Construction and Building Materials 71 (2014) 579588

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Construction and Building Materials

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Durability of limestone mortars based on quaternary binders subjected

to sulfuric acid using dryingimmersion cycles
Z. Makhlou a,, T. Bouziani a, M. Hadjoudja b, M. Bederina a
a
b

Laboratory SREML, University of Laghouat, P.O. Box 37G, Laghouat 03000, Algeria
Laboratory LRGC University of Laghouat, P.O. Box 37G, Laghouat 03000, Algeria

h i g h l i g h t s
 The quaternary binders has a positive effect vis-a-vis the durability of limestone mortars.
 The limestone ller, blast furnace slag and natural pozzolana in limestone mortars has a benec effect.
 The performances of the limestone mortars with additions are better than that of the control mortar in sulfuric acid.
 The weight loss, strength loss and pH are the quantication parameters of durability.
 Seven dryingimmersion and heatingcooling cycles accelerate the attack of mortars.

a r t i c l e

i n f o

Article history:
Received 9 April 2014
Received in revised form 21 August 2014
Accepted 27 August 2014
Available online 23 September 2014
Keywords:
Crushed limestone sand
Limestone ller
Blast furnace slag
Natural pozzolana quaternary binders
Dryingimmersion and heatingcooling
cycles
Sulfuric acid
Weight loss
Compressive strength loss
pH

a b s t r a c t
The aim of this work is to produce limestone mortars with blended-cement by substituting partially the
clinker by three mineral additions. Namely; the limestone ller, the blast furnace slag and the natural
pozzolana combined simultaneously to the cement for rates of 30%, 10% and 10% by turn. The mortar
specimens were immersed in sulfuric acid solutions, and subjected to two protocols of attack. The rst
is slow; it is a continuous immersion. Specimens are exposed to 3% solution of sulfuric acid at
23 1 C. The second protocol is accelerated, and consists to subject the mortar samples to 7 drying
immersion and heatingcooling cycles, followed by a continuous immersion up to 180 days. The drying
is done at 60 C and the exposure in lime water and 5% sulfuric acid solution at 23 1 C. In this study the
quantication parameters of durability of mortars are the weight loss and the compressive strength loss.
The follow-up (the monitoring) of pH of the exposure solutions was carried out until end of the tests. The
synergistic action of the quaternary binders has a positive effect vis-a-vis the durability of limestone mortars immersed in sulfuric acid solution and the performances of the limestone mortars with quaternary
binders are better than that of the control mortar.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Over the past two decades, the use of mineral admixtures as
partial substituent of Portland cement in concrete has become very
popular because of their technological, economic, and environmental advantages. The use of mineral additions such as limestone llers, blast furnace slag and natural pozzolana improves the
resistance of concrete to the attack of aggressive agents (sulfuric
acid), because they reduce the presence of calcium hydroxide,
which is the most vulnerable component to acid attacks [13].
The cements standards allow only the introduction of small
quantities (less than 5%) of secondary components, in cements. Sev Corresponding author.
E-mail address: z_makhlou@yahoo.fr (Z. Makhlou).
http://dx.doi.org/10.1016/j.conbuildmat.2014.08.086
0950-0618/ 2014 Elsevier Ltd. All rights reserved.

eral studies have shown that, the presence of ller and aggregate
limestones in the cementitious material increases its resistance to
the sulfuric acid attacks [4,5]. The slag has several advantages in
the manufacture of cement. First, it has a relatively constant chemical composition compared to y ash, silica fume, natural pozzolana
etc. In addition, it has other advantages such as, low heat of hydration, resistance to acids and sulfates, better workability, and higher
ultimate strength, [68]. The highest resistance to a solution of 0.5%
of sulfuric acid was achieved by a binary mixture of binder comprising more, than 60% of granulated blast furnace slag [9]. However,
Chang et al. have reported, recently, that binary binders of concrete
prepared with 60% slag and ternary binders prepared with 56% of
slag and 7% of silica fume had a lower yield (performance) than a
mixture of 100% of Portland cement, when it is immersed in a solution of 1% of sulfuric acid at a pH of 1.27 [4].

