Cite this article Research Article Keywords: chemical properties/

Torres ALT, Souza LMS, Silva MIP and de Andrade Silva F Paper 1800194 compressive strength/durability-related
Concrete degradation mechanisms by sulfuric acid attack. Received 18/04/2018; Revised 21/08/2018; properties
Magazine of Concrete Research, Accepted 30/08/2018
https://doi.org/10.1680/jmacr.18.00194
ICE Publishing: All rights reserved

Magazine of Concrete Research

Concrete degradation mechanisms

by sulfuric acid attack
Ana Luisa Tavares Torres Maria Isabel Pais da Silva
MSc student, Department of Civil and Environmental Engineering, Professor, Department of Chemical Engineering and Materials, Pontifícia
Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Universidade Católica do Rio de Janeiro (PUC-Rio), Rio de Janeiro, Brazil
Rio de Janeiro, Brazil Flávio de Andrade Silva
Lourdes Maria Silva de Souza Professor, Department of Civil and Environmental Engineering, Pontifícia
Researcher, Tecgraf Institute, Pontifícia Universidade Católica do Rio de Universidade Católica do Rio de Janeiro (PUC-Rio), Rio de Janeiro, Brazil
Janeiro (PUC-Rio), Rio de Janeiro, Brazil (corresponding author:
lmsilvadesouza@tecgraf.puc-rio.br)

Concrete degradation may occur from biochemical processes, especially in the case of sewage system networks,
owing to the production of biogenic sulfuric acid by certain types of bacteria. This study aims to investigate the
residual mechanical properties of concrete exposed to sulfuric acid solutions of different concentrations (0·5%, 1%
and 3%). Two concretes were produced: a standard concrete, with a water/cement (w/c) ratio of 0·83, and a high-
performance one, with w/c of 0·28. The samples were cured for 28 d and evaluated for immersion periods of 28 and
84 d. During immersion, changes in pH and the weight loss of the specimens were monitored. After immersion, the
residual mechanical properties were evaluated by compressive and splitting tensile tests. Composition and
microstructural changes were evaluated by phenolphthalein solution, X-ray diffraction and scanning electron
microscopy. Results show a higher mass loss in the concrete specimens with a higher percentage of cement, as well
as a greater percentage reduction of the mechanical strength.

Notation The production of biogenic sulfuric acid involves several

A original area of sample
d diameter of sample
Fu applied load
fc compressive strength
fct,sp compressive strength, as determined using the
Brazilian splitting test
L thickness of sample
λ wavelength of X-rays used for X-ray diffraction
2θ Bragg angle
Introduction
Literature review
The different mechanisms of deterioration of concrete may be
of physical, chemical or mechanical origin, as a result of exter-
nal factors or internal causes (Neville, 2011). Sewer systems,
including transport networks, access ways and manholes,
as well as other structures in environments with high levels of
pollution, such as rainwater networks (de Aguiar and Baptista,
2011), factory cooling systems (Zherebyateva et al., 1991),
underground structures and marine structures, are examples of
very aggressive environments for cementitious materials. In
these installations, deterioration can occur as a result of the
chemical and biological processes. In anaerobic conditions,
sulfate-reducing bacteria consume sulfate present in the sewage
and then release sulfide ions (O’Connell et al., 2010). These
ions react with hydrogen (H) dissolved in the sewage, forming
hydrogen sulfide (H2S) (Monteny et al., 2000). Owing to turbu-
lence, the hydrogen sulfide that was dissolved in the sewage is
released as gas (Monteny et al., 2000; Sand and Bock, 1991;
Sand et al., 1994). The hydrogen sulfide penetrates and
accumulates in the pores of the concrete walls above the liquid
level, where it reacts with oxygen (O2), forming elemental
sulfur (S) (Alexander and Fourie, 2011; De Belie et al., 2004;
Jensen et al., 2011; Monteny et al., 2000; Sand et al., 1994;
Vincke et al., 1999). Finally, sulfate-oxidising bacteria metab-
olise sulfur and produce sulfuric acid directly on the concrete
surface (Aydin et al., 2007; Monteny et al., 2000; Sand and
Bock, 1991). The processes are described in the following reac-
tions (Alexander and Fourie, 2011).
I: H2 S Ð Hþ þ HS Ð 2Hþ þ S2
II: H2 SðaqÞ þ 2O2 ! 2Hþ
ðaqÞ þ SO4ðaqÞ
2

contact between concrete elements and sulfuric acid (H2SO4).

