Journal of Advanced Concrete Technology Vol. 7, No.

2, 273-283, June 2009 / Copyright 2009 Japan Concrete Institute 273

Technical report

Resistance of Mineral Admixture Concrete to Acid Attack

Shweta Goyal1, Maneek Kumar2, Darshan Singh Sidhu3 and Bishwajit Bhattacharjee4

Received 7 August 2008, accepted 7 April 2009

Abstract
The effect of an aggressive chemical environment on concrete prepared with ordinary Portland cement and silica fume,
either as a binary combination or a ternary combination with fly ash, is investigated in the present study. The adverse
environmental conditions are simulated by using either 1% sulfuric acid, 1% hydrochloric acid or 1% nitric acid. The
corrosion process was monitored by measuring the mass loss and compressive strength for a period of one year. It was
found that the course of action of acid attack is dependent on the type of acid and solubility of the calcium salt formed.
The presence of mineral admixtures was found to lower the detrimental effect of all types of acids on concrete. Ternary
mixes with OPC, silica fume and fly ash performed better than binary mixes containing only silica fume as supplemen-
tary cementitious material.

1. Introduction concrete. However, these materials are very expensive

Resistance to aggressive chemicals is the most impor-
tant engineering property of concrete governing its du-
rability. Chemical attack from external agents on con-
crete is the main reason for the loss of durability. ACI
Committee 201 has classified chemical attacks into: (i)
acidic attack, (ii) alkali attack, (iii) carbonation, (iv)
chloride attack, (v) leaching and (vi) sulfate attack
(Zivica and Bajza 2001). Among these chemical attacks,
acid attack on hardened concrete has drawn attention
only recently owing to the widespread damage caused
by acids to concrete structures worldwide. The major
cause of acid attack is the spread of acid sources due to
the growth of both urban and industrial areas (Zivica
and Bajza 2001), which results in acid media coming in
contact with concrete structures. The sources of acid
attack include natural acidic water, acidic waste water,
acid rain and silage effluents (Zivica 1999; Belie et al.
1997; Zivica and Bajza 2001). The alkaline nature of
concrete makes it highly vulnerable to acidic attack. The
acids attack calcium hydroxide and some hydration
products of the cement matrix, causing decomposition
of these products and consequent degradation of the
mechanical properties of concrete. Independent of their
type, no hydraulic cements exhibit satisfactory and
long-term resistance against acid attack. Concrete using
melted sulfur as a binder or polymer modified binders
are more acid resistant than hydraulic cement binder
1
Lecturer, Civil Engineering Department, Thapar
University, India.
E-mail:shweta@thapar.edu
2
Professor and Head, Civil Engineering Department,
Thapar University, India.
3
Research Associate, ISIS Canada Research Network,
University of Manitoba, Canada.
4
Professor, Civil Engineering Department, IIT Delhi,
India.
compared to normal concrete. Therefore, research into
improving acid resistance of normal concrete is still
attractive (Chang et al. 2005).
The resistance of the cement matrix to acid corrosion
depends primarily on its pore structure characteristics,
the ability of matrix components to neutralize acid and
also on the products of acid corrosion (Shi and Stege-
mann 2000). Among the major components leading to
acidic attack, mineral acids such as hydrochloric acid,
nitric acid and sulfuric acid are most dangerous for con-
crete. Sulfuric acid is highly corrosive due to the fact
that apart from the dissolution caused by hydrogen ions,
sulfate ions tend to initiate sulfate attack (Hewayde et al.
2007; Attiogbe and Rizkalla 1988; Ichitsubo et al. 2006;
Kawai et al. 2005). Sulfuric acid is found in concrete
sewer pipes due to the reaction between hydrogen sul-
fide and oxygen in the presence of aerobic sulfur oxidiz-
ing bacteria (Attiogbe and Rizkalla 1988; Ichitsubo et al.
2006). Natural ground water (Fattuhi and Hughes 1988
a), acid rain, etc., (Kong and Orbison 1987; Sersale et al.
1998) may also be source of sulfuric acid. Hydrochloric
and nitric acids are strong mineral acids that dissociate
completely and whose salts are highly soluble in water
(Shi and Stegemann 2000; Huang et al. 2005).
The use of supplementary cementitious materials
(SCM) in concrete has become very popular over the
last three decades due to their benefits in terms of sus-
tainability and economy. The use of SCM such as fly
ash and silica fume is believed to increase the durability
of concrete through pore refinement and the reduction
of calcium hydroxide content of the cement paste matrix.
However, the beneficial effect of these materials on
acidic attack is still under review. While some research
works point towards improvement through the use of
silica fume or fly ash (Kim et al. 2007; Sobolev and
Yeginobali 2005; Roy et al. 2001; Fattuhi and Hughes
1988 b; Kawai et al. 2005), others works report that
silica fume and fly ash have only little or no effect on
274 S. Goyal, M. Kumar, D. S. Sidhu and B. Bhattacharjee / Journal of Advanced Concrete Technology Vol. 7, No. 2, 273-283, 2009

