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Acids attack on silica fume concrete

CONFERENCE PAPER · DECEMBER 2012

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Sriravindrarajah Rasiah
University of Technology Sydney
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Acids attack on silica fume high-strength concrete
R. Sri Ravindrarajah
Centre for Built Infrastructure Research, University of Technology, Sydney, Australia

ABSTRACT: This paper reports the results of a study on the corrosion of high strength concrete with silica
fume subjected to 15% concentration of sulphuric acid, hydrochloric acid and lactic acid. Silica fume were
used to replace 8% and 15% of the cement, by weight. The results showed that partial replacement of cement
with silica fume had no effect on lactic acid resistance, improved the hydrochloric acid resistance and
worsened the sulphuric acid attack. Sulphuric acid attack resulted in concrete disintegration at an almost
constant rate, the hydrochloric attack rate was reduced with time, whereas the lactic acid attack resulted
leaching of corrosion products, at a slower rate under stagnant condition.

1 INTRODUCTION ed to attack by lactic acid and acetic acid, formed in

spilled and soured meal-water mixtures.
Portland cement concrete is the most commonly
This paper reports the results on an investigation
used construction material for sewer system. How-
into the resistance of concrete (with and without
ever, deterioration of sewer pipes is not uncommon
silica fume) to hydrochloric acid, sulphuric acid and
due acid attack on alkaline concrete by biogenic sul-
lactic acid with time in a stagnant condition.
phuric acid (BSA), which is highly ionized mineral
acid and may results in pH less than 2. Monteny et. 1.1 Acids attack on concrete - past research
al. (2000) characterized the sulphuric acid attack by Torii and Kawamura (1994) investigated the effects
the following chemical reactions: of replacing cement with high fineness silica fume, a
Ca(OH)2 + H2SO4 = CaSO4.2H2O super-pozzolan, on compressive strength, total pore
3CaO.Al2O3.12H2O + 3(CaSO4.2H2O) + 14H2O = volume and calcium hydroxide content of mortar.
3CaO.Al2O3.3CaSO4.32H2O Table 1 summarizes their results for the physical
3CaO.SiO2.3H2O + H2SO4 = CaSO4 2H2O+ Si(OH)4 chemical properties of 28-day mortar.
The primary corrosion product formed on the
concrete surface is gypsum, an expansive product, Table 1. Properties of 28-day old silica fume mortars (Torii
which results cracking and spalling of concrete. In and Kawamura (1994))
addition, the reaction of gypsum with calcium Silica W/C Comp Total Pore vol. Ca(OH)2
aluminate phases in the cementitious matrix can fume Str. Pore vol. > 0.1 m to (%)
form highly expansive ettringite, leading to micro- (%) MPa (10-3 Total (%) by wt.
cc/g)
and macro-cracking in concrete. The main hydration
0 0.55 45.3 39.8 17.6 4.1
product of calcium silicates, namely C-S-H gel, re- 5 0.55 44.4 50.7 13.8 3.1
acts with the sulphuric acid to form silica gel. 10 0.54 45.1 36.1 11.6 2.3
In a similar way, the chemical reactions involved 20 0.54 46.6 29.0 29.0 1.3
in hydrochloric acid attack on concrete are given by: 30 0.53 50.2 28.4 28.4 0.8
Ca(OH)2 + HCl = CaCl2 + 2 H2O
3CaO.SiO2.3H2O + HCl= CaCl + Si(OH)4 The results show that the pore structure of silica
Lactic acid is commonly associated with the fume mortar is dense and homogeneous when
handling of milk, buttermilk and cheese, but also compared to plain mortar mix. 28-day compressive
present in various fermentation processes with acetic strength of mortar with 30% silica fume was higher
acid. It is highly destructive to concrete through its than that for the control mortar. In addition, the
reaction with lime in concrete to form soluble calcium hydroxide content was decreased from 4.1%
materials. Concrete floors in pig houses are subject- for the control mortar to 0.8% for mortar with 30%
silica fume.
 Table 2 shows the effect of sulphuric acid attack phases on self-compacting concrete. In phase I ex-
on the pore volume for mortar incorporating silica posure with pH threshold of 2.5 for 6 weeks, an im-
fume. The total pore volume and the amount of pore proved performance in the acid resistance was
volume greater than 0.1 m were found to increase achieved using binary, ternary and quaternary bind-
notably. Both, the principal corrosion product ers, primarily due to dilution effect of cement. In
gypsum and calcium hydroxide in the corroded phase II exposure with a pH threshold of 1.0, the
portion of the mortar were decomposed and significant mass loss was due to decomposition of
disappeared. the hydration product, C-S-H.
Yoshida et. al. (2010) studied the sulphuric acid
Table 2. Total pore volume of silica fume mortar after 1-year attack on concrete with and without blast furnace
in sulphuric acid (Torii and Kawamura (1994)) slag. The results showed that slag concrete had
