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37

Effects of mix composition on the sulfate

resistance of blended cements
A. E. AL-Salami and, A. Salem

Abstract Modern construction requires advanced concretes,

which have high strength, cost effectiveness and durability. The
influence of sodium sulfate solutions on the physical properties of
neat and blended cement has been investigated. The ordinary
Portland cement was replaced by 35% ground granulated blast
furnace slag (GGBS). The cement pastes were mixed using
water/cement ratios 0.25. The hardened cement paste samples
were immersed in sodium sulfate solutions having different
concentrations between 0 and 1.5 %, for 3, 14 and 28 days. The
results showed that, the increase of sulfate ions leads to increase
in the porosity, the relative mass loss and the relative expansion.
Also show a decrease in the bulk density and the chemical
combined water. The critical variations in these parameters
occur at a concentration 0.5%.

Index Term

Blended cement paste, combined water,

Relative mass loss, sodium sulfate, Relative expansion.

I.
INTRODUCTION
Cement is an economical and durable material that is one of
the worlds most utilized man-made building products.
Cement is utilized for its good compressive strength and
stiffness but the major drawback is that it lacks tensile
strength.
External sulfate attack is one of the durability problems
associated with concrete. Since its identification it has been
the subject of numerous studies and still not totally understood
[1]. The extent to which concrete is affected by sulfates
depends on several factors including its permeability, water to
cement (w/c) ratio, type of cement, exposure conditions and
the environment [2]. Assuming the same environmental
conditions, two factors will tend to control the resistance of a
given concrete to sulfate attack: the chemistry of the cement
and the permeability of the concrete. To control the cement
chemistry, American Standards [3] suggest a limit on the
(C3A) and (2C3A + C4AF) contents of sulfate resistant, type V,
cements as 5% and 25%, respectively. On the other hand,
cements with low C3A and C4AF compounds generally tend to
have a higher C3S/C2S ratio, and an increase in the C3S
content of cement generates a significantly higher amount of
calcium hydroxide, as the hydration of C3S produces nearly
2.2 times more calcium hydroxide (CH) than the hydration of
C2S. Calcium hydroxide is known to be responsible for the
formation of gypsum, and gypsum is known to be the first step

of the formation of ettringite, which can be considered as the

principal cause of deterioration [4]. Low C3A and low C3S
cement showed 10 times less expansion than those with a low
C3A and a high C3S content [5]. Furthermore, to control the
permeability of concrete, lower w/c ratio and/or pozzolans are
recommended [6,7]. Effect of various pozzolans on the
resistance of cements to external sulfate attack has also been
studied by other researchers [810]. Pozzolans reduce not only
the permeability but also the C3A amount if they are a partial
replacement of cement. Moreover, use of pozzolans or use of
blended cements, in general, reduces the quantity of CH due to
the pozzolanic reactions which would otherwise react with
sulfates to form gypsum.
The present work examines the effects of slag and curing time
on corrosion resistance (sulfate attack) and durability of OPC
mortars, through the improvement of the physical properties of
cementbased materials due to their pozzolanic properties.
II.
EXPERIMENTAL WORK
The starting materials used in this study were ground
granulated blast furnace slag (GGBS) of Blaine surface area
3000 cm2/g and ordinary Portland cement of Blaine surface
area 3100 cm2/g, The oxide composition of OPC and GGBS
were shown in Table I.
The blended cement pastes were prepared using ordinary
Portland cement that was partially substituted by 35% ground
granulated blast furnace slag (GGBS) by weight of cement.
The ingredients were homogenized on a roller in a porcelain
ball mill with four balls for 1 hour to assure complete
homogeneity. The pastes were prepared using the
water/cement ratios 0.25. The pastes were molded into 2 cm
cubes. The moulds were vibrated for one minute to remove
any air bubbles. The samples were kept in moulds at 100%
relative humidity for 24 hours, and then it cured under water
for 3, 14 and 28 days. The hardened cement pastes were dried
at a temperature of 105oC for 24 hours in an oven. Then, they
were kept in sodium sulfate solution of concentration 0, 5000,
10000 and 15000 ppm for 3, 14 and 28 days. Each
measurement of the physical properties was carried out for
three identical cubes of the same mix composition.
Porosity and bulk density of each cube sample are measured
according to ASTM C140-01 [11]. The procedures are as
follows:

E. AL-Salami, is the head of physics department, Faculty of Science King

Kaled University, Abha, SA (e-mail: aeslami@kku.edu.sa).
A. Salem

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Table I
Chemical analysis of the starting materials

Constituents
CaO
SiO2
Al2O3
Fe2O3
MgO
SO3
Na2O
K2O
ClI.L.