The presence of sulfuric acid in sewage systems may have a
chemical origin, through industrial discharges (Fattuhi and
III: 2H2 SðaqÞ þ O2 ! 2SðaqÞ þ 2H2 O þ 3O2ðaqÞ
Hughes, 1988), or a biogenic origin, after a series of chemical
reactions carried out by anaerobic and aerobic bacteria present ! 4Hþ
ðaqÞ þ 2SO4ðaqÞ
2

in the liquid flow and concrete walls.

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During the corrosion process, calcium hydroxide (CaOH) and
calcium aluminate are dissolved, owing to the acid environ-
ment (Aydin et al., 2007; De Belie et al., 2004; Monteny
et al., 2000, 2001; Mori et al., 1992; O’Connell et al., 2010;
Yousefi et al., 2014). The first reaction that occurs is the
reaction of sulfuric acid with calcium hydroxide, leading to the
formation of gypsum (Aydin et al., 2007; O’Connell et al.,
2010). The formation of gypsum, which generates a soft and
whitish corroded surface, leads to an expansion of the concrete
(Monteny et al., 2001), which can easily be separated from the
underlying concrete layer (Fattuhi and Hughes, 1988). The
next process that can occur is the reaction of calcium alumi-
nate with this newly formed gypsum, leading to the formation
of ettringite (Aydin et al., 2007; Monteny et al., 2000).
The action of the bacteria was discovered by Parker (1945),
who, for the first time, isolated and studied the role of the bac-
terial action in the concrete corrosion process. Some aspects
were established after several analyses of concrete samples
taken directly from sewage plants or samples deposited directly
in the sewage (Alexander and Fourie, 2011; Grengg et al.,
2015; Mori et al., 1992; Zherebyateva et al., 1991). First, the
highest incidence of corrosion occurs at the sewage level and
just above it (Mori et al., 1992); this finding is explained by
the constant supply of nutrients and the fact that the corroded
materials formed in this region are removed by the sewage
flow. Another common observation is that the biogenic process
of degradation occurs very slowly and it may take years until
the corrosion is observed (Alexander and Fourie, 2011; Hasan
et al., 2013).
Therefore, methodologies that provide faster results have been
developed. Other approaches include accelerated tests that can
be carried out with the use of chemical sulfuric acid as a cor-
rosive agent (Aydin et al., 2007; De Belie et al., 2002; Fattuhi
and Hughes, 1988; Hughes and Guest, 1978; Raju and
Dayaratnam, 1984), microbiological simulation tests through
the action of biogenic sulfuric acid (Sand et al., 1994; Vincke
et al., 1999; Yousefi et al., 2014), or through the analysis and
comparison of the results obtained by the two methods
(De Belie et al., 2004; De Muynck et al., 2009; Ehrich et al.,
1999; Monteny et al., 2001).
The research of Fattuhi and Hughes (1988) investigated mix-
tures of cement paste and concrete with different water/cement
(w/c) ratios and curing periods, immersed for up to 50 d in 2%
sulfuric acid solution. Before the chemical immersion tests,
reference samples were tested in order to analyse the compres-
sive strengths of the different mixtures. As expected, samples
with a lower w/c presented higher initial compressive strength
and density. The final strengths, however, were not measured
after the immersion tests. Nevertheless, Fattuhi and Hughes
(1988) observed that, as the w/c ratio was reduced, there was a
greater mass loss of the samples, despite the gains in the initial
properties of the specimens.
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Concrete degradation mechanisms by
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Torres, Souza, Silva and de Andrade Silva
Raju and Dayaratnam (1984) analysed the reduction of
strength and mass of specimens immersed in solutions of sulfu-
ric acid (0·1%, 1% and 5%) after 28 d of curing. Samples
immersed in the 0·1% solution showed an increase in both
strength and mass compared with the reference sample results
(without immersion). Meanwhile considerable decreases of
strength and mass were observed for 1% and 5% acid
exposures.
Research significance
Structures subjected to this corrosive process are often neg-
lected because of the difficulty of access for maintenance and
repairs. Added to this are the high costs and necessary inter-
ruptions involved in these operations (Grengg et al., 2015;
Monteny et al., 2001; O’Connell et al., 2010; Zhang et al.,
2008). In this way, the state of these structures is rarely moni-
tored. Therefore, when the corrosive process is discovered, the
structure is already badly damaged, requiring major repairs or
replacement of affected elements. Most studies on this subject
are focused on the mass loss of sample of various sizes and
different concrete dosages; mechanical behaviour and strength
loss after corrosive processes were often neglected. In the
present work, an experimental programme was developed to
analyse the durability of the structures subject to degradation
by sulfuric acid, through the analysis of the reduction of
strength and mass of concrete samples. The physical and mech-
anical properties of samples of two different types of concrete,
a high-performance concrete (HPC) and a conventional con-
crete (CC), were evaluated. The specimens were immersed for
28 and 84 d in solutions of sulfuric acid with concentrations of
0·5%, 1% and 3%. After the immersion period, their mechan-
ical properties (i.e. compressive and Brazilian splitting
strengths) were obtained and compared with those of reference
samples (which had not been exposed to acid). In addition to
the mechanical tests, the microstructural changes and variation
in the composition of the samples were evaluated after the
immersion process, comparing with reference samples. These
analyses were done through pH analysis by phenolphthalein
solution exposure, X-ray diffraction and scanning electron
microscopy.
Experimental programme
Materials and processing
The CC, with a w/c ratio of 0·83, was produced using Portland
cement CPII F-32, sand, gravel and water. The HPC had a w/c
ratio of 0·28 and contained a Brazilian slag cement type
CPVARI (high initial strength Portland cement), fly ash, silica
fume, silica 325 mesh, sand, gravel, water and superplasticiser.
Table 1 shows the composition of both concretes.
The mixes were produced using a bench-mounted mechanical
mixer with a capacity of 20 l and cast in metallic moulds with
prior application of release agent. The specimens for the
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Torres, Souza, Silva and de Andrade Silva

