Effect of Different Pozzolanic Admixtures on Sulfuric Acid

Resistance of Concrete

Masoud Moradian 1
Milad Hallaji 2
Behnam Kian i3
Mohammad Shekarchi 4
Mehdi Nemati Chari 5

ABSTRACT

Sulfuric acid environment is one of the most aggressive conditions which puts the durability of concrete
in danger in many industrial structures. In this study, 10×10 concrete cube specimens containing silica
fume, zeolite and metakaolin and also control specimens were made all with a w/c ratio of 0.45. After 28
days of water curing, specimens were placed in sulfuric acid solutions with pH=1 and pH=2. In order to
keep the pH of solutions in a constant value, daily pH control was performed and required amount of acid
added to solutions to reach the desired pH (the increase of pH value is result of reaction between concrete
and acidic solution). During exposure period, weight changes of specimens as well as sulfate penetration
depth were measured for comparing the performance of different mixtures. The results revealed that
concrete specimens including pozzolanic admixtures performed considerably better than ordinary
concrete without pozzolan.

Keywords

Blended cement, Durability, Pozzolan, Sulfuric acid, Weight change.

1
Research assistant, Construction Materials Institute (CMI), School of Civil Engineering, University of Tehran, Tehran, Iran,
Corresponding author. Tel.:+98-21-88969112; Fax: +98-21-88959740.
E-mail addresses: [email protected], URL: http://cmi.ut.ac.ir
2
Research assistant, Construction Materials Institute (CMI), School of Civil Engineering, University of Tehran, Tehran, Iran,
[email protected]
3
Research assistant, Construction Materials Institute (CMI), School of Civil Engineering, University of Tehran, Tehran, Iran,
[email protected]
4
Associate Professor, Director of Construction Materials Institute (CMI), School of Civil Engineering, University of Tehran,
Tehran, Iran, [email protected]
5
Research assistant, Construction Materials Institute (CMI), School of Civil Engineering, University of Tehran, Tehran, Iran,
[email protected]
Moradian, Hallaji, Kiani, Shekarchi and Chari

1 INTRODUCTION

Concrete is the most widely used material in construction of structures. When concrete is exposed to
environment containing sulfuric acid, it experiences severe deterioration due to neutralization reactions.
Sulfuric acid reacts with the free lime [Ca(OH)2] in the concrete forming gypsum (CaSO4·2H2O). Another
destructive action is the reaction between calcium aluminate and the gypsum crystals. These two products
form the less soluble reaction product ettringite (3CaO·Al2O3·3CaSO4·32H2O) [Moradian et al. 2010,
Clifton and Ponnersheim 1994]. Both gypsum and ettringite cause expansion which results in cracking of
concrete [Bonakdar and Mobasher 2010]. The corroded surface becomes soft and white. When the
corrosion continues, the corroded concrete structure loses its mechanical strength [Monteny et al. 2001].

To extend the life of concrete in acidic environment, it is essential to find a way to control these
processes. The rate of deterioration depends on the concentration of sulfuric acid, ambient temperature,
cement type, water to cement ratio, porosity and presence of admixtures [Tumidajski 1995]. Generally,
adding pozzolan results in a concrete with a denser structure, better able to withstand sulfate attack, but it
also reduces or eliminates the free, leachable calcium hydroxide [Pavlík and Uncík 1997].

Among all mineral admixtures, silica fume (SF) has found to have the best performance in resistance of
concrete in acidic environment [Dazko et al. 1997]. The effect of silica fume on concrete microstructure is
well reported in the literature. Silica fume is an artificial pozzolan that increases the compressive strength
of concrete as a result of making stronger transition zone as well as the increase in the rate of hydration at
early ages [Ghods et al. 2007, Shekarchi et al. 2009]. Metakaolin is silica based and active pozzolan
product that improves the mechanical properties of concrete in both short and long term [Nai-qian et al.
1990; Liguori et al. 2004; Perraki et al. 2003]. The prefix Meta refers to the calcination of kaolinite at
certain temperature and the production of Metakaolin.

However, there is another admixture which has not got enough attention and its ability to improve
performance of concrete in aggressive environments has almost left unknown. Natural zeolite (NZ) is a
crystalline mineral that has siliceous and aluminum oxide in its chemical compound that like other
mineral admixtures produces more C-S-H gel through pozzolanic activity [Ahmadi and Shekarchi 2010].
It is enunciated that 10% replacement of zeolite could lead to the production of high quality concrete with
lower water absorption, chloride ion diffusivity coefficient and permeability. Although the usage of
superplasticizer to reach the required workability is imperative [Ahmadi and Shekarchi 2010]. The
porosity reduction can only obtained by limited amount of zeolite replacement which is claimed to be
about 15% [Poon et al. 1999].

2 EXPERIMENT PROGRAM

2.1 Used Materials

Calcareous aggregate was chosen for the concrete mixes. Using calcareous aggregates instead of siliceous
type provides additional alkalinity of concrete and increases durability of concrete in sulfuric acid
environment [Barnard 1967; Thistlethwayte 1972]. The chemical analysis of aggregate is presented in
table 1. Three types of pozzolan including silica fume, Metakaolin and zeolite were used in order to
perform the tests. Table 2 includes the chemical analysis of cement as well as pozzolanic materials.

Table 1. Chemical analysis of aggregate.

Fine aggregate Coarse aggregate
Oxide
(%)

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 Effect of Different Pozzolanic

SiO2 0.4 2.34

TiO2 0.04 0.03
Al2O3 0.91 0.59
Fe2O3 0.21 0.12
CaO 46.98 47.58
MgO 0.68 0.59
Na2O 0.05 0.04
K2O 0.25 0.20
SO3 0.4 0.11
L.O.I 41.03 42.69

Table 2. Chemical analysis of cement and pozzolanic materials.

