Construction and Building Materials 43 (2013) 80–86

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Construction and Building Materials

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Sulfuric acid resistance of blended ash geopolymer concrete

M.A.M. Ariffin a, M.A.R. Bhutta b,⇑, M.W. Hussin b, M. Mohd Tahir b, Nor Aziah c
a
Faculty of Civil Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor Bahru, Malaysia
b
UTM Construction Research Centre (UTM CRC), Faculty of Civil Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor Bahru, Malaysia
c
Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor Bahru, Malaysia

h i g h l i g h t s

" Geopolymer concrete prepared with blended ash (PFA + POFA), activated by alkaline solution and 1.5 year 2% H2SO4 exposure.
" The evaluation of acid resistance in terms of visual appearance, mass change and compressive strength was examined.
" The effect of H2SO4 investigated by XRD, FTIR, TGA/DTG, SEM.
" H2SO4 exposed geopolymer concrete was superior to OPC, due to more stable cross-linked aluminosilicate polymer structure.

a r t i c l e i n f o a b s t r a c t

Article history: This study presents an investigation into the durability of geopolymer concrete prepared using blended
Received 17 November 2012 ash of pulverized fuel ash (PFA) and palm oil fuel ash (POFA) along with alkaline activators when exposed
Accepted 31 January 2013 to 2% solution of sulfuric acid for up to 18 months. Ordinary Portland Cement (OPC) concrete was also
Available online 5 March 2013
prepared as control concrete. The main parameters studied were the evaluation of mass, compressive
strength, products of degradation and microstructural changes. The deterioration was examined using
Keywords: X-ray diffraction (XRD), Fourier transform infrared (FTIR), thermogravimetry (TGA/DTG), scanning elec-
Alkaline solution
tron microscopy (SEM). The results of geopolymer and OPC concretes were compared and discussed.
Blended ash
Compressive strength
The performance of geopolymer concrete when exposed to 2% sulfuric acid solution for more than a year
Geopolymer concrete was superior to OPC concrete which is attributed to a more stable cross-linked aluminosilicate polymer
Microstructure structure formed in the geopolymer concrete.
Sulfuric acid Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Ordinary Portland Cement (OPC) is widely used binder in con-
struction practices. For a long time, OPC concrete was considered
to be a very durable material requiring a little or no maintenance.
Unfortunately, its resistance to chemical attacks such as acids and
sulphates is of concern. It is well known that OPC concrete is sus-
ceptible to acid attack because of its alkaline nature. The compo-
nents of the cement paste break down during contact with acids,
most pronounced being the dissolution of calcium hydroxide [1].
Acid attack has not traditionally attracted much attention, even
when cement composites are severely damaged by acids wherein
calcium hydroxide is dissolved and the hydrated silicate and alu-
minium phases are decomposed, and the concrete loses its
strength and deteriorates quickly [2,3].
Geopolymers are a class of binders manufactured by activation
of solid aluminosilicate source material with a highly alkaline
⇑ Corresponding author. Tel.: +6 07 5531736; fax: +6 07 5566157.
E-mail address: aamer.bhutta@gmail.com (M.A.R. Bhutta).
activating solution and aided by thermal curing. In the past few
decades, geopolymer binders have emerged as one of the possible
alternatives to OPC binders due to their reported high early
strength and resistance against acid and sulphate attack apart from
its environmental friendliness [2,4,5]. Fly ash based geopolymers
are one branch of the geopolymer family and have attracted more
attention since the 1990s. As a novel binder, the performance of fly
ash based geopolymers is promising, especially in some aggressive
situations where OPC concretes are vulnerable [6–9]. Geopolymer
binders might be a suitable alternative in the development of acid
resistant concrete. It is an inorganic binder material and can be
produced by a geopolymeric reaction of alkali activating solution
with silica and alumina rich source material from geological origin
or pozzolanic materials such as metakaolin, fly ash, and rice husk
ash [2]. Geopolymers exhibit many excellent properties such as
high early strength, low creep, low shrinkage, and good resistance
against acid and sulphate attack in addition to its environmental
friendliness [4,9,10]. Since geopolymers are novel binders that rely
on aluminasilicate rather than calcium silicate hydrate bonds
for structural integrity, they have been reported as being acid