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Z. Makhlou et al. / Construction and Building Materials 71 (2014) 579588

The natural pozzolana has been widely used as a substituent of

the Portland cement in the concretes. In addition to its environmental and economic benets, this also includes the decrease of
permeability, the increase of chemical resistance and the improving of the properties of the fresh concrete [1012]. The resistance
of mortars, with cement partially replaced by natural pozzolana,
was improved to attacks of the sulfuric and hydrochloric acids, sulfate and penetration of chloride ions [13]. The natural pozzolana
may further be used to improve the resistance of mortars and concretes to the hydrochloric acid and the limestone ller may be used
to improve the resistance to sulfuric acid [5].
It has also been shown that the use of mineral additions such as
silica fume and y ash in the concrete improves the resistance of
the concrete to the attack of sulfuric acid because of the reduction
of hydroxide calcium, which is the product the most vulnerable to
acid attack [14,15].
The application of immersiondrying cycles, the increase of the
temperature and concentration of the solution have accelerated
the degradation kinetics of cementitious materials by aggressive
solutions [1618]. The dryingimmersion cycles play an important
role in accelerating the degradation of materials exposed to aggressive environments. The U.S. Bureau of Reclamation has followed for
twenty years the dimensional changes of concrete cylinders separately subjected to dryingimmersion cycles and continuous
immersion. The results show that one year of the alternate immersion is equivalent to eight years of continuous immersion [19,20].
The main objective of this research is to achieve information
about the effect of the simultaneous incorporation of limestone ller, blast furnace slag and natural pozzolana in partial replacement
to the Portland cement on the resistance of mortars, containing
crushed limestone sand, to a solution of sulfuric acid attack. Mortar
samples were immersed in 5% sulfuric acid solution and subjected
to two protocols of degradation, one is accelerated and the second
is slow.

The sand/cement ratio is equal to 3 and the water/cement ratio is 0.50. Specimens 4  4  16 cm3 were molded and maintained for 24 h inside the molds and
during 28 days, after release from the mold, in lime saturated water.
Fig. 1 shows the mineralogical composition of the limestone ller of the sand,
determined by SEM where it is noted that the main component of the nes is CaCO3
in the form of calcite and Fig. 2 shows the mineralogical composition determined by
XRD.
Five mortars containing limestone aggregates have been made. The compositions of different binders are given in Table 3. The different compositions with
exposure environments are presented in Table 4.

3. Experimental methods
After the pre-curing for 28 days under lime water, the mortar specimens were
subjected to two protocols of degradation. The rst is a slow attack or simple degradation; it is a continuous immersion, where the mortar specimens were continuously cured in two solutions, lime water (reference exposure) and 3% sulfuric acid
(H2SO4) solution at an ordinary temperature of 23 1 C. The exposure solutions
have been changed every month. The second protocol is an accelerated attack or
accelerated degradation, where the mortar samples are subjected to dryingimmersion and heatingcooling cycles (Fig. 3a). Namely, seven dryingimmersion cycles,
each cycle lasts six days, three days of drying at 60 C in oven followed by an
immersion for three days at 23 1 C in two different environments, lime water
and 5% sulfuric acid solution (Fig. 3b). For both protocols, slow and accelerated
attacks, lime water is used as reference medium. For dryingimmersion cycles,
the exposure solutions were renewed after each dryingimmersion cycle and after
every 30 days for the continuous immersion. The different compositions of binders
and curing environments are summarized in Table 3.
The compressive strength was determined according to the European Standard
EN196-1 [23] on specimens 40  40  160 mm3. For the slow attack, compressive
strength was determined after 28 days in lime water then 30, 60, 90, 120, and
180 days of immersion in both curing solutions, after 28 days of conservation in
lime water.
For the accelerated attack, tests were carried out after 28 days of immersion in
lime water, and then at the end of 2nd, 5th, 7th cycles of dryingimmersion and at
60, 90, 120 and 180 days in both curing solutions, after 28 days of conservation in
lime water.

4. Results
4.1. Weight changes

2. Materials used
The Chemical and mineralogical compositions of different compounds of
cement, limestone, slag and natural pozzolana used in this research are presented
in Table 1. The densities of the four components are 3, 2.7, 2.8 and 2.6 consecutively. The clinker and mineral admixtures were ground separately in a laboratory
ball mill to a Blaine neness of 3500 100 cm2/g for clinker and 3800 100 cm2/g
for the mineral admixtures. The mortars were prepared from these binders, according to the European Standard EN196-1.
The sand used in this study is a crushed limestone. The grains present angular
shapes. Its granulometry presents a continuous particle size distribution with a
maximum grain diameter of approximately 2.5 mm but the proportion of grains,
which is smaller than 0.08 mm, is below 9%. It should be noted that this proportion
of ne grains remains acceptable [21].
Table 2 lists the set of physical properties of sand. The neness modulus is 2.30.
The high value of the sand equivalent which is 76.46, which are measured according to NF P 18-598 standard [22], show that the crushed sand used is clean, with
low percentage of ne clay. It remains above the limit value recommended for concrete and mortar. It is therefore an ideal for use in ordinary concrete.
Table 1
Chemical and mineralogical compositions of different compounds.
Composition