the durability of concrete under acid attack (Pavlik
1996; Grube and Rechenberg 1989; Pavlik and Uncik
1997). Some of the authors attributed this lack of per-
formance of SCM to the reduction of Ca(OH)2, which
readily reacts with acid, thereby protecting the C-S-H
from the adverse affect of acid. The improvement re-
ported by some other authors may be due to the denser
and improved microstructure of concrete resulting from
SCM incorporation.
In this study, the effect of the water-to-binder ratio
and the presence of SCM on the resistance of concrete
against acidic attack have been investigated by consid-
ering three different mineral acids.
2. Materials
The physical and chemical properties of the various
materials used in the present work are highlighted below.
2.1 Cementitious material
ASTM Type I Portland cement was used throughout the
investigation. Silica fume and fly ash was used as the
SCM. The silica fume was procured from Elkem India
and the fly ash was collected from a local thermal power
plant. The chemical, physical and other important char-
acteristics of all cementitious materials are presented in
Table 1. The properties of the cement and fly ash have
been determined following Indian Standards (IS 4043:
part 1-15, IS 1786). Properties of the silica fume includ-
ing particle size have been provided by the manufac-
turer and are determined according to the relevant In-
dian standard.
2.2 Aggregates
Crushed granite with a maximum nominal size of 10
mm was used as coarse aggregate and natural river sand
conforming to Zone II of IS 383-1970 with a fineness
modulus of 2.52 was used as fine aggregate. The proper-
ties of the aggregates are listed in Table 2.
2.3 Superplasticizer
Polycarboxylic group based superplasticizer, Structro
100 (a product of Fosroc chemicals), was used to main-
tain required workability of the mix. The specific grav-
ity of the superplasticizer is 1.2 and the solid content is
40 percent by mass.
3. Experimental program
To explore the effect of the water-to-binder ratio on the
acidic resistance of concrete, the study was carried out
using three water binder ratios, 0.45, 0.35 and 0.25. The
three series obtained from these three water binder ra-
tios are designated as M1, M2 and M3 respectively. The

Table 1 Characteristics of binders used in this study.

Characteristic OPC Silica Fume Fly Ash
Normal consistency (%) 32 - -
Setting time Vicat (hour:minute) - -
Initial 2:10
Final 4:08
Specific gravity 3.12 2.2 2.42
Soundness: Le-Chatelier (mm) 1.5 - -
Fineness (% retained on 90 micron sieve) 3.2 - -
Mean particle diameter (m) 0.1 19.6
Specific surface (m2/kg)
Blain 287.8 - 250
Nitrogen adsorption 21,000
Lime reactivity (MPa) - 98 -
Compressive strength (MPa) - - -
fc (3 days) 26.5 - -
fc (7 days) 36.2 - -
fc (28 days) 47.3 - -
Chemical composition (%)
CaO 61.7 0.5 1.7
SiO2 22.4 90.7 56.8
Al2O3 5.93 0.68 25.8
Fe2O3 4.91 2.2 6.43
SO3 2.28 - 1.4
MgO 1.5 1.47 0.6
K 2O 0.65 0.9 0.79
Na2O 0.122 0.86 0.36
Loss on ignition 1.27 2.5 2.15
Insoluble residue 4.52 - 84.9
 S. Goyal, M. Kumar, D. S. Sidhu and B. Bhattacharjee / Journal of Advanced Concrete Technology Vol. 7, No. 2, 273-283, 2009 275

Table 2 Properties of aggregates.