Table 1. Mix proportions of the concrete samples containers and completely immersed in the solutions. Then the
Concrete sample Proportion: kg/m 3 containers were covered and stored within a fume hood.

CC Every week, the weight of each sample was recorded and the
CPII F-32 297·06
pH of the solution was measured using pH indicator strips
Sand 906·37
Gravel 849·09 (pH range, 0–6). As the solutions would get neutralised by the
Water 247·44 reactions, every couple of weeks the solutions were changed.
HPC At the end of each month, the samples were cleaned to remove
Gravel 492·00 poorly adhered corroded material. The specimens were
0·15 < sand < 0·85 826·80
weighed and photographed before and after the cleaning.
0·85 < sand < 4·80 99·60
Silica 325 mesh 70·00
CPV ARI 360·00 In the eighth week of immersion in the 3% solution, it was
Fly ash 168·00 observed that the state of deterioration of the HPC discs was
Silica fume 45·00 very advanced. So, these samples were tested after 56 d of
Water 166·40
immersion. For the other HPC and CC samples, the immer-
Superplasticiser 19·80
sion periods were 28 and 84 d.

compressive tests were cylindrical, 5 cm in dia. and 10 cm Compressive strength test

high. For the Brazilian splitting tests, the specimens were discs,
10 cm in dia. and 2 cm thick, cut from cylindrical specimens
of 10  20 cm. For each solution, three specimens of each type
of concrete were tested, thus totalling 24 cylinders and 24 discs
for the HPC and CC concretes.
The CC samples were moulded in four layers and each layer
was compacted with 30 socket beats. For HPC samples, light
beats were made on the sides of the form as casting occurred.
On the day after casting, the samples were unmoulded, marked
with the type and date of casting and cured in tap water for
28 d. Prior to testing, the specimens were properly levelled.
The reference specimens were subjected to the mechanical tests
after 28 d curing, while the other samples were submitted to
immersion.
For the X-ray diffraction analysis, samples were made without
aggregate, keeping the other components at the same dosage.
The omission of the sand aimed at a better analysis of the be-
haviour and changes occurring in the cement components,
since sand is not affected by acid. For each concrete, cylindri-
cal specimens measuring 2·5  5 cm were moulded into PVC
tubes. Two samples of HPC and CC were immersed for 7 d in
3% sulfuric acid solution, while the remaining samples contin-
ued the cure for the same period, totalling 35 d of cure in
water. At the end of the 1-week period, the corroded material
of the external layer of the samples was submitted to chemical
testing and the material of the reference samples was collected
for X-ray diffraction analysis.
Experimental testing procedure
Chemical test method
Sulfuric acid solutions with concentrations of 0·5%, 1% and
3% per volume were made by diluting sulfuric acid p.a. (98%)
with deionised water. The samples were placed in plastic
The compressive strength test was conducted under an actuator
displacement control regime on an MTS testing system, model
810, with a load capacity of 500 kN, at a displacement rate of
0·4 mm/min. The axial displacements of the specimens were
measured using two linear variable displacement transducers,
with lengths of 70 mm, coupled with acrylic rings positioned
around the specimen, with the distance measured (L0) equal to
72 mm. A metal ball joint was placed on top of the cylinder
and the whole system was centralised with the test machine, as
shown in Figure 1(a). Three (cylindrical) specimens were tested
for each experimental condition. The compressive strength ( fc)
was obtained as the applied load (Fu) divided by the original
area (A) of the sample, as
Fu
1: fc ¼
A
Brazilian splitting test
For the Brazilian splitting tests, the same mechanical test
machine was used, but with a displacement rate of
0·3 mm/min. The crack opening was measured using a linear
variable displacement transducer fixed between two acrylic
plates at a distance of 30 mm. Wooden strips of width 5 mm
and height 3 mm were used at the top and bottom of each
disc, for better load distribution. A metal ball joint was placed
on top of the disc and the whole system was centralised with
the test machine, as shown in Figure 1(b). As in the compres-
sive strength test, three specimens (discs) were tested for each
experimental condition. For a better evaluation of the results,
the strength ( fct,sp) was calculated from the applied load (Fu),
considering the original dimensions of diameter (d) and thick-
ness (L) of the samples, as
2Fu
2: fct;sp ¼
πdL