Cement

Limestone

Slag

Pozzolana

SiO2
Al2O3
Fe2O3
CaO
MgO
K2O
Na2O
SO3
Cl
LOI

21.38
5.59
3.21
65.26
1.72
0.47
0.19
0.56
0.02
0.58

0.76
0.41
0.23
54.9
0.61
0.24
0.04
0.61
0.005
36.3

39.38
5.64
2.3
40.3
4.50
0.46
0.13
0.90

0.8

57.10
15.82
6.16
5.95
2.09
2.0
1.1
0.28
1.40
1.2

Mineralogical cement
(%)

C2S
15.64

C3S
60.97

C3A
9.39

C4AF
9.76

Some authors consider the weight loss as an acceptable indicator for evaluating the resistance of concrete to the attack by sulfuric acid [24]. The weight change of mortar samples immersed in
sulfuric acid solution during the protocol of accelerated degradation is shown in Figs. 46. From Fig. 4, it is found that during the
dryingimmersion cycles there is a prominent decrease of weight
of the mortars up to the 7th cycle. Beyond the 7th cycle there is
a pronounced increase in weight concerning all mortars, especially
mortars with mineral additions up to the 60th day, followed by
stabilization or a slight decrease for mortars with mineral additions, less important than that of control mortars F0 until the
120th day. Beyond this age, the weight loss is most signicant.
However, the weight loss of control mortars F0 is very obvious.
The pronouncing increase of weight after immersiondrying cycles
up to the 60th day may be due to the absorption of solution by
materials.

Table 2
Physical properties of sands used.
Physical characteristics

Values

Specic density (g/cm3)

Apparent density (g/cm3)
Compactness (%)
Porosity (%)
Fineness modulus
Visual sand equivalent (%)
Piston sand equivalent (%)
Absorption coefcient (%)

2.7
1.53
56.7
43.3
2.30
71.34
76.46
4.3

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Z. Makhlou et al. / Construction and Building Materials 71 (2014) 579588

(a) Visualization of fillers grains by SEM

(G=5000)

(b) S.E.M. of crushed limestone sand

G=36.

Fig. 1. Crushed sand and ller limestone used.

Ca

Ca

Ca
D

Ca : Calcite
D : Dolomite
Q : Quarts

Ca

Ca

Ca

Ca
Ca
Ca
Ca
Ca
Q

Fig. 2. Diffractogram of X-ray of the ne crushed limestone.

Table 3
Composition of binders.
Composition (%)

Clinker
Gypsum
Limestone
Slag
Pozzolana

95
5
0
0
0

47.5
2.5
30
10
10

47.5
2.5
10
30
10

47.5
2.5
10
10
30

47.5
2.5
16.67
16.67
16.67

Table 4
Different compositions and exposure environments.
Exposure environments

A: Lime water
F: Sulfuric acid solution

Compositions
0

A0
F0

A1
F1

A2
F2

A3
F3

A4
F4

Comparing the weight gain of mortars in both environments

(Fig. 5), it was noted that in the lime water all mortars have had
a gain of weight, and mortars A2, with 30% slag have more weight
gain than other mortars, and mortars A2 and A3 have the higher
weight gain than mortars A1. whereas, in sulfuric acid solution,
control mortars F0 show a gain loss higher than that of mortars
with mineral admixtures F1, F2, F3 and F4. The rate of weight loss
of mortars F0 is 6%, while mortars F2, F3, F4 and F1 is 0.4%, 0.8%,
1.1% and 1.2% successively.
The richness of interstitial solution in silicates and Ca2+ ions
allows the development of pozzolanic reaction that continue to