Property Fine Aggregate Coarse Aggregate
Bulk density (kg/m3) 1.692 1.68
Relative density 2.54 2.64
Percentage absorption (%) 1.95 1.12
Sieve Analysis Results
Sieve Size Cumulative percentage retained (%)
20mm 0 0
10 mm 0 2.5
4.75 mm 5.05 92.8
2.36 mm 9.55 98.6
1.18 mm 17.6 100
600 44.6 100
300 80.15 100

mixes were designed per the British (DoE) guidelines. similar strength. The ternary mix however is more eco-
The details of the control concrete mixes are listed in nomical than the binary mix. The purpose of inclusion
Table 3. The three mixes chosen for each water-to- of both these mixes in the experimental scheme was to
binder ratio are control mix, binary mix containing 5% study the relative performance of the ternary mix vis--
of silica fume as replacement of cement, and ternary vis the binary mix against aggressive chemicals in expo-
mix containing a combination of 5% silica fume and sure.
15% fly ash as cement replacement. The basic proper- 150 mm size cubes were cast for all the mixes. Before
ties of these mixes are presented in Table 4, including immersion in the acidic medium, the specimens were
the standard 28 day cube compressive strength and 90 subjected to a realistic curing practice, in which the
day moist curing strength. In both cases, specimens specimens were cured in a water tank maintained at a
were cured continuously under water submerged condi- temperature of 27 2C for 7 days followed by con-
tion. From strength studies, it was observed that the tinuous air curing in the lab environment at around 27
binary mix with 5% silica fume, and the ternary mix 5C and 50 10% RH until the age of 90 days. This
with 5% silica fume and 15% fly ash, exhibit almost curing regime was chosen so that the specimens would
reach a consistent level of hydration before immersion
in the aggressive solution. After subjecting the speci-
Table 3 Mix proportions for control mixes. mens to the above-mentioned curing regime for three
Water Mix proportions (kg/m3) months, the specimens were kept in the respective ag-
binder Cement Aggregates Water gressive solutions for a period of up to one year.
ratio Fine Coarse
0.25 520 521 1340 130
4. Test solution and measurements
0.35 457 524 1283 160 In order to evaluate the prepared specimens against re-
0.45 422 557 1183 190 sistance to acid attack, they were exposed to three envi-
ronments, namely 1% sulfuric acid (H2SO4) solution,

Table 4 Details of mixes.