OPC
(%)
62.56
20.85
4.70
3.86
1.23
2.79
0.49
0.12
--2.82

GGBS
(%)
33.76
38.60
13.20
3.53
5.36
0.55
1.33
0.66
0.07
2.94

Immerse the specimens in water at room temperature (22 oC)

for 24 h. Weigh the specimens while suspended by a thin wire
and completely submerged in water and record W i (immersed
weight). Remove the specimens from water and allow water to
drain for 1 min by placing them on a wire mesh, removing
visible surface water with a damp cloth; weigh and record as
Ws (saturated weight). Then, dry all specimens in a ventilated
oven at 105 oC for not less than 24 h and two successive
weightings at intervals of 2 h show an increment of loss not
greater than 0.2% of the last previously determined weight of
the specimen. Record the weight of dried specimens as W d
(oven-dry weight).

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(1-a,b). In general, the bulk density increases gradually with

increasing, the hydration age of the cement pastes. This is due
to the decrease in the total porosity with increasing hydration
age as a result of the filling of pores by the hydration products.
The results of figure (1-a) indicate that the bulk density of the
hardened cement pastes increases at concentration 5000 ppm
of Na2 SO4, then decreases gradually with increasing of Na2
SO4. The increase of bulk density at 5000 ppm is due to
formation of ettringite and gypsum. Therefore the samples
with higher C3S content that decreases bulk density, the
sulfate attack may have involved a complex mechanism of
ettringite expansion, gypsum formation, and decalcification of
the C-S-H. Obviously, the bulk density of blended cement
pastes containing 35% slag increases as the concentration of
sodium sulfate increases. This is mainly due to decrease of the
amount of clinker and then the C3A (tray calcium aluminates)
which produce sulphoaluminate as a results of C3A and
Na2SO4 reaction. This is leading to increase the bulk density
with the concentration of Na2SO4 in the samples as illustrated
in figure (1-b). The increase of the bulk density is mainly due
to the activation of blended cement with sulfate ions in the
samples forming hydrated products which fill some open
pores in the samples [12-14].

The absorption and oven-dry density are calculated as

Absorption% = [(Ws - Wd)/Wd] x 100;
Density (kg/m3) = [ (Wd/(Ws - Wi) x 1000
Where Wi, Ws, Wd are in kg
loss of weight (Lw )
Lw=(Wd-Ig)/Wd x100
Where Ig is the ignited weight at any temperature level (g).
Combined water (Wn)
Wn= [Wd-W'/W'] - L
Where W' : is the ignited weight of specimen (g) for one hour
at 10000c, then caold in a dissicator then weighted.
L ; is the ignition loss of un hydrated specimen, an is equal to
(W'-W10000C).

III.

RESULTS AND DISCUSSION

The physical properties of cement pastes subjected to different

concentration of Na2SO4 were studied to clarify its physical
performance affected during sodium sulfate expunger.
The results of bulk density of the hardened cement pastes,
which exposed to a different concentration of Na2SO4 in
absence and presence of slag are graphically illustrated in fig

Fig. (1-a,b). Variation of the bulk density of the hardened cement pastes
versus Na2 SO4 concentration f at different curing ages; (a) without slag; (b)
with 35% slag

Figures (2-a,b) shows the variation in the mass loss verses the
concentration of Na2 SO4 at different curing ages . It is clear
that the rate of mass loss increases with increasing the curing
age due to the precipitation of hydrated phases in to the
available pores of cement pastes. But in fig.(2-a) the rate of
the of mass loss increases with the concentration of Na2SO4 in
the samples, and that is related to the increase and formation
of gypsum and ettringite which are produced by the chemical

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reaction of sulfate salt with CH and C3A. The rate of

formation of gypsum and ettringite plays an important role in
the increase of mass loss, where the gypsum results makes the
samples softening and brittle as well as the hydration product
of the (C-S-H) phase converts to gypsum ,and this leads to
mass loss. In fig (2-b) the rate of the mass loss decreases with
increasing of Na2SO4 in the samples, that is due to the slag
reacts with the liberated lime from the hydration of clinker,
hence, the free lime is nearly consumed. So there is no chance
to reaction of lime with sulfate group, and that is leading to
decreasing in the formation of gypsum, which is responsible to
increasing the mass of the samples [15,16].

Fig. (3a,b). The variation of the total porosity as a function of the different
concentration of Na2SO4 in the cement pastes at different curing age (a)
without slag, (b) with 35% slag.

The increase in the total porosity values of hardened

blended cement pastes after the concentration 5000 ppm is
related to the increase of gypsum and other products which
increase the total porosity with the concentration of Na 2SO4 in
the samples. The variation of the total porosity in fig(3-b) is
decreasing with increasing of Na2SO4 in the specimens. That
is due to the formation of mush amounts of (C-S-H) [reaction
of slag with CH, also the content of slag in the opc matrix to
decrease the interaction of the liberated lime (C-H) with the
sulfate group SO42- to form gypsum, which is increase the
total porosity.
Fig. (2-a,b). Variation of the mass loss of the hardened cement pastes with the
Na2SO4 concentration at different curing ages: (a) without slag;(b) with 35%
slag.