use silicates for to produce CSH, that are less leachable than
the portlandite. However, the weigh decrease of mortars F0 without mineral additions is remarkable, which are rich in portlandite,
this is due to the fact that the maximum hydration reaction was
completed. These mortars do not contain enough silicates for to
develop CSH to produce pozzolanic reaction and therefore, the
amount of these CSH will be limited.
The weight gain of mortars with mineral additions during the
period of 75 and 120 days in sulfuric acid solution can be attributed to the continued hydration of cement and pozzolanic reaction,
as well as the action caused by sulfate ions (SO
4 ) leading to the formation of gypsum and ettringite. This weight gain can be also
attributed to the increased water absorption of mortar samples.
The weight loss, after 120135 days may be due to the dissolution
caused by the latecomer action of hydrogen ions caused by action
of sulfate ions [25], and erosive action of acid on the outer surface
of mortar samples. It was noticed, the deposit of altered products
at the background of the conservation tanks, especially for mortars
F0. However, the formation of gypsum and ettringite may rst lead
to a weight gain and nally a loss of the latter caused by expansion
causing cracking [2]. Fig. 6 shows the comparison of weight change
of mortars in sulfuric acid solution in the two degradation protocols, slow and accelerated attacks, at 180 days. During slow attack,
a weight gain for all mortars has been registered. The highest rate
concerns mortars F3 and the most important mainly concerns mortar F0. With respect to the protocol of accelerated attack, there is a
weight loss of all mortars. Mortars F0 are most affected by weight
loss, while the least affected are mortars F2. The acceleration of
attack by dryingimmersion and heatingcooling cycles and

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Z. Makhlou et al. / Construction and Building Materials 71 (2014) 579588

0 days
A

42 days
28 days 0 days
Procedure of slow aack: Simple degradaon
LW
LW
Connuous immersion

LW

Procedure of accelerated aack: accelerated degradaon

LW 7 cycles D-Im.
Connuous immersion

LW

Acide

180 days
Time

Procedure of slow aack: Simple degradaon

LW

Connuous immersion

Procedure of accelerated aack: accelerated degradaon

Acide 7 cycles D-Im.
Connuous immersion

(a) Detail of the two procedures of conservation (Dryingimmersion and heating-cooling) and for the two environments (lime water (LW)
and sulfuric acid).
Dr 7 cycles of 6 days (drying-immersion)
yi
ng
Im
me
rsi
on
Im
me
rsi
on

1 cycle of connuous immersion of 138 days

Time

180 days of aack

b: Procedure of accelerated attack: accelerated degradation
1 cycle of connuous immersion of 180 days
a: Procedure of slow attack: Simple degradation

(b) Details of Procedure of slow and accelerated attack.

Fig. 3. Different process and environments used.

Fig. 4. Weight changes of mortars after immersion in sulfuric acid solution during
the accelerated attack.

increasing concentration of sulfuric acid solutions, therefore has a

clear effect on the weight loss of mortar samples.
4.2. Development of the compressive strengths
In Fig. 7 were grouped the compressive strength values at
28 days of mortar samples stored in lime water after demolding.
The test results of compressive strength of mortars, stored in two
environments were presented in Table 5.
The compressive strength according to immersion time of all
mortars stored in both environments increases continuously over
time. At all ages, the strength of mortars with mineral additions
is less than those of the control mortar.
From Fig. 7, the higher compressive strength is that of slag, followed by that of natural pozzolana and nally that of limestone l-

Fig. 5. Weight changes of mortars in both media, at 180 days after accelerated
attack.

ler. The pozzolanicity of mineral additions affects the rate of

hydration. The low long-term strength of limestone ller can be
attributed mainly to its low reactivity. The addition of limestone
as a partial substituent of cement has a higher strength at shortterm. The opposite effect is approved by slag and pozzolana. It
should be noted that according to time factor, the strength of mortars with mineral additions, especially mortars F2, gets closer that
the control mortars. At long-term, the cements with pozzolanic
materials have a compressive strength, which is signicantly
higher than that of Portland cement and Portland limestone
cement [2628]. In acid solution, mortars F2 with 30% slag present
the best strength followed by mortars F3 with 30% pozzolana and
mortars F4 with 16, 6% of each addition and nally mortar F1 with
30% limestone.

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Z. Makhlou et al. / Construction and Building Materials 71 (2014) 579588

pozzolana with released lime to form additional CSH that contribute to the development of compressive strength of limestone
mortar.

4.3. Relative compressive strength

Fig. 6. Weight changes of mortars immersed in sulfuric acid solutions, for both
types of damages to 180 days.

Fig. 7. Compressive strength of mortars kept in lime water for 28 days.

