mixtures
were 27.4, 44.2, 162 and 327 kSJ cm*, respectively. The
steel in Mix #l 1 concrete specimens, however, exhibited
consistently very low R, values varying from 89.7 to
6.81 kR cm2 after 14 and 44 months of exposure,
respectively.
In summary, the R, results indicated that the steel
bars embedded in concrete Mixes #4, 7, 10, 15, and to
a lesser degree Mix #14, had relatively high R, values
after 44 months of exposure, compared with the other
concrete mixes.
Discussion of results
In order to compare the performance of the various
reinforced concrete mixtures in the magnesium-sodium
sulphate test solution after a relatively long-term expo-
sure period of 44 months, the data generated in this
investigation is summarized in Table 3. Discussion on
these results follows.
Sulphate deterioration and reinforcement corrosion
failure criteria
The long-term results in Table 3 showed a significant
variation in the performance of the 15 reinforced
concrete mixtures in terms of weight loss, corrosion
potential and polarization resistance. Therefore, three
failure criteria have to be set for each of the different
tests in order to compare the performance of the
various mixtures.
Sulphate attack failure criterion. As mentioned in
the introduction, concrete deterioration due to mag-
nesiurr-sodium sulphate solutions is typically manifested
by a progressive degradation leading to deterioration
and weight loss and is also associated with increased
softening and disintegration of the hardened cement
matrix, characterized by noncohesiveness and spalling
of the surfaces. Figure 5 presents visual documentation
of the physical condition of the various concrete
mixtures and depicts the mode and degree of deteriora-
tion after an exposure period of 44 months. These
features of binder decomposition akin to eating away of
the hydrated cement paste leaving the aggregates
exposed are best assessed by the weight loss of concrete
material (i.e. the strength reduction criterion is not
applicable for the type of specimens used in this investi-
Construction and Building Materials 1995 Volume 9 Number 3 153
Table 3 Summary of the durability performance of concrete mixtures
after a 44 month exposure to the mixed-sulphate environment
Performance of reinforced concrete mixtures: 0. S. B. Al-Amoudi
N mu
5
iii 4,u
7
* Mix #4 .D Mix #l
,,.
Do
G
q
. .
0 ...,.
\
+ Mix #5 + Mix #2
.., .
.., .
o . . . . + Mix #3
Mix
number
I
7
;
4
;
7
x
9
IO
II
I2
I?
14
I5
IO 15 20 25 XI 55 40 15 50
Exposure Period, Months
N $rm
___
E

$ 9
T
10 15 M
Expokre Piiod, Mkths
40 i5 5i
T
10 15 20
Expoke Piiod, Mkths
40 45 50
Figure 4 Polarization resistance-time records for the various rein-
forced concrete mixtures: (a) Mixes #I to 5; (b) Mixes #6 to IO:
(c) Mixes #I 1 to I5
gation while the length change criterion is not suitable
for this type of sulphate attack).
With regard to establishing a failure criterion based
on weight loss, Cohen and Mather have reported that
a loss of mass of 5% (for beams) and 2.5% (for cubes)
is to be adopted. In the present investigation, the 5%
loss in weight was accepted due to the cylindrical shape
and half-immersion of specimens as well as the duration
of exposure.
Reinforcement corrosion failure criteria. The elec-
trochemical characteristics of reinforcing steel in the
various concrete mixtures was evaluated by monitoring
both the corrosion potentials and resistance to polariza-
Concrete Corrosion Polarization
weight potential, SCE resistance
loss (%I) (-mV) (kR cm2)
0.86 395.1 56.7
23.1 0.93 681.1 331.1 24. 76.6 I
8.99 252. I 844
37.4 3.13 696.2 577.9 70.7 12.8
8.88 259.4 696
I I.6 670.7 8.92
14.8 652.2 30.5
4.72 188.5 386
44.0 669.4 6.81
18.5 713.0 27.4
I I.0 668.8 44.2
Il.6 503.3 162
15.5 350.8 327
Figure 5 Visual documentation for the various reinforced concrete
mixtures: (a) Mixes #I to 5: (b) Mixes #6 to IO: (c) Mixes #I I to I5
154 Construction and Building Materials 1995 Volume 9 Number 3
tion. It is worth mentioning that although the corrosion
potentials were not recorded after about 500 days of
exposure due to the minimal changes in their values
(Figure 2), the potentials were measured at the end of
exposure and their values are incorporated in Table 3.