Silica In water In 2% sulphuric acid
fume Total Pore Pore vol.
significantly increased the resistance of concrete to
Tot. Pore Pore vol.
(%) vol. (10-3 > 0.1 m to vol. (10-3 > 0.1 m acid attack. The weight loss after 26 weeks of acid
cc/g) total (%) cc/g) to total attack was reduced from 82% for the control
(%) concrete to 45% for the concrete with 60% slag con-
0 33.8 22.1 47.0 45.7 tent in the blended cement. This indicates that the
5 30.1 11.6 57.2 43.3 sulphuric acid attack is closely related to Ca(OH)2
10 44.7 22.6 66.7 40.5
20 33.8 17.8 21.1 32.2
content in the concrete.
30 17.8 36.5 26.7 33.7 De Ceukelarie (1992) observed that the changing
mineralogy due to leaching processes causing
Table 3: Sulphuric acid attack on silica fume concrete strength loss in concrete subjected to hydrochloric
(Sri Ravindrarajah and Mercer (1993)) acid attack. Zivica (1999) reported that the use of
Cement Silica 560-day Weight loss (%) chemically modified silica fume was found to reduce
(%) Fume Cube str. after 12 weeks the intensity of hydrochloric acid attack.
(%) (MPa) 5% H2SO4 15% H2SO4
100 0 89.7 54.1 51.5
De Belie et. al. (1997) studied the corrosion of
92% 8 76.9 61.5 68.9 concrete subjected to a combination of lactic and
85% 15 102.1 60.2 60.9 acetic acids, as a function of the binder materials
types. They found that the addition of 10% fly ash
Sri Ravindrarajah and Mercer (1993) investigated by weight of cement to a high-quality concrete made
the sulphuric acid attack on 560-day old high with cement had significantly reduced the corrosion
strength concrete. Tables 3 and 4 summarizes the of concrete by these organic acids.
weight loss in concrete specimens after exposing to
5% (pH = 0.54) and 15% (pH = 0.08) sulphuric acid 2 EXPERIMENTAL INVESTIGATION
for 12 weeks. 2.1 Materials
Table 4. Curing effect on sulphuric acid attack on silica fume General purpose cement confirming to AS3972 was
concrete (Sri Ravindrarajah and Mercer (1993)) used in the production of the high strength concrete
Cement Silica H2SO4 Weight loss (%) mixes. Condensed silica fume from Norway was
(%) Fume (%) after 12 weeks used in two of the mixes. Table 5 shows the compo-
(%) Water-cured Air-stored
100 0 5 54.1 40.1
sitions of the concrete mixes used for acid resistance
100 0 15 51.5 29.1 test. The silica fume content was 0%, 8% and 15%
92 8 5 61.5 53.2 of the of the binder materials, by weight. A high
92 8 15 68.9 48.0 range water reducing admixture (superplasticiser)
was used to obtain workable concrete mixes.
The sulphuric acid attack on matured high
strength concrete was: (a) increased when cement Table 5. Compositions for the high-strength concrete mixes
was partially replaced with silica fume and fly ash; Mix Cement Silica Silica Agg. Water
(b) generally increased with the increase in the acid (kg/m3) Fume Fume (kg/m3) (kg/m3)
(kg/m3) (%)
concentration; and (c) increased for moist-cured 1 500 0 0 1805 150
concrete. The increased acid attack for silica fume 2 460 40 8 1815 180
concrete may be partly due to the increased amount 3 410 90 15 1815 138
of acid sensitive C-S-H gel due to pozzolanic reac-
tions of reactive silica and lime. Similar observa- 2.2 Casting, curing & testing of concrete specimens
tions with silca fume concrete were reported by Me-
High strength concrete mixes were prepared in a pan
hta (1978), Berke (1989), Yamato et. al. (1989), and
type concrete mixer and a number of 100mm diame-
Sri Ravindrarajah (1992).
ter by 200mm high cylindrical specimens were cast
Bassuoni and Nehdi (2007) studied the effect of
in steel moulds for compressive strength test and
cement replacement with silica fume, fly ash, slag
acid resistance tests. A vibrating table was used to
and limestone on the sulphuric acid attack in two
obtain full compaction in the cast specimens. The
specimens were demoulded after 24 hours of casting
and stored either in water at 20oC or in laboratory
conditions of 20 + 2oC and 60 + 10 % R.H. until
testing.
The compressive strength of high strength con-
crete mixes at 28 days was about 80MPa. The corro-
sion resistance of concrete to 15% concentration of
hydrochloric acid, sulphuric acid and lactic acid
were carried out on 6 months old water-cured and
air-stored concrete cylindrical specimens. During
the acid resistance test, one-half of the 200mm high
cylinders were immersed in the acid solutions in
separate plastic containers in the laboratory envi-
acid is expected to be the highest due to very low
pH.
Figures 1 to 3 show the weight loss for the high
strength concrete, with and without silica fume due
to corrosion of concrete by hydrochloric acid, sul-
phuric acid and lactic acid. The corrosion rate is
found to be affected by the type of acid. Sulphuric
acid attack on high strength concrete was more
severe compared to hydrochloric acid and lactic ac-
id. In addition, a steady rate of acid corrosion was
recorded with sulphuric acid.
25
20
0% SF