At long-term, the strength of mortars with blended-cement

especially, mortar F3 is similar to that of control mortars, whereas
that of mortars F2 exceeds that of control mortar. During drying
immersion cycles, there is a rapid decrease of strength, while during continuous immersion after the dryingimmersion cycles; a
slight decrease of strength was noted, up to 180 days. The control
mortar is the rst to undergo the decrease of strength at 28 days.
The increase of strength during the immersiondrying cycles can
be attributed to two types of reactions; a continuous hydration
of unhydrated cement components in order to form hydration
products, in addition to the reaction of silicates of slag and

Figs. 8 and 9 show the development of compressive strength of

mortars in both environments, relative to the compressive strength
of mortars preserved in lime water during 28 days.
These results show that the incorporation of mineral additions
leads to a gain or a loss of strength, which the percentage differs
from a mortar to another according to the substitution rate and
the exposure medium. In this case of degradation (attack) procedure, the loss of strength becomes more pronouncing for the control mortar. However, in lime water mortars A2 and A3 have a
signicant strength gain, which can reach 57%, followed by mortars
A1 and A4 comes in the last place the control mortar with 17% of
strength gain.
This explains why the binders of mortars with mineral additions continue to develop their pozzolanic reaction in lime water.
On the contrary, in the sulfuric acid solution, during the drying
immersion cycles, there is an increase of rate in strength gain of
mortars with mineral additions at the second cycle (12 days), especially for mortars F1, F2 and F3, which their rates are prominent.
Beyond the second cycle, there is a fall of strength gain of mortars
with mineral additions until the end of these cycles. Beyond these
cycles, the fall becomes lighter for all mortars. As for, the mortars
F0 and F4, a continuous decrease was noted up to 180 days. During
the dryingimmersion cycles, the fall was accentuated. After the
cycles, the decrease becomes less pronounced. The rate of strength
loss of mortars F1, F2 and F3 is lesser than those mortars F0 and F4.
This explains why the binders with mineral additions continue to
develop their pozzolanic reaction in lime water. By cons, in the sulfuric acid solution, during the dryingimmersion cycles, there is an
increase in the rate of strength gain of mortars with mineral additions up to the second cycle (12 days), especially for mortars F1, F2
and F3, which their rates are pronounced. Beyond the second cycle,
there is a decrease of strength gain of mortars with mineral additions up to the end of these cycles. Beyond these cycles, the fall
becomes lighter for all mortars. As for, the mortars F0 and F4 a continuous decrease was noted until 180 days. During the drying
immersion cycles, the fall was accentuated after the cycles, the
decrease becomes less pronounced. The rate of strength loss of
mortars F1, F2 and F3 is lower than those of mortars F0 and F4.
The rate of loss of strength is 17%, 18% and 21% for mortars F1,
F2 and F3 successively, and 49% and 37% for the mortars F0 and F1.
It should be noted that when comparing the rate of change of
compressive strength of mortars exposed in both environments

Table 5
Compressive strengths (MPa).
Slow attack: Continuous immersion
Time (days)

A0
F0
A1
F1
A2
F2
A3
F3
A4
F4

28 days in limewater

30 days

60 days

90 days

120 days

180 days

43.52
43.52
21.66
21.66
30.48
30.48
25.25
25.25
26.98
26.98

52.63
52.08
30.83
28.38
37.69
34.10
35.51
27.76
31.43
29.08

54.06
49.91
31.65
30.18
41.05
36.36
36.75
30.18
35.13
34.42

54.46
47.16
33.75
31.67
47.67
38.96
40.76
31.36
40.37
36.09

58.42
45.73
34.61
32.47
52.32
40.04
42.40
32.31
41.96
34.96

61.03
40.08
36.79
29.38
55.03
43.71
43.91
34.97
43.09
33.04

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Z. Makhlou et al. / Construction and Building Materials 71 (2014) 579588

Fig. 8. Relative strength of mortars immersed in lime water.