Mix type W/B Notation SCM (% Optimum SP Slump Compressive
replacement dosage (wt. % of (mm) strength (MPa)
of cement) binder)
SF FA 28 days 90 days
Control 0.45 M1-I - - 0.2 205 38.2 45.6
mixes 0.35 M2-I - - 1.25 211 69.3 72.5
0.25 M3-I - - 4 184 88.6 92.3
Binary 0.45 M1-II 5 - 0.3 194 49.4 55.4
mixes 0.35 M2-II 5 - 1.5 204 83.5 86.3
0.25 M3-II 5 - 3.75 196 104.9 108.3
Ternary 0.45 M1-III 5 15 0.1 198 46.5 53.4
mixes 0.35 M2-III 5 15 1 207 70.5 82.9
0.25 M3-III 5 15 3.25 205 92.2 104.2
W= water, C = cement, SCM =supplementary cementitious materials, SF = silica fume, FA = fly ash
276 S. Goyal, M. Kumar, D. S. Sidhu and B. Bhattacharjee / Journal of Advanced Concrete Technology Vol. 7, No. 2, 273-283, 2009
1% hydrochloric acid (HCl) solution, and 1% nitric acid
(HNO3) solution. The pH value obtained by using the
above-mentioned concentration of acids comes under
the category of strong chemical attack per DIN EN 206
Standard (Beddoe and Doner 2005). Although many
studies in the past have used pH value as an indicator of
aggressiveness, recently it has been observed that the
pH value being dependent on the degree of dissociation
of radicals, it may not be a true indicator of the concen-
tration of acid in the solution (Monteny et al. 2000;
Zivica and Bajza 2002). Therefore, in the present study,
the concentration is used directly as an indicator of the
aggressiveness of the exposure environment. The solu-
tion was renewed on a monthly basis in order to main-
tain uniform concentration and pH throughout the test-
ing period. The specimens were stored in 200 litre ca-
pacity drums with up to 6 specimens immersed in about
120-100 litres of solution. The test program was con-
cluded after 48 weeks. During this test period, meas-
urements were done to study the effect of aggressive
environments on the specimens. The tests were done in
triplicate to confirm the reproducibility of the test re-
sults.
4.1 Mass loss
The mass loss of specimens was monitored initially at
1-week intervals until 4 weeks, then at 2-week intervals
until 8 weeks, and then once every 4 weeks until the end
of the testing period of 48 weeks. Mass loss was meas-
ured using a balance with 0.5 gram sensitivity. At the
time of measurement, the cubes were rinsed with tap
water and brushed gently with a wire brush to remove
loose surface debris, and then dried at 105-110C for 48
hours or more until they attained nearly constant mass
indicated by negligibly small mass loss on further dry-
ing. After measurement, the cubes were returned to the
acid channel. The mass loss (ML) of material was then
determined as follows:
Wr Ws
ML = 100
Wr
where Wr is the average initial weight in grams of three
specimen before immersion in the acid solution (after
the end of initial curing regime) and Ws is the average
weight in grams of the specimens after it is immersed in
acid for the required period of time. A 48 hour drying
out period was applied.
4.2 Compressive strength loss
Mass loss is a simple traditional test in the context of
acid attack. However, mass change results may depend
on sample size and cement type, and are also influenced
by the way the decomposed cement paste and other re-
action products on samples are treated during testing
(Chang et al. 2005). Therefore, along with mass loss test,
compressive strength is considered to be a more reliable
measure to judge the performance of concrete subjected
to acid attack. Compressive strength is monitored at the
end of 8, 16, 24, 32, 40 and 48 weeks of exposure by
removing the specimen from the tank. The exposures
resulted in mass loss up to the depth about 3-4 mm from
the surface after cleaning and brush treatment. The sur-
face was finished again by applying a rich cement mor-
tar finish (1:3 cement mortars) i.e., end capping was
applied consistently for all specimens. The compressive
strength loss (CSL) is calculated as follows:
f cr f cs
CSL = 100 (2)
f cr
where f cr is the reference compressive strength of
specimen before immersion in the acid solution in MPa
and f cs is the average compressive strength of the
specimens after immersion in acid solutions for the re-
quired period of time.
5. Results and discussions
5.1 Behavior under sulfuric acid exposure
Figure 1 (a, b and c) presents the mass change data of
specimens as a function of time for different water-to-
binder ratios of 0.45, 0.35 and 0.25, respectively, when
exposed to 1% sulfuric acid. Figure 2 (a, b and c) pre-
sents the relative strength loss with respect to time for
all three water-to-binder ratios.
While analyzing mass loss, it was observed that irre-
spective of the water-to-binder ratio and type of mix, the
mass of specimens increased until around 4 to 5 weeks,
and thereafter decreased gradually. This initial mass
gain cannot be attributed to absorbed free moisture con-
tent of specimens as drying for 48 hours or more to
nearly constant mass would have removed the free
moisture present before weighing. However, chemically
combined water or adsorbed water (that is not removed
at 105-110C) after exposure could have also caused the
initial gain in mass. Further, when sulfuric acid comes
in contact with concrete, it reacts with portlandite and
calcium aluminate hydrate to form gypsum and ettring-
(1) ite, leading to an increase in initial weight. This is ex-
pressed in the following reaction (Monteny et al. 2000)
H 2SO 4 + Ca(OH) 2 CaSO 4 .2H 2O
(3)
portlandite gypsum
3(CaSO 4 .2H 2O) + 3CaO.Al2O 3 .12H 2O +14H 2O
calcium alumnate hydrate
(4)
3CaO.Al2O 3 .3CaSO 4 .32H 2O
ettringite
The solubility of the calcium sulfate (CaSO4) so
formed is low (0.22 gm/100 gm of water at 0C) (Pavlik
1994; Zivica and Bajza 2001) and therefore its dissolu-
tion does not take place. On the other hand, these reac-
tion products have very low structural stability in com-
parison to the reactants they replace. They involve an
increase in volume and therefore occupy the space
available as voids in concrete, leading to an increase in
 S. Goyal, M. Kumar, D. S. Sidhu and B. Bhattacharjee / Journal of Advanced Concrete Technology Vol. 7, No. 2, 273-283, 2009 277