Weight Loss (%)

ronment. The corrosion test specimens were re- 8% SF
moved from the acid solutions at 7 days interval and 15 15% SF
subjected to wire-brush cleaning under running tap
water to remove the corrosion products. This proce- 10
dure subjected new concrete surface to acid attack.
The specimens were surface dried and weighed to 5
determine the weight loss, which indicates the inten-
sity of acid attack on concrete. 0
0 10 20 30 40
Table 6: Changes in pH of the acid solutions (15% )
Type of Acid Initial pH pH after 14 days Duration (days)
Hydrochloric 0.22 1.97 Figure 2. Sulphuric acid attack on silica fume concrete
Lactic 1.78 3.25
Sulphuric 0.08 0.36
6
At the end of 14 days, the acid solutions were 5 0% SF
Weight loss (%)

discarded and new solutions were used to maintain 4 8% SF

the concentration of the acid. The changes in pH of
the acid solutions after 14 days of corrosive activity 3 15% SF
are given in Table 6. It was not possible to maintain 2
the same pH throughout the acid resistance test. 1
Although the concentration of the acids was the 0
same, pH of them was found to vary noticeably. 0 5 10 15 20 25
7 Duration (days)
6 Figure 3. Lactic acid attack on silica fume concrete
Weight loss (%)