Fig. 9. Relative strength of mortars immersed in sulfuric acid solution.

at 180 days, from Fig. 10, in lime water it was noted a gain of
strength, on the contrary, in the sulfuric acid solution there is a loss
of strength and this concerns all the mortars.

begins to increase rapidly for reaching values of about 9.92 at the

30th day, depending on the nature of additions. Beyond this time,
the pH of all acid solutions decreases for reaching values in range
of 2.65.33 at 180 days. However, for accelerated degradation testing, during the dryingimmersion cycles, the pH begins to uctuate, but the pH values are constantly low, about 1.2. After these
immersiondrying cycles, there was a further increase until
60 days. The pH values are in the range of 3.825.30, and again
the pH of all solutions begins to decrease slightly up to the 180th
day to attain values between 2.5 and 4.37.
Fig. 12 shows that at 180 days, the pH values of sulfuric acid
solutions of mortars having undergone an accelerated degradation
are smaller than, those of mortars solutions, which have undergone
a simple degradation. This explains that the mortars, which have
undergone an accelerated degradation, were decalcied in a roughest manner than the mortars having been subjected to a simple
degradation. The accelerated degradation leads to a more intensive
decalcication of mortars, and a higher diffusion of Ca2+ in the pore
of interstitial solution during the degradation, from where at longterm, cementitious materials to the surface of the specimens will
be devoid or almost in calcium. Therefore, the conservation medium will be less and less alkaline over time and of lower and lower
pH values.
Moreover, the pH values of the solutions of mortars F2 and F3
are the lowest in comparison with those of solutions of mortars
F0 and F1. Since for mortars F1 and F0 containing more lime and
calcium carbonate, the diffusion of calcium ions to the conservation solutions will be greater than that of solutions of mortars with
slag and pozzolana, which contain less lime. However, the portlandite has been impoverished after the pozzolanic reaction, thus the
amount of calcium diffused to the conservation solution will be
lower in this case, and therefore the solution is less alkaline and
the pH value is lower.
The pH of conservation solutions of mortars decreased slightly
over time, this is due to decalcication of binders, where rstly,
it was noted a decalcication of portlandite followed by that of
the CSH. This decalcication leads to a progressive impoverishment of mortars in Ca2+ ions. Indeed, the quaternary binders contribute to the dilution effect of Portland cement due to the
replacement by a quantity of slag and pozzolan more or less rich
in silica, which reduces the amount of calcium hydroxide available
for reaction with the acid [29].

4.4. Evolution of pH of conservation solutions

4.5. Relationship weight loss and compressive strength loss
Fig. 11 and Table 6 show the pH change of exposure solutions of
mortars. First, the pH of the sulfuric acid solution alone without
mortar specimens is in the vicinity of 1.30. During the simple degradation, once the samples are immersed in the solution, the pH

Tests on sulfuric acid solutions revealed that there is a signicant correlation between the weight loss and the of compressive
strength loss [30]. Conversely, discrepancies between weight loss

Fig. 10. Relative strength of mortars in both media 180 days.

Fig. 11. Changes in pH of sulfuric acid solutions during the accelerated attack.

Z. Makhlou et al. / Construction and Building Materials 71 (2014) 579588

Table 6
PH values of acid solutions of the two attack protocols at 30, 60 and 180 days.
30 days

60 days

180 days

Accelerated attack

F0
F1
F2
F3
F4

1.21
1.18
1.23
1.10
1.26

5.30
5.17
4.53
3.82
4.72

4.37
4.30
2.79
2.50
3.60

Slow attack

F0
F1
F2
F3
F4

9.92
8.97
8.35
7.95
8.46

8.75
5.81
6.34
5.97
4.14

5.33
4.82
3.01
2.60
3.88

and strength loss after exposure in acidic environments have also

been reported by other researchers [31,6].
It may be noted, in fact, from Fig. 13, there is a correlation
between weight loss and strength loss during accelerated testing
for dryingimmersion cycles and continuous immersion taken separately for all mortars, but there is no correlation when considering
both procedures simultaneously. The correlation coefcients
determined are approximately 0.99 for all samples.
It should be noted that, during the continuous immersion and
up to 120 days of exposure of the specimens in the acid solution,
when there is a decrease of weight loss there will be a decrease
of strength loss for the mortars with mineral additions. Note,
equally, that the highest strength losses are proportional with
the increased weight losses for control mortars.
While during the dryingimmersion cycles, when the weight
loss increased the strength loss increased as well. At the end of
the dryingimmersion cycles, there was a slight decrease in weight
loss for mortars with mineral additions.
The fundamental factors that govern weight loss of the exposed
surface to the conservation solution are calcium hydroxide content
and the existence of a degraded or protective zone. These last have
an important role in slowing down the kinetics of the acid reaction
by reducing the diffusion of cations and anions of the acid in the
healthy matrix of mortars.
It should be noted that, for weight loss percentages are close to
each other. The increasing of strength loss is greater for mortars F0
and F4 than for mortars F2, F3 and F1 in the dryingimmersion
cycles and continuous immersion.
In this case of accelerated degradation, there is a strength loss
which is probably due to the dissolution of Ca(OH)2, since the degradation is accelerated. Samples were at rst quickly decalcied,
which consequently increased the porosity. On the other hand,

Fig. 12. pH values of sulfuric acid solutions in the two protocols of attack at
180 days.