Cement Silica Fume Metakaolin Zeolite
Oxide
(%)
SiO2 22.71 93.16 51.85 67.79
Al2O3 4.91 1.13 43.87 13.66
Fe2O3 2.93 0.72 0.99 1.44
CaO 59.55 - 0.2 1.68
MgO 2.81 1.6 0.18 1.6
Na2O 0.32 - 0.01 2.04
K2O 0.87 - - 1.42
SO3 2.99 0.05 - 0.5
L.O.I 2.31 1.58 0.57 10.23

2.2 Mix Design

The mix design is presented in Table 3. The water to binder ratio was kept 0.45 in all the batches and
cubic 10×10×10 cm specimens were made for placing in the acid solution. Moreover, polycarboxylate
superplasticizer was employed to reach the slump of near 20 cm.

Table 3. Concrete mix design.

Cement Silica fume Zeolite Metakaolin Slump
Code W/C
(Kg/m3) (% replacement) (% of replacement) (% of replacement) (cm)
MC 400 0.45 - - - 22
MSF 370 0.45 7.5 - - 20
MZE 360 0.45 - 10 - 22
MME 360 0.45 - - 10 21

2.3 Performed Tests

Concrete specimens were put in sulfuric acid solution after 28 days of moist curing. The pH of solutions
were kept 1 by adding additional sulfuric acid. Figure 1 shows the pH increase of solution during a period
of 150 days. The weight change and also sulfate penetration in depth of concrete were measures in order
to compare the performance of each specimen. For weighing of specimens, they were taken out of the
tanks and let them be out for 4 hours for drying of their surfaces. Then weighting was performed using
digital balance. For measuring the depth of sulfate penetration, concrete powder samples were taken from
four different depths of specimens. The sulfate measurement was performed using gravimetric analysis.

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Moradian, Hallaji, Kiani, Shekarchi and Chari

In addition, some specimens were put in a solution of the pH=2 and the visual observation were assessed
for this group.

Figure 1. pH change of solution.

3 RESULTS AND DISCUSSION

As expected, the concrete surface was corroded uniformly because of the calcareous base of aggregate.
Existence of gypsum is the sign of sulfuric acid attack occurrence. However, considerable amount of
efflorescence dissolve in solution and disappear from the specimen surface because of strong sulfuric
acid. But, gypsum is visible on the surface of specimens which were placed in solution with pH=2. Figure
2 shows the specimens appearance after 120 days of exposure in sulfuric acid solution with pH=1.

Cont ZE SF

Figure 2. Specimens after 120 days exposure in sulfuric acid (pH=1).

The specimens are visually resemble and no definite conclusion could be drawn. However, the specimen
containing zeolite seems to have more efflorescence on its surface. Figure 3 shows the weight change of
specimens after 200 day (each data is the average of results of 3 specimens). After 200 days of exposure
in sulfuric acid with pH of 1 no weight loss was observable in none of specimens. The weight gain could
be the result of completion of hydration reaction and also filling of pores by expansive products like
gypsum and ettringite. It is possible that they experience weight loss after an undetermined period.

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 Effect of Different Pozzolanic

The specimens made with metakaolin showed more weight gain compared to other pozzolanic material.
Control specimens weight changed less than three other codes as well. It could be concluded that using
pozzolans improves the resistance of concrete exposed to acidic environments.

Figure 3. Weight change of specimens in acid sulfuric (pH=1).

Sulfate profiles in depth of concrete are presented in Fig. 4. This test could be more expressive than
weight change of concrete. The surface sulfate in specimen congaing zeolite is more than others.
However the amount of sulfate of this specimen in depth of concrete is less than three other specimens.
This test could support the idea of confident using of zeolite for making resistant concrete in sulfuric acid
environment. The control specimen showed the worst performance and this implies the necessity of using
pozzolanic for controlling the rate of deterioration in acidic environment.

Figure 4. Sulfate profile in depth of concrete.

It is noted that formation of effloresce on the surface of concrete decrease the rate of deterioration and
could be a protective layer against aggressive agents. Figure 5 shows the formation of this layer on the
surface of concrete in sulfuric acid with pH of 2. In the case that aggregates are calcareous, this layer is
thicker and more considerable. However, effloresce in stronger acid solution dissolves rapidly and has
less important effect.

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Moradian, Hallaji, Kiani, Shekarchi and Chari

Figure 5. Formation of protective layer on the surface of concrete in sulfuric acid solution (pH=2).

4 CONCLUSIONS

Investigation of concrete in sulfuric acid is important for simulation of concrete in environments like
sewage pipes or industrial plants. In this paper, three different pozzolans were tested for comparing the
performance of them in sulfuric acid environment. Based on the results of tests, the following conclusions
could be drawn:
• Calcareous aggregate improves the properties of concrete exposed to acidic environment, because
calcareous aggregates provide more alkalinity for concrete.
• Pozzolans improves mechanical and durability properties of concrete. Using pozzolans is one of
the easiest ways to increase the resistance of concrete in acid sulfuric environment.
• Efflorescence formation occurred on the surface of concrete. This suggests the sulfate attack
existence in concrete.
• In spite of elapsing near 200 days of exposure, the specimens not only did not lose their weight,
but also gain weight. This is attributed to completion of hydration reaction and also filling the
pores with the products of sulfate attack. The specimens contained metakaolin showed more
weight gain.
• The specimens contained zeolite had the greatest amount of surface sulfate. However, the sulfate
in depth of specimen is least.

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