5
4 After 21 days of exposure to lactic acid, the
3 0% SF
8% SF
2
1 15% SF
0 the hydration products of cement and the soluble
0 10 20 30
Duration (days)
Figure 1. Hydrochloric acid attack on silica fume concrete
3 RESULTS AND DISCUSSION
3.1 Effect of acid type on acid resistance of concrete
Sulphuric acid solution had the lowest pH of 0.08
compared to 1.78 for the lactic acid solution and
0.22 for the hydrochloric acid solution. Considering
the acidity of these acids, the attack by the sulphuric
weight loss for high strength concrete specimens
was around 5.0%. During the first 14 days, the pH of
lactic acid solution was found to increase from 1.78
to 3.25. This indicates that the lactic acid attacked
40 corrosion products diluted the acid solution. The ini-
tial corrosion rate for concrete by lactic acid is low
and once the new surface was exposed by the re-
moval of the corrosion products and the new lactic
acid solution was replaced the diluted acid, the rate
of corrosion was increased significantly, as seen
from Figure 3..
Figure 4 shows the high-strength concrete surface
which was subjected to sulphuric acid after 20
weeks of acid exposure. The sulphuric acid attack
was very severe and significantly high intensity of
concrete corrosion was observed. Once the interfa-
cial bond between the aggregate particles and ce-
ment paste was weakened by the acid attach, the
wire brushing action removed any loose aggregate
particles and contributed to increased weight loss as
observed by Sri Ravindrarajah and Mercer (1993).
Figure 4. 15% Sulphuric acid attack on high-strength concrete
after 20 weeks
Figure 5. 15% Lactic acid attack on high-strength concrete af-
ter 20 weeks
Less corrosive acids such as hydrochloric acid
and lactic acid were unable to dislocate a significant
amount of aggregate particles from the concrete, as
seen from Figure 5. The acid attack caused precipi-
tation of white corrosion products at the surface of
the concrete and some loss in the surface mortar was
observed. However, there was no loss of aggregate
from the concrete.
3.2 Effect of cement replacement by silica fume on
acid resistance of concrete
It is well-known that the use of silica fume in con-
crete decreases the permeability of concrete through
pore volume reduction and pore-size modification
due to the pozzolanic reaction of reactive silica with
calcium hydroxide, as shown in Table 1. In addition,
silica fume also reduces the calcium hydroxide con-
tent in concrete. However, C-S-H gel component in
silica fume concrete is increased and this in turn im-
proves the strength of concrete.
When silica fume concrete is subjected to high
concentration of corrosive acids such as sulphuric
acid, C-S-H gel is attacked by the acids and concrete
corrosion is becoming more significant. As the re-
sults, strength and stiffness of the attacked part of
the concrete specimens are seriously reduced, result-
ing cracking and spalling.
The results shown in Figure 1 to 3, clearly indi-
cates that the acid resistance of concrete containing
silica fume is dependent on the type of acid used.
Figure 3 shows that the lactic acid attack on high
strength concrete is insensitive to the cement re-
placement by 8% or 15% by silica fume.
The hydrochloric acid resistance to high strength
concrete is improved with the increase in the cement
replacement with silica fume (Figure 1). However,
the sulphuric acid attack is increased when cement
was partially replaced with silica fume (Figure 2).
This confirms finding of Mehta (1978), Berke
(1989), Yamato et. al. (1989).
4 CONCLUSIONS
Based on the reported results on the acid resistance
of high-strength concrete with silica fume the fol-
lowing conclusions are made.
(a) Acid attack on high strength concrete, with and
without silica fume, is mainly influenced by the
type of acid, even though they may have the
same high concentration of 15%.
(b) Lactic acid is the least corrosive acid and the
soft and soluble corrosion products formed rap-
idly at the acid-exposed concrete surface to neu-
tralise the acidity of the lactic acid solution.
(c) Hydrochloric acid attack is not severe and
slowed down with exposure time.
(d) Sulphuric acid attack is very severe and signifi-
cant weight loss was recorded. The depth of
corrosion increased due to the degradation of
the interfacial bond between aggregate particles
and cement paste matrix.
(e) Partial replacement of cement with silica fume
up to 15% by weight caused: (i) no effect on the
lactic acid attack; (ii) reduced the hydrochloric
acid attack; and (iii) worsened the sulphuric ac-
id attack.
(f) The general opinion of improved durability of
concrete by incorporating silica fume is found to
have serious limitation when even the high
strength concrete is subjected to acidic envi-
ronment.
5 REFERENCES
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