Hence, the ASTM C 876 criterion35 can be used to indi-
cate whether the rebars were in an active state of corro-
sion or not.
The R, values can also be used to predict the time to
initiation of reinforcement corrosion for the embedded
rebars in the various mixtures via the use of the follow-
ing relationship:
Z
corr = B/R, (9)
where Z,,,, = corrosion current density @A cm-*), R, =
polarization resistance (kn cm*), B = @,*&)/[2.3(p, +
B,)] and p, and & = anodic and cathodic Tafel
constants, respectively.
In the absence of sufficient data on & and j3, for steel
in concrete, a value of B equal to 26 in the active state
of corrosion is frequently used32,38. Further, if the corro-
sion current density (Z,,,J is greater than 0.3 PA cm-
(corresponding to an R, value of 87 kL2 cm*), the rein-
forcing steel will certainly be in an active state, and if
Z,,rr is less than 0.1 ,uA cm-* (corresponding to an R,
value of 260 kL2 cm*), it is certainly passive38. It is there-
fore logical to set the polarization resistance value of
87 kR cm2 as a threshold value (i.e. failure criterion)
for corrosion activation.
Role of C,A content
It is interesting to observe that although there were
three types of ASTM C 150 Portland cements used in
this investigation, with a C,A content varying in the
range of 3.5 to 8.5% (Table I ), the results of weight loss,
corrosion potential and polarization resistance did not
vary significantly with the type of cement. In fact, the
highest weight loss was observed in Type II cement
(C,A = 5.8%) followed by Type V cement (C,A =
3.5%), which indicates that sulphate attack, at least for
the present solution and for the range of C,A content
used, is not totally or predominantly controlled by the
C,A content. This situation can also be visually
substantiated by the physical condition of the various
specimens, as documented in Figure 5. Many earlier
studies have clearly pointed to this fact, particularly
when cement paste and mortar specimens are exposed
to MgSO, dominated enviromnents4~3J4~22--26. Neville25
reported that the type of cement did not have any
significant effect due to exposure of concrete specimens
made with Type I (C,A = 9/s) and Type V cements in
both weak and saturated MgSO, solutions. He attrib-
uted such behaviour to the unusually low C,A of Type
I cement, which was only 1% above the allowable C,A
for Type II cement which is, by definition, moderately
sulphate resistant. Furthermore, according to Mehta4,
about 8% C,A is typically needed to consume the
gypsum that is invariably added to regulate the time of
set during the early hydration of cement. Consequently,
in Type I cement (8.5% C,A) used in the present inves-
tigation, only 0.5% C,A will be available to react with
sulphates, which is unlikely to cause extensive damage.
Kalousek et aLz3 indicated that their enormous quantity
of data confirms that limitations on C,A and C,AF
contents are not the ultimate answer to the problem of
sulphate attack. From another perspective, this situa-
tion may also be explained from the mechanisms
described previously (Equations (1) through (7)). Since
ettringite ceases to be a deteriorating parameter in
mixed-sulphate environments13, the role of C,A content
in sulphate attack (Equations (3) to (5)) will not be
effective. Accordingly, the sulphate attack in plain
cements will be initiated by Equations (1) and (2) and
will proceed directly to Equations (6) and (7). These
reactions (i.e. Equations (l), (2) and (6), (7)) do not
involve any aluminate phase in the deterioration mech-
anisms and, therefore, the ettringite formation will prac-
tically be inhibited. Consequently, the influence of C,A
content on the sulphate attack in mixed-sulphate envi-
ronments does not appear to be as crucial as it is, for
example, in Na,SO, environments.
It should also be mentioned that although all the
plain Portland cement concrete specimens were in an
excellent condition after 44 months of exposure and
were well below the 5% weight loss failure criterion,
their embedded reinforcing steel was in an active state
of corrosion (i.e. the corrosion potentials were more
negative than -270 mV and the R, values were less than
87 kR cm2, as shown in Table 3). This point will be
discussed later. Furthermore, both the corrosion poten-
tials and R, values also indicate that resistance to rein-
forcement corrosion in plain cement concrete mixtures
is not dependent on the C,A content (as it is for a chlor-
ide-bearing environment, for example).