585

the surfaces of specimens have been eroded by the action of acid,

and therefore a loss of mechanical performance of mortars.
It was noticed in the case of slow attack, there was an increase
in the loss of strength, This may be due to the dissolution of
Ca(OH)2, followed by reduction of the strength loss, which may
be due to the protective zone formed on the surface of the specimens and the formation of new CSH. These latter, which will
contribute to the increase of the compressive strength, because
the development of the compressive strength of the cement is
strongly inuenced by the rate of CSH, formed during the hydration of cement.
Any relationship between weight loss and compressive strength
loss should be taken with prudence, because both mechanisms are
governed by different factors and are not directly linked [4,31].
4.6. Comparison between slow attack and accelerated attack
The nal product of degradation by an acid may be a silica gel
resulting from a complete decalcication of CSH, according to
Grube and Rechenberg [32], it may have a role in protecting the
concrete surface and slow down the reactions. These authors also
emphasize that the conditions of transport of the aggressive agent
is more important than its concentration.
The acid attack leads to the dissolution of calcium hydroxide
and CSH. The sulfuric acid H2SO4, is very aggressive vis-a-vis
the concrete following a double mechanism of acid attack and sulfate attack as in reactions (1) and (2):

CaOH2 H2 SO4 ! CaSO4 2H2 O

and

3CaO  Al2 O3 CaSO4 32H2 O

! 3CaO  Al2 O3  3CaSO4  32H2 O

Table 7, Figs. 14 and 15 show that, the compressive strength of

all mortars, immersed in both environments, increases continuously, at all ages and are higher than those of mortars, which
underwent an accelerated degradation.
In lime water, the compressive strengths of mortars having
undergone an accelerated degradation (immersiondrying cycles,
followed by a continuous immersion) are lower than those of mortars having undergone a simple degradation (one continuous
immersion) of 180 days (Fig. 14). In both protocols of degradation,
for mortars with mineral additions, mortars F2 have the largest
strength followed by the mortars F3 then F4 and nally F1, but
the control mortars have always a higher strength than those of
mortars with mineral additions.

Fig. 13. Weight changes according to the variation of the compressive strength
after 24 weeks of exposure to the sulfuric acid solution.

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Z. Makhlou et al. / Construction and Building Materials 71 (2014) 579588

Table 7
Compressive strengths (MPa).
Accelerated attack
Lime water

Dryingimmersion cycles

Continuous immersion

28 days

2th im. (12d.)

5th im. (30d.)

7th im. (42d.)

60 days

90 days

120 days

180 days

A0
F0

43.52
43.52

44.78
40.79

43.97
33.19

44.61
28.82

45.21
27.08

46.88
25.44

47.63
24.02

51.01
22.14

A1
F1

21.66
21.66

22.78
23.89

23.89
22.93

25.81
21.74

25.90
20.61

25.99
20.02

26.87
19.13

27.24
18.00

A2
F2

30.48
30.48

33.10
35.31

33.53
33.17

34.86
30.67

36.41
28.00

41.12
27.66

43.97
25.82

47.71
23.94

A3
F3

25.25
25.25

29.56
29.18

31.33
28.77

34.07
23.38

34.19
23.00

34.39
22.11

36.67
21.18

39.32
20.71

A4
F4

26.98
26.98

28.41
22.97

29.98
21.75

31.95
19.98

32.07
19.07

32.15
18.60

33.45
17.76

34.73
16.98

Fig. 14. Compressive strength of mortars in lime water at 180 days.

Fig. 15. Compressive strength of the mortars in sulfuric acid solution at 180 days.