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.01.018
 M.A.M. Ariffin et al. / Construction and Building Materials 43 (2013) 80–86 81

resistant. Bakharev studied the resistance of geopolymer materials specimens. The specimens were cured in water to achieve for 28 days. The initial
compressive strengths were determined 27 and 28 MPa, for OPC and BAG concretes
prepared from fly ash against 5% sulfuric acid up to 5 months expo-
[13].
sure and concluded that geopolymer materials have better resis- The specimens were then exposed to 2% sulfuric acid immersion up to
tance than OPC concrete [3]. Wallah and Rangan have shown 18 months. The solution of sulfuric acid had pH 1.0. The pH levels of the sulfuric
that geopolymer composites possess excellent durability proper- acid solutions were monitored weekly using a portable digital pH meter. Concen-
ties in a study conducted to evaluate the long term properties of trated sulfuric acid was periodically added to the solutions to maintain the pH lev-
els within an acceptable range of the designated concentrations. The choice of acid
fly ash based geopolymers [6].
solution and the concentration was based on practical utilization of concrete as a
Malaysia is the largest producer of palm oil and palm products construction material in sewage pipes, mining and food processing industries.
in the world. The palm oil shell and husk, by-products, are used as The testing media were replaced monthly with fresh solutions. The compressive
fuel in a boiler in the palm oil mill to produce steam for electricity strength of cube specimens was determined at 1, 3, 6, 12 up to 18 months to acid
exposure. OPC concrete with water/cement (w/c) ratio 0.59 was used for compari-
generating plant and palm oil extraction process. Although large
son in the tests. The specimens containing of Portland cement at w/c = 0.59 had the
amounts of POFA is being used in landfill and ash ponds which same consistency as the geopolymer specimens of alkaline solution/binder (S/
causes an environmental problem, there is still a huge volume of B) = 0.4. Thus, the specimens were compared as having the same consistency at
POFA which is not utilized. POFA is an agricultural waste and one the time of moulding. The compressive strengths of OPC and BAG concrete at the
of the pozzolanic materials used as partial replacement of Ordinary age of 28 days were 27 MPa and 28 MPa, respectively.
The deterioration was examined by X-ray diffraction (XRD), Fourier transform
Portland cement in conventional concrete to enhance the strength
infrared spectroscopy (FTIR), Thermogravimetry (TGA/DTG) and Scanning electron
and durability [11,12]. In this paper, POFA was blended with PFA microscopy with energy dispersive X-ray (SEM/EDX). For the analysis, the samples
and this blended ash (BA) was used as a source material to prepare were taken from the concrete specimens before and after sulfuric acid exposure.
geopolymer concrete along with alkaline activator and its resis- The crushed concrete samples were grounded in a grinding machine in order to ob-
tain the powder form (40 lm). X-ray diffraction (XRD) analysis was performed
tance to 2% sulfuric acid was investigated for 18 months.
through scanning from 5° to 65° 2h, with a 0.02° step size and 2 s/step count time.
Fourier transform infrared (FTIR) analysis was performed using the KBr pellet meth-
od (1 mg sample per 100 mg KBr) on a spectrometer, with 32 scans per sample col-
2. Materials and methods lected from 4000 to 400 cm 1 at 4 cm 1 resolution. Thermogravimetry was
conducted by transferring samples to an alumina crucible, held under isothermal
2.1. Materials conditions for 60 min at 40 °C to equilibrate in a nitrogen environment (N2 flowing
at 200 ml/min), and then heated to 900 °C at 10 °C/min in the same gas environ-
Dry pulverized fuel ash (PFA) acquired from the silos of Kapar Power Station, ment. Scanning electron microscopy (SEM), with energy dispersive X-ray (EDX)
Selangor, Malaysia and palm oil fuel ash (POFA) was obtained from the burning analysis, was performed by coating samples with platinum prior to SEM analysis,
of the palm oil shell and husk from Kahang mill in Johor, Malaysia were used. and EDX was performed at an accelerating voltage of 15 KV. The specimens ana-
The PFA and POFA have a mean particle size of 45 lm. The chemical compositions lysed by SEM analysis were taken from fractured pieces of the samples.
of the ashes are shown in Table 1. To activate the blended ash, PFA + POFA (BA), a
commercial grade sodium hydroxide (NaOH) and sodium silicate (Na2SiO3), alkaline
solution was used as alkaline activator. Local crushed granite sand as fine aggregate
3. Results and discussion
with a specific gravity of 2.62 and coarse aggregates with a specific gravity of 2.68
were used for making concrete. In order to enhance the workability of BA concrete, 3.1. Visual appearance
a super plasticizer was added to the mixture.
Fig. 1 shows the visual appearance of the concrete specimens
after 18 months of sulfuric acid exposure. BAG concrete specimens
2.2. Testing procedures had no significant change in appearance after 18 months exposure
in sulfuric acid. The specimens were seen to remain structurally in-
All blended ash geopolymer (BAG) concrete specimens were prepared with an
alkaline solution to blended ash ratio of 0.4 by mass. The ratio of sodium silicate tact though surface turned a little softer. The visual observation of
(Na2SiO3) to sodium hydroxide (NaOH) was 2.5 by mass. The mix proportion for OPC concrete specimens showed severe deterioration as shown in
BAGC is given in Table 2. Both coarse and fine aggregates were used in saturated Fig. 1. In a short period of sulfuric acid exposure, OPC concrete
surface dry condition. The blended ash and the aggregates were first dry mixed in specimens showed deterioration that is consistent with high con-
80 l capacity pan mixer for 5 min. The alkaline solution containing sodium hydrox-
tent of calcium in the specimens. The deterioration of the surface
ide and sodium silicate was added and mixed for another 5 min. The super plasti-
cizer was used to achieve the workability of BAG concrete in between 80 and was seen to increase with time though the extent of deterioration
100 mm slump. The cube specimens of size 100  100  100 mm were moulded among the samples could not be easily differentiated through vi-
and compacted in two layers followed by compaction on a vibration table for 10 s sual inspection.
to remove the air voids. After casting, the specimens were covered using vacuum
bagging film to avoid the evaporation of alkaline solution. The test specimens were
subjected to room temperature (28 °C) for 28 days. OPC concrete was also prepared 3.2. Mass change
with water to cement ratio of 0.59 by mass as shown in Table 3 as control
Fig. 2 represents the mass change of specimens exposed to sul-
furic acid up to 18 months. The results showed that both OPC and
Table 1
Chemical compositions of PFA, POFA and OPC.
BAG concrete specimens had gained mass to 1.8% and 1.2% respec-
tively in first month of exposure. After 1 month exposure period,
Type SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O LOI the mass of both OPC and BAG concrete specimens had gradually
PFA 46.7 35.9 5.0 3.9 0.8 0.6 0.5 1.0 decreased with an increase in exposure period. As shown in
POFA 53.5 1.9 1.1 8.3 4.1 1.3 6.5 18.0 Fig. 2, the mass loss for BAG concrete specimens was 8%, consider-
OPC 43.1 5.0 2.6 46.0 1.1 0.2 0.5 1.3
ably smaller than the mass loss of OPC concrete specimens which
exhibited 20% after 18 months sulfuric acid exposure. This can be