25 80

Compressive strength loss (%)

M1-I M1-I
20 70
M1-II M1-II
Mass loss (%)

60
15 M1-III M1-III
50
10
40
5 30
0 20
0 4 8 12 16 20 24 28 32 36 40 44 48 52
-5 10
0
-10
0 4 8 12 16 20 24 28 32 36 40 44 48 52
Exposure time (weeks)
Exposure time (weeks)
(a) w/c ratio 0.45 (a) w/c ratio 0.45
30 70

Compressive strength loss (%)

M2-I M2-I
25 60
M2-II M2-II
20 50
M2-III M2-III
Mass loss (%)

15
40

30
10
20
5
10
0
0 4 8 12 16 20 24 28 32 36 40 44 48 52 0
-5 0 4 8 12 16 20 24 28 32 36 40 44 48 52
Exposure time (weeks)
Exposure time (weeks)
(b) w/c ratio 0.35 (b) w/c ratio 0.35

40 70
Compressive strength loss (%)

35 M3-I M3-I
60
M3-II M3-II
30
Mass loss (%)

M3-III 50
25 M3-III
40
20
15 30

10 20
5 10
0 0
-5 0 4 8 12 16 20 24 28 32 36 40 44 48 52 0 4 8 12 16 20 24 28 32 36 40 44 48 52
Exposure time (weeks)
Exposure time (weeks)
(c) w/c ratio 0.25 (c) w/c ratio 0.25

Fig. 1 Weight loss of specimens under sulfuric acid Fig. 2 Compressive strength loss of specimens under
exposure. sulfuric acid exposure.