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(a) (b)
Figure 1. Setup for (a) compressive strength test and
(b) Brazilian splitting test
Surface pH by phenolphthalein solution
The purpose of this test method was to determine the depth of
the corroded layer on the surface of hardened concrete using a
phenolphthalein-based indicator. The indicator solution was
produced according to Rilem Recommendations (Rilem,
1988), from a mixture of 1% of phenolphthalein powder with
ethanol of 70% concentration. This solution changes colour
when it comes into contact with lower-pH surfaces: for pH
values greater than 9·5, the solution is pink; however, for pH
values less than 9·5, the solution becomes transparent (Neville,
2011). Immediately after the mechanical tests, the specimens
were sprayed with phenolphthalein solution, in order to
observe pH changes in the regions near the exposed surfaces.
Thus, it was possible to observe the concrete thickness affected
by the sulfuric acid solutions.
Characterisation and microstructural analysis
X-ray diffraction analyses were performed in order to observe
changes in the crystalline phases of the two types of concrete
samples after 7 d of immersion in 3% solution. A Bruker dif-
fractometer model D8 Discover X-ray powder diffractometer
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Concrete degradation mechanisms by
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Torres, Souza, Silva and de Andrade Silva
with copper radiation (Cu K-α, λ = 1·5418 Å) operating at
40 kV and 40 mA was used to perform this procedure. To
determine the crystalline phases, scans were performed at an
angular velocity of 0·02° per second and the interval between
Bragg angles (2θ) 0° and 80° was measured.
For the microstructural analysis, samples of both mixtures
were first analysed in an optical microscope. The images were
captured at the edge of the samples and only showed signifi-
cant results for the CC sample. Thus, for the microstructural
analysis of the CC sample, a JSM-6510 LN scanning electron
microscope was used, operating at 20 kV, with a spot size
equal to 66. It was necessary to coat the sample with carbon.
For this, a Balzers sputter coater (model SCD 050) was used.
Obviously corroded areas and apparently unaffected areas
were analysed.
Results and analysis
Immersion for 28 d
Figure 2 shows the results of the compressive strength tests
and Brazilian splitting tests performed on specimens exposed
to sulfuric acid solutions (0·5%, 1% and 3%) for 28 d prior to
testing. The reference samples, which were not exposed to any
solution, are referred to as ‘NI’ (for ‘not immersed’).
For both tests it is possible to observe higher strength loss for
the HPC samples compared with CC samples subject to the
same conditions. The reduction of the strength observed for
the HPC samples was directly related to the increase of the
concentration of the solution. Comparing the compressive
strength obtained for the reference samples (without immer-
sion) and that for the specimens exposed to 3% sulfuric acid
solution, a loss of almost 75% is noted.
Conversely, the CC samples presented a slight decline in
strength in both types of mechanical test, slightly more pro-
nounced for the Brazilian splitting test results. In fact, the
values of CC in the compressive test for the samples
without immersion (18·7 ± 1·2 MPa) and in the solutions
of 0·5% (20·7 ± 2·6 MPa), 1% (18·8 ± 2·6 MPa) and 3%
(16·8 ± 2·1 MPa) were quite close and may even be con-
sidered identical, considering the standard deviation. In the
case of the Brazilian splitting tests, the specimens exposed
to 0·5% solution had a strength close to that of the reference
(2·3 ± 0·0 MPa and 2·4 ± 0·1 MPa, respectively). The specimens
exposed to 1% and 3% solutions presented similar strength
values, 1·7 ± 0·0 MPa and 1·6 ± 0·1 MPa, both smaller than
that of the reference.
Figure 3 shows the representative stress–strain curves obtained
in the axial compression tests for the HPC and CC samples
before and after immersion for 28 d in the 3% sulfuric acid
solution. In this way it is possible to notice that there was a
reduction of the elastic modulus due to the immersion for both
 Magazine of Concrete Research Concrete degradation mechanisms by
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Torres, Souza, Silva and de Andrade Silva