The total porosity of the blended cement pastes cured for 3,14
and 28 days are graphically represented as a function of the
concentration of Na2SO4 in the samples in fig(3-a,b). It is clear
that the total porosity decreases with curing time for all
hardened cement pastes. This is due to the filling up of a part
of the available pore volume with the hydration products, as
the hydration proceeds. In fig (3-a) the total porosity
decreasing up 5000 ppm , then increasing with the
concentration of Na2SO4 in the samples. This variation mainly
depending on the rate of the geometrical random arrangement
of the material hydrated phases during the hydration
mechanism inside the matrix of the sample [17].

The relative expansion of the blended cement pastes as a

function in the concentration of the Na2SO4 and at different
curing time were represent in fig(4-a,b). The general behavior
of the relative expansion is decreasing with increasing the
curing time duo to the precipitation of hydrated phases into the
pores of the system, and that is leading to decreasing in the
relative expansion of the samples.
In fig (4-a) the relative expansion increasing with increase the
concentration of Na2SO4 in the sample, and that is attributed to
the chemical interaction of the sulfate group with the C3A,
producing the ettringite formation, and this reaction depending
on the concentration of Na2SO4 in cement paste.
The ettringite formation results in expansion of the material
and that are related to the water absorption of crystalline
ettringite, the morphology and size of the ettringite crystal.
But in fig(4-b) the relative expansion decreasing with
increasing Na2SO4 in the samples after the concentration
5000( ppm), and that is due to the random arrangement of the

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hydrated phases in the cement matrix. The decreasing in the
relative expansion with Na2SO4 is mainly duo to the increase
of the slag hydration, in the cement matrix, and that is leading
to decrease the contents of C3A in the cement clinker, and
decrease the rate of formation the ettringite interaction of C 3A
with Na2SO4.

40

hydrated lime (CH) and traycalcium aluminate (C3A) in the

cement paste, result in the formation of gypsum and ettringite
(has a large specific volume), which causes undesirable effects
on the physico-mechanical properties, that may produce
failure of the cement paste. The present of the pozzolanic
material (slag) in the cement matrix can be improved the
physico-mechanical properties by reducing the (CH) phase
C3A content in ordinary Portland cement, and producing the
(C-S-H) hydrate phase.

Fig. (4-a,b). The variation of the relative expansion of the hardened cement
pastes versus the concentration of Na2SO4 at different curing age (a) without
slag (b) with 35% slag

The results of the chemically combined water contents (water

represents that part of water retained by the cement paste after
the free water has been removed it has been determined as a
measure of the degree of hydration for the blended cement
pastes hydrated for 3,7 and 28 days, are graphically
represented as a function in the concentration of Na2SO4 in
fig(5-a,b). In general in this figure (5-a,b) the chemical
combined water increases with the curing time, and that is
related to the increase of formation of the hydration phases
with curing time, that is leading to increase the combined
water inside the samples [18-20].
In fig(5-a) the combined water decreasing with increasing the
concentration of Na2SO4 in the samples. that is attributed to
the interaction of sulfate group with hydrated phases CH and
(C-S-H) and producing un hydrated phases [ gypsum and
ettringite ], that is leading to decrease in the combined water
inside the matrix. But in fig (5-b) it is clear that the combined
water content of the blended cement pastes increase with the
Na2SO4. This is duo to high pozzolanic activity of slag with
the limestone (C-H) during the hydration mechanism, forming
additional amounts of calcium silicate hydrates (C-S-H).
There fore, the combined water tends to increase [21]. Finally
the reactions between the sulphate group SO42- and the

Fig. (5-a,b). The variation of the combined water contents in the blended
cement pastes with the concentration of Na2SO4 at different curing age (a)
with out slag (b) with 35% slag

IV. CONCLUSIONS
The results are summarized as follows.
1- When cement paste phases are exposed to sodium
sulfate gypsum and ettringite are produced depending
on the concentration of sodium sulfate in the sample,
by chemical reaction of sulfate with Ca(OH)2 and
C3A.
2- The formation of gypsum plays an important role in
the decrease in the balk density and mass loss and
combined water, where the gypsum results makes the
specimen material brittle and softening.
3- Ettringite formation results in cracking and expansion
of the material and this expansion leads to a increase
in the total porosity and the relative expansion of the
cement matrix, and that is related to the water
absorption of crystalline ettringite , the morphology
and size of the ettringite crystal .

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4- The physico- mechanical are affected by the present

of sulfate solt in cement paste, and that is leads to
decrease the durability of cement paste.
5- The variation in the physicomechanical properties
occurs at the concentration 5000 ppm can be
regarded as a geometrical random arrangement of
material phases in the samples.
6- The pozzolanic addition (slag) to the blended cement
past improved the durability of the physicomechanical properties and corrosion inhibitor. This is
because the interaction the active pozzolanic material
(slag) with the free lime (CH) during the hydration
mechanism leading to form the (C-S-H) phases, and
consequently decreasing the formation rate of
gypsum and ettringite [interaction of So42- with CH].

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