initial weight. However, after some time, the continued the mass loss of concrete that starts after approximately
expansion causes cracking that ultimately leads to peel- one month of exposure to the sulfuric acid solution.
ing off of the surface layer of concrete, as indicated by
278 S. Goyal, M. Kumar, D. S. Sidhu and B. Bhattacharjee / Journal of Advanced Concrete Technology Vol. 7, No. 2, 273-283, 2009
(1) Effect of water-to-binder ratio
While comparing the effect of water-to-binder ratio on
the deterioration caused by the sulfuric acid solution, it
was observed that the mass loss and strength loss ex-
hibit contradictory outcomes. When the ultimate mass
loss and compressive strength loss of all three mixes
prepared with three water-to-binder ratios at the end of
48 weeks was compared, (Fig. 3 and Fig. 4), it was no-
ticed that for all the mixes, while mass loss increases
with decreases in the water-to-binder ratio, the compres-
sive strength loss decreases with decreases in the water-
to-binder ratio. In fact, with decreases in the water-to-
binder ratio, a combination of opposite effects takes
place. On the one hand, due to the lower water-to-binder
ratio, porosity decreases, which implicates lower corro-
sion, whereas on the other hand, the relative amount of
cement increases, which implicates higher corrosion
(Monteny et al. 2000). Mass loss is a surface phenome-
non and therefore, reflects only one effect of water-
binder-ratio lowering, i.e. a relative increase in cement
content that leads to greater formation of gypsum on the
surface layer, causing expansion and ultimately disrup-
tion of the surface layer. Also, due to brushing of the
specimens, the loose debris is removed, leading to more
40
35
Mass loss (%)
30
25
20
15
10
5
0
Control
Mixes
Fig. 3 Final mass loss of mixes at different water-to-
binder ratios exposed to sulfuric acid.
80
Compressive strength loss (%)
70
60
50
40
30
20
10
0 The ultimate weight loss and compressive strength loss
Control
Fig. 4 Final strength loss of mixes at different water-
to-binder ratios exposed to sulfuric acid.
reduction in weight with decreases in the water-to-
binder ratio. On the other hand, strength measurement
takes into consideration the properties of the concrete
matrix as a whole. Lower strength loss indicates that
although the mass loss is high, the deterioration has
taken place only on the surface and the inner matrix is
still unaffected by the acid attack. This shows that low-
ering of the water-to-binder ratio is beneficial in acidic
attack. A contradictory view is presented in some re-
search works that conclude that the rate of corrosion is
increased with decreases in water cement ratio (Pavlik
and Uncik 1997; Hewayde et al. 2007; Fattuhi and
Hughes 1988 a). In these works, only mass loss is taken
as the parameter for judging corrosion. This leads to the
conclusion that mass loss is not a reliable index for
measuring efficiency against acidic media and can lead
to misleading conclusions.
(2) Effect of SCM
At the same water-to-binder ratio, the use of supplemen-
tary cementitious materials helps in arresting both mass
loss and compressive strength loss. With the addition of
SCM, due to the pozzolanic reaction, permeability is
reduced, which helps reduce the detrimental effect of
the sulfuric acid solution. On comparing binary mixes
containing only silica fume and ternary mixes contain-
0.45 0.35 0.25 ing a combination of silica fume and fly ash, it is found
that ternary mixes are better in terms of resistance to
sulfuric acid attack than binary mixes containing similar
percentage of silica fume.
5.2 Behaviour under hydrochloric acid expo-
sure
Figure 5 (a, b and c) presents the mass change data of
specimens as a function of time at water-to-binder ratios
of 0.45, 0.35 and 0.25 respectively, when exposed to 1%
BS1 TC1
hydrochloric acid, whereas Fig. 6 (a, b and c) presents
relative strength loss with respect to time for all three
water-to-binder ratios.
One particular observation that is unique to hydro-
chloric acid attack is the identification of brownish belts
on the surface of specimens (Chandra 1988; De Ceuke-
laire 1992). These belts are probably due to the presence
0.45 0.35 0.25 of ferric hydroxide. A similar observation was also
made by other researchers (Chandra 1988; De Ceuke-
laire 1992). Further, with the passage of time, the sur-
face layer, in the case of hydrochloric acid attack, is
completely peeled off. Due to the peeling off of the sur-
face, the specimens undergo a higher amount of mass
loss compared to what is experienced in sulfuric acid
attack.
(1) Effect of water-to-binder ratio
BS1 TC1 of all the three mixes prepared at three water-to-binder
Mixes ratios at the end of 48 weeks is compared in Figs. 7 and
8, respectively. It is observed from the figures that with
decreases in water-to-binder ratio, mass loss increases
 S. Goyal, M. Kumar, D. S. Sidhu and B. Bhattacharjee / Journal of Advanced Concrete Technology Vol. 7, No. 2, 273-283, 2009 279

and compressive strength loss decreases. This observa-
tion echoes that made in the case of sulfuric acid attack.
However, the difference in the values is not as high as
the ones observed in the case of sulfuric acid attack,
which indicates that hydrochloric acid attack does not
depend much on the variation in water-to-binder ratio.
The phenomenon of sulfuric acid and that of hydrochlo-
ric acid attack are different. In fact, the mechanism of
concrete deterioration by acidic attack can be schemati-
cally represented as shown in Fig. 11. As can be seen in

35 45
M1-I

Compressive strength loss (%)

30 40 M1-I
M1-II
Mass loss (%)

35 M1-II
25 M1-III
30 M1-III
20
25
15 20
10 15
10
5
5
0
0
0 4 8 12 16 20 24 28 32 36 40 44 48 52
0 4 8 12 16 20 24 28 32 36 40 44 48 52
Exposure time (weeks)
Exposure time (weeks)
(a) w/c ratio 0.45 (a) w/c ratio 0.45
40
40
Compressive strength loss (%)

M2-I
35 M2-I 35
M2-II
Mass loss (%)

30 M2-II 30
M2-III M2-III
25 25
20 20
15
15
10
10
5
5
0
0 4 8 12 16 20 24 28 32 36 40 44 48 52 0
0 4 8 12 16 20 24 28 32 36 40 44 48 52
Exposure time (weeks)
Exposure time (weeks)
(b) w/c ratio 0.35 (b) w/c ratio 0.35
50 35
Compressive strength loss (%)

45 M3-I
M3-I 30
Mass loss (%)

40 M3-II
M3-II
35 25 M3-III
M3-III
30
20
25
20 15
15 10
10
5 5
0 0
0 4 8 12 16 20 24 28 32 36 40 44 48 52
0 4 8 12 16 20 24 28 32 36 40 44 48 52
Exposure time (weeks)
Exposure time (weeks)