Role of w/c ratio
The data in Figure 2 for the low and high water-to-
cement (w/c) ratio concrete mixtures made with plain
Portland (Type I and Type V) cements indicates that a
reduction in the w/c ratio enhanced the weight loss of
the concrete material for both types of plain cements.
Quantitatively, Mixes #l and 2 (both had w/c = 0.5)
had a weight loss of 0.86 and 0.93% after an exposure
period of 44 months compared with 8.88 and 4.72% for
the same cements (Mixes #7 and 10) prepared at a w/c
of 0.35, respectively. Thus, and contrary to the expected
belief, dense concrete mixtures aggravated the deterio-
ration process attributable to sulphate attack. Such a
phenomenon is also reported in the literature23~228~42.
Hughes2* reported that the susceptibility to sulphate
attack was not a simple function of water permeability.
This type of attack is not physical in nature, whereby a
dense, impermeable cement matrix may deteriorate less
than a porous, high w/c ratio cement. Similarly,
Kalousek et a1.23 stated that the actual effect of high
mixing water content (i.e. high w/c ratio) on sulphate
resistance is not clearly understood. The author*( has
recently observed that mortar specimens prepared with
Performance of reinforced concrete mixtures: 0. S. l3. Al-Amoudi
Construction and Building Materials 1995 Volume 9 Number 3 155
Performance of reinforced concrete mixtures: 0. S. 6. Al-Amoudi
Type I cement and exposed to a MgSO, environment
exhibited an increase in strength reduction following a
reduction of the wit ratio. When the same specimens
were placed in a Na,SO, environment prepared with the
same SO, concentration, the strength reduction
decreased with a decrease in the w/c ratio. Therefore, it
is very likely that the enhanced deterioration in the
MgSO, environment was attributed to the dense
microstructure in the low w/c ratio specimens which
provides less space for the sulphate reaction products to
occupy.
Despite the higher degree of sulphate deterioration in
low w/c ratio concrete mixtures, the low negative corro-
sion potentials and high R, values reveal that their
embedded reinforcing steel was still in a passive state
compared with those prepared at a higher w/c ratio of
0.5. This point will be discussed in a subsequent section.
in plain cement concrete specimens (Mixes # 1, 2 and 6)
leading to depassivation of steel. Conversely, the dense
microstructure of the SF cement concrete mixtures and
the beneficial effect of SF material on the cement
pasteeaggregate transition zone were successful in
inhibiting the diffusion of SO, to the steelconcrete
interface despite the aggravated MgSO, attack. It is
relevant to point out that the damaging effect of Mg
is only superficial.29.30,43 and their internal matrix was
so dense that the sulphate ions could not diffuse
through the concrete cover, hence preserving the
integrity of the internal matrix and the steel passivity.
Role of mineral admixtures
There is a concern nowadays regarding the fact that
blended cements, particularly those prepared with high
profile silica fume and blast-furnace slag materials,
deteriorate at a faster rate following exposure to a
magnesium-based sulphate environment, due to their
susceptibility to Mg-oriented attack9~..-? ..This is
also visualized in this investigation whereby the replace-
ment of Type I cement by FA, SF and BFS indicated an
increase in weight loss from 0.86% to 23.1, 8.99 and
37.4%, respectively. Similarly, the replacement of Type
V cement by FA and SF resulted in an increase in
weight loss from 0.93% to 11.6 and 14.8%, respectively.
It should be noted that although these blended cement
concrete mixtures (Mixes #3, 4, 5, 8 and 9) exhibited a
weight loss which was more than the 5% failure criter-
ion, the type of parent cement (Type 1 or Type V) did
not seem to play a significant role in the deterioration.
The dense microstructure of silica fume cement
concrete also increases the electrical resistivity of these
concrete mixtures, which impedes the flow of electrical
current from anodic to cathodic sites and also signifi-
cantly retards the availability of oxygen at the
steel-concrete interface3x. In the same context, this
interpretation may also explain the passive state of the
rebars in the low w/c ratio plain cement concrete speci-
mens (Mixes #7 and 10) compared to their counterparts
prepared at 0.5 w/c ratio (Mixes #l and 2).