100 8

HPC HPC
CC CC
80
6
Stress: MPa

Stress: MPa
60
4
40

2
20

0 0
NI 0·5% 1% 3% NI 0·5% 1% 3%
Concentration Concentration
(a) (b)

Figure 2. Results for HPC and CC, not immersed in solutions (NI) and exposed to solutions of 0·5%, 1% and 3% of sulfuric acid for
28 d in: (a) compressive strength test; (b) Brazilian splitting test

100 100

No immersion No immersion
3% 3%
80 80

60 60
Stress: MPa

Stress: MPa

40 40

20 20

0 0
0 0·002 0·004 0·006 0 0·002 0·004 0·006
Strain: mm/mm Strain: mm/mm
(a) (b)

Figure 3. Compressive strength test: stress as a function of strain after 28 d of immersion: (a) HPC; (b) CC

types of concrete, with this reduction more evident in the
sample of HPC. The graphs of stress plotted against crack
opening shown in Figure 4 also exhibit a reduction of the
strength in the Brazilian splitting tests.
Images of the cylindrical samples with no immersion and after
the immersion period in sulfuric acid solution are shown in
Figure 5. Table 2 shows the mass variations that occurred in
the cylinders and discs after the 28 d immersion period. It can
be observed that the HPC samples exhibited higher surface
deterioration than the CC samples, leading to a greater
material loss, especially with the higher concentrations of sul-
furic acid in the solutions. Similar results were described by
Raju and Dayaratnam (1984), since greater mass loss and
reduction in strength were observed for a higher concentration
of sulfuric acid solution (5%), while inferior losses were associ-
ated with a lower concentration (1%).
The difference between the mass losses for the different con-
cretes can be justified by their compositions. The large mass
loss in the HPC is related to the large volume of cementitious
material in the mixture and consequently the higher amount of

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7 7

6 6 No immersion
3%
5 5
No immersion
Stress: MPa

Stress: MPa
3%
4 4

3 3

2 2

1 1

0 0
0 0·01 0·02 0·03 0·04 0 0·01 0·02 0·03 0·04
Crack opening: mm Crack opening: mm
(a) (b)

Figure 4. Brazilian splitting test of stress plotted against crack opening after 28 d of immersion: (a) HPC; (b) CC