(c) w/c ratio 0.25 (c) w/c ratio 0.25

Fig. 5 Weight loss of specimens under hydrochloric Fig. 6 Compressive strength loss of specimens under
acid exposure. hydrochloric acid exposure.
280 S. Goyal, M. Kumar, D. S. Sidhu and B. Bhattacharjee / Journal of Advanced Concrete Technology Vol. 7, No. 2, 273-283, 2009
50
45
40
Mass loss (%)
35
30
25
20
15
10
5 terials helps in arresting both mass loss and compressive
0
Control
Mixes
Fig. 7 Final mass loss of mixes at different water-to-
binder ratios exposed to hydrochloric acid attack.
45
Compressive strength loss (%)
40
35
30
25
20
15
10
5 While analyzing the mass loss and compressive strength
0 loss of all three mixes prepared with three different wa-
Control
Mixes
Fig. 8 Final compressive strength loss of mixes at dif-
ferent water-to-binder ratios exposed to hydrochloric
acid attack.
this figure, there are two courses of action in acidic at-
tack. The first course of action is the one in which the
salt formed is soluble and hence can be leached out,
which has a major effect on mass loss without introduc-
ing any internal stresses that can cause micro cracking
and hence major loss of strength. This course of action
is adopted during hydrochloric acid attack, in which
when calcium hydroxide dissolves in acid, the reaction
product that is formed is calcium chloride, which is
highly soluble in water (279.3g/100g of water at 0C)
and therefore is leached out of the mortar without form-
ing micro cracks that can affect the internal structure
and hence the strength characteristics of concrete. This
type of action has more effect on the mass loss, as has
been observed from the peeling off of the surface of
specimens in hydrochloric acid attack. On the other
hand, the second course of action is the one in which
reaction products are not soluble but are expansive in
nature, which therefore can cause micro cracking and
high loss of strength and lesser mass loss. This course of
action is adopted by sulfuric acid attack, as has already
been explained. Therefore, while the mass loss is greater
0.45 0.35 0.25 in hydrochloric acid attack due to continuous leaching
of the reaction products, the strength loss is very small
compared to the loss observed in sulfuric acid attack.
(2) Effect of SCM
Similar to the observation made in sulfuric acid attack,
Figs. 5 and 6 show that for the entire water-to-binder
ratio range, the use of supplementary cementitious ma-
strength loss. At each water-to-binder ratio, the mass
loss and compressive strength loss of ternary mixes with
BS1 TC1
a combination of silica fume and fly ash is lesser than
the corresponding binary mixes with only silica fume as
the mineral admixture. This shows that ternary mixes
perform better than binary mixes in hydrochloric acid
exposure also.
5.3 Behaviour under nitric acid exposure
Figure 9 (a, b and c) presents the mass loss data of
0.45 0.35 0.25 specimens as a function of time at the water-to-binder
ratios of 0.45, 0.35 and 0.25, respectively, when ex-
posed to 1% nitric acid, whereas Fig. 10 (a, b and c)
presents the relative strength loss with respect to time
for all three water-to-binder ratios.
(1) Effect of water-to-binder ratio and mineral
admixtures
BS1 TC1 ter-to-binder ratios, it is clear that the effect of nitric
acid is similar to the effect of hydrochloric acid attack,
with the only difference being that the strength losses
are comparatively lesser in nitric acid attack. This may
be due to the higher solubility of calcium chloride
(279.3g/100g of water at 0C) compared to calcium
nitrate (266g/100g of water at 0C) (Pavlik 1994).
However, the difference in solubility is very small and
therefore, the presence of some other factor cannot be
overruled. A detailed investigation considering other
parameters that involves microstructural studies is in
order for a clearer understanding of nitric acid attack.
5.4 Additional discussions on performance of
SCM
The service life of reinforced concrete (RC) elements
with reference to acid attack may be considered as the
time required for reduction of the cover depth to an un-
acceptable level due to mass loss or the time at which
loss of strength and section area renders the RC element
unacceptable due to reduction in its load carrying capac-
ity, whichever occurs earlier. Thus both mass loss and
strength loss are relevant performance indicators against
acid attack. Incorporation of SCM in concrete makes
concrete less porous and hence more impervious. Pore
sizes also become finer. On the other hand, it also re-
sults in reduction in Ca(OH)2. The C-S-H gel when ex-
 S. Goyal, M. Kumar, D. S. Sidhu and B. Bhattacharjee / Journal of Advanced Concrete Technology Vol. 7, No. 2, 273-283, 2009 281