The inferior performance of both FA and BFS
blended cement concrete mixtures (Mixes #3, 8 and 5,
respectively) in terms of corrosion resistance after 44
months could be attributed to the advanced stage of
deterioration at this period whereby a weight loss of
23.1%, 11.6% and 37.4% was recorded (Table 3). Such a
high degree of deterioration could not preserve the
integrity of the internal structure of these blended
cement concrete mixtures, thus enabling the SO, ions
to diffuse to the steel, leading to corrosion of reinforc-
ing steel.
The corrosion potential and polarization resistance
values (Table 3) point to the fact that the rebars in silica
fume concrete specimens (Mixes #4 and 9) exhibited
some discrepancy in their performance. While the steel
embedded in Mix #9 (SF + Type V cement at w/cm =
0.50) was observed to be in an active state of corrosion,
the reinforcing steel in Mix #4 (SF + Type 1 cement at
w/cm = 0.50) was in a passive state despite its advanced
stage of deterioration, which was well ahead of the
weight loss failure criterion. The inconsistency of the
corrosion test results of Mix #9, which could also be
verified from the results of Mixes #14 and 15, might be
attributed to some experimental errors and should not
therefore be considered as reliable. On the contrary, the
specimens made with plain Type I and Type V cement
concretes (Mixes #1 and 2, respectively) exhibited an
excellent resistance to sulphate attack, although their
rebars were in an active state of corrosion (i.e. their R,,
values were less than 87 k&J cmz and their corrosion
potentials were also more negative than -270 mV SCE
after 44 months). This might be attributed to the mech-
anisms of MgSO, attack as well as to the diffusion of
SO, ions. Within the 44 month duration, the sulphate
ions succeeded in reaching the steelconcrete interface
Svngergistic role of w/cm and blended materials
The incorporation of blending materials in cement
concrete mixtures with an attendant reduction in the
water-to-cementitious materials (w/cm) ratio is
presently the trend to produce high strength and high
performance concretes. Upon exposure to mixed-
sulphate environments, however, such denseness may be
detrimental. The results of the present investigation
indicate that decreasing the w/cm ratio of blended
cement concrete mixtures would enhance the sulphate
attack, as it did on plain Portland cement concrete
mixtures made with a w/c ratio of 0.35. Concrete
mixtures prepared with silica fume and both Type I and
Type V cements prepared at a w/cm ratio of 0.5 (Mixes
#4 and 9) had a weight loss of 8.99 and 14.8%, respec-
tively, which increased to 11.6 and 15.5% upon decreas-
ing the w/cm ratio to 0.35 (Mixes #14 and 15). Such an
increase in weight loss (1.7% on the average) could be
considered as marginal compared with that observed
previously with the reduction in w/c ratio for plain
cement concrete mixtures. On the contrary, fly ash
cement concrete mixtures made with a w/cm ratio of 0.5
(Mixes #3 and 8) indicated a weight loss of 23.1 and
11.6% which then mildly decreased to 18.5 and 11.0%
(Mixes #12 and 13) upon decreasing the w/cm ratio to
0.35. In the same way, the weight loss of BFS cement
156 Construction and Building Materials 1995 Volume 9 Number 3
Performance of reinforced concrete mixtures: 0. S. B. Al-Amoudi
concrete mixtures increased from 37.4 to 44.0% when
the w/cm ratio was decreased from 0.50 to 0.35.
Therefore, the role of water-to-cementitious materials
ratio was not very consistent, as it was for the plain
cement concretes. However, all the weight loss data for
the low w/cm ratio blended cement concrete mixtures
was more than the 5% failure criterion.
It should be noted that although Mixes #14 and 15
exhibited a significant weight loss of 11.6 and 15.5%,
respectively, which were much higher than the 5%
failure criterion, the rebars in these concrete specimens
were still in a passive state after 44 months of exposure
to the aggressive test solution as can be inferred from
the R, values, which were greater than the 87 kQ cm*
failure criterion (note that the higher negative potentials
for rebars in Mixes #14 and 15 were attributed to the
fact that one specimen exhibited a very high negative
potential and this was reflected on the average reading
for each of the three specimens). However, comparison
of the R, values of steel in Mixes #14 and 15 with that
in Mix #4 (SF + Type I cement at w/cm = 0.50) indi-
cates that reducing the w/cm ratio was associated with
a reduction in the R, values and hence provided less
resistance to reinforcement corrosion. This same trend
can generally be observed for FA and BFS blended
cement concrete mixtures. In summary, there was no
significant benefit associated with the reduction in
water-to-binder ratio for all blended cement concrete
mixtures in terms of either sulphate deterioration or
reinforcement corrosion.