cement hydration. Once in contact with the acid, these pro-
ducts are dissolved, leading to the deterioration of the concrete
samples (O’Connell et al., 2010). Similar results were observed
by Amin and Bassuoni (2018). This corroded material exhib-
ited a pasty texture and was poorly adhered to the samples;
therefore, it was easily removed during the cleaning process.
Meanwhile CC consisted of a large percentage of sand, which
is a siliceous material. This material is not reactive and it is
not attacked by the sulfuric acid. Therefore, the amount of cor-
rosion of the cementitious matrix in the CC is smaller than
that observed in the HPC. Fattuhi and Hughes (1988) came to
the same conclusion, once it was observed that as the w/c
ratios of the mixtures were increased – that is, there was a
lower volume of cementitious materials in the mixture – the
samples had a lower weight loss.
Thus, apparently, the reduction in the strength is directly
related to the mass loss of the samples during the immersion
period. After the 28 d immersion period, a greater mass
loss was observed for the HPC cylindrical samples when com-
pared with the CC samples for the 1% and 3% solutions.
Moreover, the weight loss of both types of HPC samples
increased as the concentration of sulfuric acid in the solution
increased. Conversely, all the CC samples recorded a small
variation of mass for all the sulfuric acid solutions during the
time tested.
A small increase in weight was registered for both types of
sample (cylinders and discs) and both types of concrete matrix
(HPC and CC) in the case of the 0·5% sulfuric acid solution.
The mass increase of the samples is most probably related to
the formation of expansion products, such as gypsum, owing
to the reaction between sulfuric acid and cement hydration
products, as discussed by several researchers (Aydin et al.,
2007; Monteny et al., 2000; O’Connell et al., 2010). The study
of Raju and Dayaratnam (1984), of samples immersed in 0·1%
sulfuric acid solution, showed similar results, with a small
increase of strength and weight, especially after longer periods
of immersion. Cylindrical HPC samples immersed in a 0·5%
solution presented an increase between 0·1 and 0·3 mm in the
sample diameter. In the case of CC, this increase was 0·2 mm
and 0·1 mm for cylindrical samples immersed in 0·5% and 3%
solutions, respectively.
Immersion for 84 d
Figure 6 shows the results of the compressive strength tests
and Brazilian splitting tests after increasing the period of
immersion. Once the immersion time was increased, both
types of concrete showed greater strength variation in both
tests, following similar trends as observed for the specimens
immersed for 28 d. In both tests, HPC samples showed the
greatest strength loss, which, as previously observed, increases
as the concentration of sulfuric acid in the solution increases.
For cylindrical CC samples, there was a slightly larger loss of
resistance relative to that observed in the 28 d immersion test.
For the cylindrical CC samples immersed in 3% sulfuric acid
solution, the strength loss was close to 42%. The greatest
reduction of strength occurred for the cylindrical samples
of HPC immersed in the 3% solution. This reduction was
approximately 88%, compared with the HPC reference con-
crete, and approximately 48% of the strength obtained after
only 28 d of immersion.
As reported in the previous section, the weight loss obtained is
directly related to the reduction of strength of the materials.

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(a) (b) (c) (d)

(e) (f) (g) (h)

Figure 5. Cylindrical samples of HPC analysed after 28 d of immersion: (a) reference sample without immersion; (b) 0·5%; (c) 1%;
(d) 3%. Cylindrical samples of CC analysed after 28 d of immersion: (e) reference without immersion; (f) 0·5%; (g) 1%; (h) 3%

Table 2. Weight variation of cylinders (C.) and discs (D.) after The results of the mass loss percentage of both types of
28 d of immersion samples and concrete are shown in Table 3. Once the immer-
sion period increased, a greater loss of material, especially in
0·5% sulfuric 1% sulfuric 3% sulfuric
acid acid acid samples immersed in 3% solution was noted. In Figure 7, it
can be seen that CC cylindrical samples showed less signs of
C.HPC 0·95 ± 0·02 −1·21 ± 0·51 −25·07 ± 1·00 deterioration than HPC samples.
D.HPC 1·08 ± 0·06 −1·03 ± 0·44 −20·31 ± 0·97
C.CC 1·01 ± 0·03 1·04 ± 0·05 0·92 ± 0·09
D.CC 0·74 ± 0·05 −0·95 ± 0·28 −0·49 ± 0·24 In the HPC cylinders, especially those immersed in the 3% sol-
ution, a higher level of degradation can be observed. In this

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100 8

HPC HPC
CC CC
80
6
Stress: MPa

Stress: MPa
60
4
40

2
20

0 0
NI 0·5% 1% 3% NI 0·5% 1% 3%
Concentration Concentration
(a) (b)

Figure 6. Results for HPC and CC, not immersed in solutions (NI) and exposed to solutions of 0·5%, 1% and 3% of sulfuric acid for the
longest immersion period in: (a) compressive strength test; (b) Brazilian splitting test