Table 2
Mix proportions of BAG concrete.

Ratio BA S/B Mix proportions (kg/m3)

Na2SiO3 NaOH PFA POFA Sand Aggregate Admixture
70:30 0.40 119 48 290 124 530 1234 8.3
82 M.A.M. Ariffin et al. / Construction and Building Materials 43 (2013) 80–86

Table 3
Mix proportions OPC concrete.

w/c ratio Mix proportions (kg/m3)

Water Cement Sand Aggregate
0.59 192 384 898 861

attributed primarily to the reaction between calcium hydroxide

presented in the OPC concrete specimens and the acid, which can
induce tensile stress, resulting in cracking and scaling of concrete.

3.3. Compressive strength

Fig. 3 shows the evolution of the compressive strength of the Fig. 2. Mass change of concrete specimens in sulfuric acid for 18 months.
specimens exposed to the sulfuric acid solution. The BAG concrete
had the best performance with an average of 7.3% strength decline
in the first month of the exposure and additional 1.6% strength de-
cline every month afterward. The BAG concrete specimens had 35%
strength loss after 18 months exposure. This may be attributed to
the breakage of aluminosilicate bonding in BAG concrete caused
by the sulfuric acid attack [3], because aluminosilicate bonding is
important as it gives strength to BAG concrete. In contrast, the
OPC concrete specimens started deteriorating in the first month
of the exposure and had 68% strength loss and were severely dete-
riorated after 18 months of sulfuric acid exposure.