35 40

Compressive strength loss (%)

M1-I 35 M1-I
30
Mass loss (%)

M1-II M1-II
30
25
M1-III M1-III
25
20
20
15
15
10
10
5
5
0
0
0 4 8 12 16 20 24 28 32 36 40 44 48 52
0 4 8 12 16 20 24 28 32 36 40 44 48 52
Exposure time (weeks)
Exposure time (weeks)

(a) w/c ratio 0.45 (a) w/c ratio 0.45

40 35

Compressive strength loss (%)

35 M2-I M2-I
30
M2-II M2-II
Mass loss (%)

30
M2-III 25
M2-III
25
20
20
15
15

10 10

5 5
0
0
0 4 8 12 16 20 24 28 32 36 40 44 48 52
0 4 8 12 16 20 24 28 32 36 40 44 48 52
Exposure time (weeks)
Exposure time (weeks)

(b) w/c ratio 0.35 (b) w/c ratio 0.35

40 30
Compressive strength loss (%)

M3-I M3-I
35
25 M3-II
Mass loss (%)

M3-II
30
M3-III 20 M3-III
25
20 15
15
10
10
5 5

0 0
0 4 8 12 16 20 24 28 32 36 40 44 48 52 0 4 8 12 16 20 24 28 32 36 40 44 48 52

Exposure time (weeks) Exposure time (weeks)

(c) w/c ratio 0.25 (c) w/c ratio 0.25

Fig. 9 Weight loss of specimens under nitric acid Fig. 10 Compressive strength loss of specimens under
exposure. nitric acid exposure.

posed to an acidic environment in the absence of alka- and hence mass loss at the surface than a concrete that is
line materials may be less stable and hence disintegrate. less impervious but more alkaline. Thus performance,
For an impervious concrete having reduced alkalinity, when based on surface mass loss, in some cases is likely
the surface is more vulnerable to surface disintegration to exhibit poor performance for concrete that incorpo-
282 S. Goyal, M. Kumar, D. S. Sidhu and B. Bhattacharjee / Journal of Advanced Concrete Technology Vol. 7, No. 2, 273-283, 2009
rates SCM compared to concrete that does not. Further,
concrete with a denser microstructure would exhibit
more resistance against mass loss as well. Thus in some
cases, one may experience better performance of con-
crete incorporating SCM concrete from a mass loss
viewpoint as well. Strength on the other hand is a func-
tion of porosity and pore size. Strength declines with
increases in porosity and pore size. Thus an impervious
concrete would provide protection against leaching and
increases in porosity and pore sizes. Hence, judged on
the basis of strength loss, concrete that incorporates
SCM will always exhibit better performance in acid
attack. The results obtained in this work thus indicate
better performance for concrete that incorporates SCM.
6. Conclusions
Based on the experimental study carried out to access
the detrimental effect of acid attack on concrete made
with and without supplementary cementitious materials,
the following conclusions can be drawn.
(1) Mass loss alone is not a reliable index to measure
the durability of concrete in acid attack and must
be supplemented by strength studies.
(2) The presence of SCM lowers the detrimental effect
of all types of acids on concrete. Among binary
and ternary mixes, ternary mixes perform better
than binary mixes containing only silica fume as
mineral admixture.
(3) The course of action of acid attack is dependent on
the type of acid present. In the case of hydrochloric
acid and nitric acid attack, the calcium salt formed
is soluble in water, leading to higher mass loss. On
the other hand, in the case of sulfuric acid attack,
the calcium salt formed is not soluble in water, get-
ting deposited in the voids and causing internal
stresses leading to disruption and strength loss of
the matrix.
Acknowledgements
This research has been supported by Department of Sci-
ence and Technology (DST) Grant No. 92780. The au-
thors would like to acknowledge the authorities con-
cerned for their assistance in carrying out the research.
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