Table 3. Weight variation of cylinders (C.) and discs (D.) after the solution. Even without the application of the phenolphthalein
longest immersion period solution on the surface of the HPC disc immersed for 56 d, it
0·5% sulfuric 1% sulfuric 3% sulfuric
is possible to observe two different regions. On the outside, an
acid acid acid altered layer shows signs of corrosion. When the phenolphtha-
lein solution was applied to this region, it became transparent,
C.HPC 0·52 ± 0·24 −11·33 ± 1·11 −71·44 ± 1·00
indicating changes in concrete pH due to contact with the
D.HPC 0·05 ± 0·11 −12·18 ± 1·90 −65·46 ± 2·44
C.CC 0·00 ± 0·14 −0·76 ± 0·01 −3·61 ± 0·60 sulfuric acid. The solution on the inner fraction, conversely,
D.CC −0·52 ± 0·17 −0·6 ± 0·13 −5·97 ± 1·07 remained almost unchanged, showing a pink coloration, indi-
cating that the pH remained high. On increasing the concen-
tration of the solution, the corrosive process increased for both
types of concrete. In addition, for both concretes, it was also
noted that, with the increase of immersion time, the outer
case, the gravel is quite visible and almost detached from the
cementitious matrix in some cases. layer seems to be thicker than that observed for an immersion
period of only 28 d. Thus, for the samples with the same con-
centration but different immersion periods, it was noticed that,
The size variations of both types of samples of HPC and
CC, as a result of the corrosive process were recorded. when the immersion time was increased, there was a greater
corrosion and consequently reduction of the non-corroded
The cylindrical samples of HPC in 0·5% (50·36 ± 0·07 mm),
concrete layer.
1% (48·62 ± 0·92 mm) and 3% (28·43 ± 0·70 mm) solutions
registered a higher loss of diameter as the concentration
As shown in Figure 8, the inner layer of the HPC disc samples
of sulfuric acid increased. Conversely, the variations in
exhibits a reduction in thickness. Therefore, in the case of the
cylindrical CC samples in 0·5% (49·90 ± 0·10 mm), 1%
(50·04 ± 0·06 mm) and 3% (49·43 ± 0·04 mm) solutions were HPC discs, it is plausible to consider that the corrosion
process by the acid solutions occurred in stages. As the outer
not significant. Thus, once again, a higher degradation of the
layers were corroded by sulfuric acid, these regions became
HPC samples was observed in comparison with the CC
samples. poorly adhered, and detached from the sample. As the loss
of material took place, the corrosive process advanced to a
new layer, moving towards the inner part of the sample.
Chemical and microstructural analysis Therefore, a great reduction of thickness occurred as the con-
To estimate the penetration depth of the acid, a phenolphtha- centration of sulfuric acid in the solution increased.
lein solution was sprayed on the specimens after testing. Conversely, for the CC disc samples, shown in Figure 9, an
Figures 8 and 9, respectively, show HPC and CC discs sub- increase in the thickness of the external layer of corroded
jected to two immersion periods in the 3% sulfuric acid material was observed. Thus, despite the action of the

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 Magazine of Concrete Research Concrete degradation mechanisms by
sulfuric acid attack
Torres, Souza, Silva and de Andrade Silva

(a) (b) (c) (d)

(d) (e) (f) (g)

Figure 7. Cylindrical samples of HPC analysed after 84 d of immersion: (a) reference without immersion; (b) 0·5%; (c) 1%; (d) 3%.
Cylindrical samples of CC analysed after 84 d of immersion: (e) reference without immersion; (f) 0·5%; (g) 1%; (h) 3%

corrosive process, much of the corroded outer layer did not
detach from the sample.
For the microstructural analysis, HPC and CC samples after
28 d of immersion in 3% solution were first analysed under
an optical microscope. Prior to observation under the micro-
scope, the samples had to be cut using a saw. This might have
caused a loss of material of the corroded layer of HPC, since it
already had a fragile structure. The images were captured at
the edge of the samples and reveal in detail the corroded and
non-attacked areas, as well as the limits between them, as
shown in Figure 10. The corroded layer of HPC is thin and
irregular, not allowing further analysis. However, in the CC
sample it is possible to note differences between the two
regions.
Therefore, for scanning electron microscopy, only the CC
sample was analysed. On examining the internal zone, appar-
ently without attack (Figure 11(a)), and the corroded region,
located in the external area (Figure 11(b)), a change in the

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 Magazine of Concrete Research
(a) (b)
Figure 8. HPC disc samples after immersion in the 3% sulfuric
acid solution for: (a) 28 d; (b) 56 d
(a) (b)
Figure 9. CC disc samples after immersion in the 3% sulfuric
acid solution for: (a) 28 d; (b) 84 d
surface is visible. The corroded area appears denser and with
irregular aggregates. By contrast, the inner area looks more
regular.
For analysis by X-ray diffraction, samples were first cured
for 28 d in water. In the reference samples of HPC and CC,
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Magazine of Concrete Research
Concrete degradation mechanisms by
sulfuric acid attack
Torres, Souza, Silva and de Andrade Silva
(a)
(b)
Figure 10. Optical micrographs of samples immersed for 28 d in
3% sulfuric acid solution: (a) HPC; (b) CC
as shown in Figures 12(a) and 12(b), respectively, peaks
were identified for calcium hydroxide and calcite. These
materials come from the hydration process of the cementitious
matrices. For the HPC concrete, a peak of silica was formed;
this peak is due to the dosage of HPC containing silica-based
additives.
Figures 12(a) and 12(b) also show the results for the HPC and
CC corroded material after the immersion process. It is
possible to notice that several gypsum peaks were formed for
both concretes, and that the peaks for calcium hydroxide and
calcite are no longer observed. The absence of these peaks in
the corroded material indicates that the process of dissolution
of these cementitious products occurred due to the reaction
with the sulfuric acid, consequently leading to the corrosion of
the concrete.
Recommendations for the design and
construction of sewage systems
The present study allowed the influence of the content of
cementitious materials of the mixtures to be associated with
 Magazine of Concrete Research Concrete degradation mechanisms by
sulfuric acid attack
Torres, Souza, Silva and de Andrade Silva