3.4. Analysis of samples before sulfuric acid exposure

3.4.1. X-ray diffraction

Mineralogical characterization of the reaction product of alkali
activation of the BAG concrete in Fig. 4 shows crystalline quartz
(Q), and gmelinite (Gm). The reaction between PFA, POFA and the
sodium silicate activator resulted in amorphous to partial crystal-
line phases. The main phase detected was a crystalline N–A–S–H
phase, similar to albite (NaAlSi3O8, PDF03-0451) [14–17]. Other
phases in BAG concrete were gmelinite and sodalite which was
produced from the reaction product of geopolymerisation and its
represent the nanostructure of the zeolite precursor [18–20]. In
contrast, the OPC concrete had a different crystalline C–S–H phase
which was similar to anorthite (CaAl2Si2O8, PDF10-0379)
[21,28,29].
3.4.2. Fourier transform infrared spectroscopy
The FTIR spectra in Fig. 5 indicates major bands at approxi-
mately 3440, 1645, 1425, 1010 cm 1 in OPC concrete and 3465,
1645, 1425, 1040 cm 1 in BAG concrete. The structure of molecular
water in the system was characterized by the O–H stretching band,
from 3200 to 3700 cm 1, while the bending of the chemically
bonded H–O–H was located at 1645 cm 1. Thus, the bands at
1010–1040 cm 1 and 780 cm 1 were assigned to quartz as the
crystalline phase in the both samples [22]. Conversely, the carbon-
ate in the system was characterized by absorption at 1425 cm 1,
which was consistent with the presence of anorthite and calcite
Fig. 3. Compressive strength of concrete specimens exposed to sulfuric acid for
18 months.
particularly in OPC samples [28,29]. The main binder gel band ap-
peared at 1010 cm 1, assigned to the asymmetric stretching mode
of the C–S–H structure formed in OPC samples whereas the posi-
tion at 1040 cm 1 is consistent with N–A–S–H gels formed in geo-
polymer binder systems derived from solid precursor used
[15,28,29]. In alkali-activated materials only based on slag or fly
ash, this vibration band had usually been identified between 950
and 1100 cm 1, and it was typically associated with the binding
gels (C–(A)–S–H for slag and N–A–S–H for fly ash), with a lower
wavenumber indicating a depolymerized or more highly substi-
tuted silicate gel, and higher wavenumbers being due to more
crosslinked and highly siliceous gels [16,23].
3.4.3. Thermogravimetry (TGA/DTG)
Fig. 6a shows the TGA profiles for OPC concrete showing mass
loss 18% whereas BAG concrete showing only 10% mass loss during
the measurement period. The mass loss profiles of BAG concrete
begin to reach a plateau after approximately 700 °C compared to

OPC concrete specimens BAG concrete specimens

Fig. 1. Appearance of concrete specimens exposed to sulfuric acid for 18 months.

 M.A.M. Ariffin et al. / Construction and Building Materials 43 (2013) 80–86 83

OPC concrete, only after 800 °C to reach it. Differential thermo- 100
grams (DTG) of both concretes as shown in Fig. 6b, where detect- 98
able peaks occured at various temperatures, marked as 1–4. The 96

Weight (%)
first peak, 1 and 2 was observed at a temperature below 100 °C 94
for OPC and BAG concretes. This was consistent with the removal
92 BAG concrete
of free evaporable water which was present in the pores of the
90
gel products, either C–S–H type or N–A–S–H (zeolite-like) gels OPC concrete
88
[24]. A large shoulder just below 200 °C was attributed to the
dehydration of the calcium-rich silicate gel. At the location marked 86
with 3, a weak mass loss effect at 264 °C in the sample was as- 84
0 200 400 600 800
signed to the dehydration of gypsum (OPC) and gmelinite (BAG);
this phase was identified by XRD in both samples [28,29]. At loca- Temperature (°C)
tion 4, approximately 714 °C, there were broad mass loss peaks ob- (a) Themogravimetric data (TGA)
served in the OPC samples, attributed to the decomposition of the
carbonate minerals as identified by FTIR. The decomposition tem- 1 2 3 4
perature of anorthite and calcite was reported to be between 741 OPC concrete

and 797 °C [25,28,29].