Conclusions
The performance of 15 reinforced concrete mixtures in
an aggressive mixed-sulphate environment was evalu-
ated for an exposure period of 44 months. Based on the
data developed in this investigation, the following
conclusions can be drawn:
The three plain cements, with a C,A content varying
from 3.5% to 8.5%, exhibited an almost similar
performance in terms of both sulphate attack of
concrete and corrosion of reinforcing steel. Such
behaviour indicates that the sulphate attack and
reinforcement corrosion in concrete exposed to
MgSO,Na,SO, environments are not totally
controlled by the C,A content of the cement.
Blended cement concrete mixtures exhibited an
advanced stage of deterioration when compared to
plain cement concrete mixtures. Silica fume cement
concrete mixtures performed better than fly ash
cement concretes. The most inferior performance
was exhibited by blast-furnace slag cement
concretes.
Within the initial 500 days of monitoring, the corro-
sion potential-time curves for steel in all plain and
blended cement concrete specimens (Figure 3) indi-
cated passivity according to the ASTM C 876 criter-
ion. This might be attributed to the low diffusivity
of sulphate ions to the steel surface.
Despite the advanced stage of deterioration
observed in both the silica fume and low w/c ratio
plain cement concrete specimens, their dense
microstructures preserved the passivity of the
embedded reinforcing steel.
Reducing the water-to-binder ratio in plain and
blended cement concrete mixtures generally tended
to accentuate the sulphate attack in mixed-sulphate
environments. Further, their reinforcement corro-
sion resistance was not greatly improved with such a
reduction.
The use of silica fume concrete mixtures at a w/cm
ratio of 0.5 would be the rational approach to
protect reinforced concrete structural members
exposed to mixed-sulphate environments from rein-
forcement corrosion perspectives.
Recommendations
The results of the present investigation indicate that in
order to protect reinforced concrete substructures
placed in mixed-sulphate environments from both
sulphate attack and reinforcement corrosion, a rational
approach would be to use silica fume cement concrete
mixtures at a w/cm ratio of 0.5 in addition to the appli-
cation of a water-resistant epoxy-based coating on the
exterior members that are directly exposed to the
sulphate solution in order to protect such structures
from sulphate deterioration. In fact, such a recommen-
dation has recently been endorsed for reinforced
concrete substructures placed in high sulphate-chloride
sabkha environments44,45. This recommendation has
substantial applications for the construction industry in
Saudi Arabia as well as in the Arabian Gulf states,
where both sulphate and chloride ions are available in
high and variable concentrations along the coastal
plains, and where urbanization and industrialization
have been ongoing since the upsurge in oil prices of the
early 1970s.
Acknowledgement
The author would like to express his sincere gratitude to
the late Professor Rasheeduzzafar, who died on Friday,
November 4, 1994, for his unparalleled guidance during
the authors graduate studies at King Fahd University
of Petroleum and Minerals.
References
Al-Amoudi, 0. S. B. and Maslehuddin, M. Comments on rein-
forcement corrosion and sulfate attack in plain and blended
cement concretes exposed to mixed-sulfate environments. in
preparation
Guyot, R., Rant, R. and Varizat, A. Comparison of the resis-
tance to sulfate solutions and to sea water of different Portland
cements with and without secondary constituents. In Proc. ACI
SP-79, American Concrete Institute, Detroit, 1983, pp 453-569
Lawrence, C. D. Sulfate attack on concrete. Mug. Goner. Res.
1990, 42( 153), 249-264
Al-Amoudi, 0. S. B. Studies on soil-foundation interaction in the
Sabkha environment of Eastern Province of Saudi Arabia. PhD
Dissertation, Dept. of Civil Engg., King Fahd University of
Construction and Building Materials 1995 Volume 9 Number 3 157
Performance of reinforced concrete mixtures: 0. S. 6. Al-Amoudi
5
6
7
8
Y
IO
II
I2
13
14
15
16
17
18
19
20
21
22
23
24
25
Petroleum and Minerals, Dhahran, Saudi Arabia. I992
Standard Test Method for Length Change oj Hydraulic-Cement
Mortars Exposed to a Mi.ued Sodium and Magnesium Sulfite
Solution, American Society for Testing and Materials.