12 000

Gypsum
HPC
Reference

Gypsum

Gypsum
Corroded

Gypsum
8000

Gypsum
Silica
Count

Gypsum
Gypsum
4000

Silica
Silica

Calcite
CH

CH
0
0 20 40 60 80
(a)
2θ
(a)

12 000

Gypsum
CC
Reference
Gypsum

Gypsum
Corroded
Gypsum
8000 Gypsum
Count

Gypsum
Gypsum

4000
Calcite
CH
CH

Calcite
CH
CH

(b)
0
0 20 40 60 80
Figure 11. Scanning electron micrographs of CC sample:
(a) non-attacked area (internal); (b) corroded area (external) 2θ
(b)

Figure 12. X-ray diffractograms of material extracted from

the corrosion mechanisms of the concrete. There is a common
idea that a lower w/c ratio or the addition of other cementi-
tious components produces a more durable concrete, overall
more resistant to different deleterious processes. However, as
observed in the results this research and in the study of Amin
and Bassuoni (2018), concretes with a higher content of
cementitious materials, even though less permeable, presented
an increase in the loss of mass and strength. Higher contents
of cementitious materials led to higher volumes of cement
hydration products and these are directly attacked by sulfuric
acid attacks. Therefore, a higher w/c ratio (i.e. a lower cement
content) can improve the durability against sulfuric attack,
since there will be a smaller volume of cement hydration pro-
ducts and a larger percentage of siliceous material, which is
not reactive with the sulfuric acid.
Other solutions can be sought to increase the strength and
durability of concrete structures to sulfuric acid. The solutions
reference and corroded paste samples immersed for 7 d in 3%
sulfuric acid: (a) HPC; (b) CC. In both cases, peaks related to
gypsum were observed in the diffractograms of corroded samples
include the use of calcium aluminate cement (Alexander and
Fourie, 2011; Ehrich et al., 1999; Sand et al., 1994), replace-
ment of the aggregate (De Belie et al., 2004; Grengg et al.,
2015) and use of fibres as discrete reinforcement in order to
improve the resistance against expansive spalling of concrete
elements. Zhang et al. (2008) proposed solutions to control the
hydrogen sulfide emission, thus inhibiting the growth of the
aerobic bacteria that produce sulfuric acid. However, these
solutions are temporary and involve high costs.
Conclusions
As the immersion time in the sulfuric acid solutions increased,
a greater variation of the weight of the samples occurred. In

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 Magazine of Concrete Research
the same way, a reduction of the strengths of the two types of
concrete was registered by increasing the concentration and
time of immersion in the solutions, especially for the HPC
samples.
In this way, it was possible to perceive that the different con-
crete compositions showed different mechanical behaviours.
The CC did not present a great loss of mass. This was reflected
in the mechanical behaviour of the samples, since no signifi-
cant reductions of strength associated with immersion in 0·5%
and 1% solutions were recorded.
Conversely, the HPC concrete used in the study, owing to the
large volume of cement and consequently the higher formation
of hydration products, presented a great loss of material. This
leads to the weakening of the cementitious matrix and conse-
quently loss of mechanical resistance, observed mainly for
solutions with a higher concentration of sulfuric acid.
Likewise, the strength loss occurred more sharply compared
with the CC samples.
From the microstructural analysis it is possible to observe the
differences between the concretes after the corrosion process;
the HPC presented a more fragile structure than did the CC.
Finally, the results observed using X-ray diffraction analysis
demonstrated the occurrence of a dissolution process of cemen-
titious materials that led to the production of gypsum, as
described in several studies.
Thus, from the results collected during the study, it is possible
to conclude that the CC presents better behaviour in relation
to sulfuric acid chemical corrosion, as compared with HPC.
Acknowledgements
The authors gratefully acknowledge CNPq, CAPES and
FAPERJ (Brazilian National Science Foundations) for partial
financial support for this work.
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