Idem for sulfuric acid solutions, the compressive strength of

mortars having undergone accelerated degradations are lower than
those of mortars, which have undergone a simple degradation at
180 days (Fig. 15).
In both degradation protocols, for mortars with mineral additions, mortars F2 have the highest strength followed by mortars
F3 then F4 and nally F1, but in this case the control mortars have
strength lower than those of mortars F2.
In the case of simple degradation, at the age of 180 days, the
strength of mortars F0, F1, F2 and F3 are 40, 29, 44 and 35 MPa
consecutively, while in the case of accelerated degradation, the
strength values are 22, 18, 24, 21 MPa.
From Fig. 16, it is shown that the loss of strength of mortars
immersed in the solutions of sulfuric acid at 180 days concerns
especially those, which have undergone an accelerated degradation. In contrast, during the simple degradation, mortars had a gain
of strength. During the protocol of accelerated degradation, the
loss of strength is most pronouncing, especially for mortars F4 then
F0; it is 45% and 16% successively. The mortars least affected by the
accelerated degradation are F2 and F3, with losses of strength of
about 7%, while in lime water it is 15% and 12%. On the contrary,
mortars F1 are the only ones, which had a gain of strength of about
10%. While in the case of simple degradation, the control mortars
are the only ones, which have suffered a loss of strength of about
5%, but all other mortars have had a gain of strength, which is
around 30.27% and 26% for mortars F2, F3 and F1 successively.
From these results, it was concluded that the dryingimmersion
and heatingcooling cycles have did accelerate the decalcication

process of mortars, by activating the diffusion of ions and the dissolution-precipitation of the newly formed minerals, and consequently accelerating the degradation of mortars [3336].
The drying phase promotes the diffusion of ions in the open
pores and causes deviations to the equilibrium during the rise of
temperature. The immersion phase allows the wetting of dried
material and further promotes the release of ions called actives
and physically tied to the surface of CSH [3742]. The pH value
plays also a signicant role in the degradation processes.

Fig. 16. Relative compressive strength of mortars immersed in sulfuric acid

solution at 180 days.

Z. Makhlou et al. / Construction and Building Materials 71 (2014) 579588

5. Conclusions
The test results showed that the addition of limestone ller,
blast furnace slag, and natural pozzolana, incorporated simultaneously in cement improves the mechanical behavior of these
materials. In addition, acquires resistance to attacks of sulfuric acid
solution in the case of accelerated degradation, interesting according to the proportion and the type of mineral addition incorporated
into cement. From test, results it was also concluded that:
 The immersiondrying and heatingcooling cycles and the
increasing of concentration of sulfuric acid solution have accelerated the degradation of mortars. These cycles allow a faster
decalcication of the hydrated compounds of cement in the acid
solutions, especially the portlandite. The degradation touched
rst the control mortars F0 then F1 and mortars, which contain
more of calcium carbonate and lime. Mortars F2 and F3 are less
sensitive, as that contain less portlandite, since it has been consumed by slag and pozzolana in the pozzolanic reactions.
 In the sulfuric acid solution during the dryingimmersion
cycles, there was a decrease of weight of all mortars up to the
7th cycle. Beyond this cycle, there has been an increased weight
until the 60th day, followed by stabilization or a slight decrease
in weight of mortars with lower mineral additions than the control mortar F0 up to the 120th day. Beyond this age, the weight
loss is most signicant.
 In the lime water, all mortars had a weight gain over time, up to
180 days. Mortars A2 with 30% slag had highest gain of weight.
In sulfuric acid solution during the protocol of slow degradation, a slight gain of weight was recorded. In contrast, during
the protocol of accelerated degradation, a weight loss of all
mortars was noticed, especially that of the control mortar F0.
 The pH values of sulfuric acid solutions of mortars having
undergone an accelerated degradation are lower than those of
solutions of mortars which have undergone a simple degradation. This reects that mortars having undergone an accelerated
degradation presented a more severe leaching or an accentuated decalcication than mortars having undergone a simple
degradation. Consequently, a greater diffusion of Ca2+ ions to
the curing solution during the accelerated degradation.
Whence, at long-term, on the surface of mortar specimens,
the material is poor in calcium and as a consequence an exposure solutions less and less alkaline over the time.
 Replacement of part of Portland cement by 30% of limestone,
10% of blast furnace slag and 10% of natural pozzolana,
improves the behavior of mortars in sulfuric acid solution. It
is noticeable that the addition of high level of calcium in the
cement is detrimental for the durability of concrete. Therefore,
the simultaneous incorporation of the slag and the natural pozzolana with the limestone ller decreases the effect of compromise of the latter when added in high amount of about 30% in
concrete.

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