Philadelphia, ASTM C 1012-84, Vol. 4, No. 1, 1986, pp 617-621
Thorvaldson, T. Chemical aspects of the durability of cement
products. In Proc. 3rd International Symposium on the Chemistry
of Cement, London 1952, pp 436466
Kind, V. V. Some questions and problems in the field of corro-
sion of concrete used in hydrotechnical structures. In Proc.
Conference on Corrosion of Concrele. Moscow.*, 1953. English
Translation, I.P.S.T., Jerusalem. 1962. pp 31-38
Biczok, I. Concrete Corrosion, Concrete Protection. 8th edn.
Akademiai Kiado, Budapest, 1980
Mangat, P.S. and El Khatib, J. M. Influence of initial curing on
sulphate resistance of blended cement concrete. Cement Corur.
Res. 1992, 22(6) 1089-I 100
Rasheeduzzafar, Al-Mana. A. I., Haneef, M. and Maslehuddin.
M. Effect of cement replacement, content, and type on the dura-
bility performance of fly ash concrete in the Middle East.
Cemenl, Concr. Aggreg. 1986, 8(2), 8696
Mather, M. Field and laboratory studies of the sulphate resis-
tance of concrete. In Performance t/f Concrete, ed. Swenson, E.
G., University of Toronto Press, 1968. pp 6676
Cohen, M. D. and Bentur, A. Durability of Portland cement-
silica fume pastes in magnesium and sodium sulfate solutions.
ACI Mafer. J. 1988, 85 (3). 148-157
Rasheeduzzafar, Al-Amoudi, 0. S. B.. Abduljauwad, S. N. and
Maslehuddin, M. Magnesium-sodium sulfate attack in plain and
blended cements. ASCE J. Mater. Civ. Eng. 1994, 6(2), 201 222
Calleja, J. Durability. In Proc. 7th International Congress on
Chemistry of Cement, Editions Septima, Paris, Sub-Theme VII-2.
Vol. I, 1980, pp VII: 2/l-VII: 2148
Lea, F. M. The Chemistry of Cement and Concrete. 3rd edn.
Edward Arnold, London, 1970
Mehta, P. K. and Gjorv, 0. E. A new test for sulfate reistance of
cements. J. Test. Eva/. 1974, 2(6). 510 514
Rasheeduzzafar, Dakhil, F. H. and Al-Gahtani, A. S. The deter-
ioration of concrete structures in the environment of eastern
Saudi Arabia. Arab. J. Sci. Eng. 1982, 3(3), I91 -209
Stratful, R. F. Effect on reinforced concrete in sodium chloride
and sodium sulfate environments, Mater. Protwt. 1964. 3( 12).
7480
Al-Amoudi, 0. S. B. and Maslehuddin, M. The effect of chloride
and sulfate ions on reinforcement corrosion. Cement Comr. Res.
1993, 23(l), 139-146
Khan, M. S. and Al-Tayyib, A. J. Rebar corrosion in MgSO,
solution. ASCE J. Mater. Civ. Eng. 1992, 4(3), 292-299
Al-Amoudi, 0. S. B., Rasheeduzzafx, Maslehuddin, M. and
Abduijauwad, S. N. Influence of chloride ions on sulfate deterio-
ration in plain and blended cements. Msg. Concr. Res. 1994. 46
(167) 113-123
Rasheeduzzafar, Dakhil, F. H.. Al-Gahtani, A.S.. Al-Saadoun,
S.S. and Bader. M. A. Influence of cement composition on the
corrosion of reinforcement and sulfate resistance of concrete.
ACI Mater. J. 1990, 87(2), 114-122
Kalousek, G. L., Porter, L. C. and Benton, E. J. Concrete fog
long-time-service in sulfate environment. Cement Concr. Res
1972, 2 (1) 79989
Figg, J. W. Chemical attack on hardened concrete. effect ol
sulphates and chlorides. Bull. Inst. Corros. Sci. Twhnol. July
1979, 75, 12-23
Neville, A. Behaviour of concrete in saturated and weak solu-
tions of magnesium sulphate or calcium chloride. ASTM J.
Mater. 1969. 4(4), 78 I-8 I6
26
27
28
29
30
31
32
33
34
35
36
37
3x
39
40
41
42
43
44
45
Al-Amoudi, 0. S. B., Maslehuddin, M. and Saadi, M. M. Effect
of magnesium sulfate and sodium sulfate on the durability
performance of plain and blended cements. ACI Mater. J. 1995.
92(l), 15-24
Tikalsky, P. J. and Carrasquillo, R. L. Influence of fly ash on the
sulfate resistance of concrete. AU Mater. J. 1992, 89(l), 69-75
Hughes, D. C. Sulphate resistance of OPC, OPC/fly ash and
SRPC pastes: pore structure and permeability. Cement Concr.
Res. 1985. U(6), 1003-1012
Bonen, D. and Cohen, M. D.. Magnesium sulfate attack on
Portland cement paste I. Microstructural analysis. Cement
Concr. Res. 1992, 22(l), 16YY180
Lawrence, C. D. The influence of binder type on sulfate attack.
Cement Concr. Rex 1992, 22(6), 1047~1058
Bonen, D. A microstructural study of the effect produced by
magnesium sulfate on plain and silica fume-bearing Portland
cement mortars, Cement Concr. Res. 1993, 23(3), 541-553
Andrade, C., Castelo V., Alonso, C. and Gonzalez, J. A. The
determination of the corrosion rate of steel embedded in concrete
by the polarization resistance and AC impedance methods. In
Proc. ASTM STP 906. American Society for Testing and
Materials, Philadelphia, 1986, pp 43-63
Al-Amoudi. 0. S. B., Rasheeduzzafar, Maslehuddin, M. and
Abduljauwad, S. N. Influence of sulfate ions on chloride-induced
reinforcement corrosion in plain and blended cement concretes.
Cement, Concr. Aggreg. 1994, 16(l), 3- 1 I
Brown, P. W. An evaluation of the sulfate resistance of cements
in a controlled environment. Cement Concr. Res. 1981, 11,
719. 727
Standard Test Method for Half Ceil Potentials of tincoated
Reinforcing Steel in Concrete, ASTM C 876-87, American
Society for Testing and Materials, Philadelphia, Vol. 4.02,
Concrete and Mineral Aggregates, 1988, pp 420424
Arup, H. The mechanism of the protection of steel by concrete.
Corrosion of Reinforcement in Concrete Structures. ed. Crane, A.
P., Ellis Horwood, London, 1985, pp 15lll57
Maslehuddin, M., Al-Mana, A.I., Saricimen, H. and Shamim.
M. Corrosion of reinforcing steel in concrete containing slag or
pozzolan. Cement, Concr. Aggreg. 1990, 12(l), 24-31
Al Amoudi. 0. S. B. Durability of reinforced concrete in aggres-
sive sabkha environments. ACI Mater. J. in press
Macphee. D. E. and Cao, H. T. Theoretical description of blast
furnace slag (BFS) on steel passivation in concrete. Mag. Comr.
Rex 1993, 45( 162) 63-69
Cohen, M. D. and Mather, B. Sulfate attack on concrete
research needs. ACI Mater. J. 1991, 88(l), 62269
Mehta, P. K. Effect of cement composition on corrosion of rein-
forcing steel in concrete. In Proc. ASTM STP 629, American
Society for Testing and Materials, Philadelphia, 1977, pp 12~ I9
Al-Amoudi, 0. S. B., Maslehuddin, M. and Abdul-Al, Y. A. B.
Role of chloride ions on expansion and strength reduction in
plain and blended cements in sulfate environments. .f. Cbnstr.
Build. Mater. 1994, 8(3). in press
Gollop. R. S. and Taylor, H. F. W. Microstructural and
microanlytical studies of sulfate attack. I. Ordinary Portland
cement paste. Cement Cow. Res. 1992, 22(6), 1027-103X
Al-Amoudi. 0. S. B., Maslehuddin, M.. Rasheeduzzafar and
Abduljauwad, S. N. Durability considerations for construction of
substructures in sabkha environments. In Proc. 4th International
Ctmferenw on Structural Failure, Durabilit_) and Retrofitting,
Singapore, July IY93. pp 280-287
Al-Amoudi, 0. S. B. A review of the geotechnical and construc-
tion problems in sabkha environments and methods of treatment.
Arab. J. Sci.. in press
158 Construction and Building Materials 1995 Volume 9 Number 3