3.5. Analysis of samples after sulfuric acid exposure

BAG concrete
3.5.1. X-ray diffraction
Fig. 7 exhibits the XRD patterns for the OPC and BAG concretes
after 18 months sulfuric acid exposure. The main phases those had
been detected in Fig. 4, were still remaining in the BAG concrete
samples. A quantity of albite and gmelinite was still visible in the 0 200 400 600 800
samples. A sodalite and natrolite were also identified which were
Temperature (°C)
the reaction products of geopolymerisation and represent the zeo-
lite precursor of BAG concrete [20,26,27]. On the other hand, the (b) Differential thermograms (DTG)
gypsum (CaCO3, PDF00-033-0268) was formed, probably resulting
Fig. 6. Themogravimetry data (TGA–DTG) of OPC & BAG concretes before sulfuric
from reactions involving atmospheric CO2, as discussed before, no acid exposure. (a) Thermogravimetric data (TGA). (b) Differential thermograms
ettringite was detected in geopolymer, consistent with the low Ca/ (DTG).
Si ratio of these systems. The Al was expected to participate in the
formation of N–A–S–H type gels, and thus less available for ettring-
ite formation than in Portland cement [16,17]. Similar findings for
alkali activated slag mortars were reported by Bakharev [3]. 3.5.2. Fourier transform infrared spectroscopy
Fig. 8 shows the FTIR spectra of the samples after exposure to
H2SO4, as the figure depicts there was no distinct difference be-
Q = quartz A = albite An = anorthite Gm = gmelinite tween the exposed and unexposed in the BAG samples. The water
G = gypsum C = calcite E = ettringite Sd = sodalite
component of O–H stretching band at 3465 cm 1 and the bending
An,C-S-H
of the chemically bonded water, H–O–H at 1650 cm 1 were not al-
Q
tered by the exposure to sulfuric acid. The Si–O asymmetric
E
G C
OPC concrete
stretching vibration mode at 1040 cm 1 also showed no significant
shift after exposure. This suggested that sulfuric exposure did not
Q
significantly alter the chemical structures (gmelinite) of the main
A,N-A-SH
binder products in the BAG concrete studied here.
Gm Conversely, the reaction of the OPC concrete samples in sulfuric
Sd BAG concrete
acid showed marked decomposition of the C–S–H and O–H phase
in the microstructure, and Fig. 8 gives distinct differences between
0 10 20 30 40 50 60
the spectra obtained from the exposed specimens when compared
2θ (degrees)
with the unexposed specimens. The water component at
Fig. 4. XRD data for OPC and BAG concretes before sulfuric acid exposure.
3435 cm 1 had been changed to 3405–3555 cm 1 and the chemi-
cally bonded water at 1625 cm 1 also changed to 1625–
1690 cm 1 which were contributed by the presence of gypsum
[28,29]. It was evident that the OPC concrete were altered by the
OPC concrete
exposure of sulfuric acid. There also appeared to be a slight change
of peak position of network Al–O band, i.e. there was a shift to a
1645
780 lower wavenumber (600–670 cm 1) which was consistent with
3440 BAG concrete
1425 the presence of gypsum [28,29]. Finally, the decomposition of the
1010
main binder, C–S–H gel was associated with the shifting to the
1645 new bands at 1145 cm 1 in the samples in acid was also consistent
1425 780 with the degradation of the binder, which assigned to the presence
3465 1040
of calcite [28,29]. The diffractograms in OPC concrete samples,
4000 3500 3000 2500 2000 1500 1000 500 however, presented a different picture when examining sulfuric
-1 acid attack on the concrete. The sample preparation as discussed
wavenumber (cm )
before was taken for the XRD analysis. Gypsum crystals showed
Fig. 5. FTIR spectra of OPC and BAG concretes before sulfuric acid exposure. a much more intense presence in these systems. The C–S–H type
84 M.A.M. Ariffin et al. / Construction and Building Materials 43 (2013) 80–86

Gm - gmelinite G - gypsum C - calcite

G Sd - Sodalite Nt - Natrolite E- Ettringite
G
Q C
opc concrete after immersion in H2 SO4

An,C-S-H
Q
E G opc concrete before immersion H2 SO4

G A,N-A-S-H
Gm
Sd Nt BAG concrete after immersion in H 2 SO4
Q

A,N-A-S-H
Gm
Sd BAG concrete before immersion in H 2 SO4

0 10 20 30 40 50 60
2θ (degrees)

Fig. 7. X-ray diffractograms of OPC and BAG concrete samples.

OPC concrete before immersion in H 2 SO 4

100
1690
780 98
1425
3435 1010 96
OPC concrete after immersion in H 2SO4
94
1690
1425 780 92
1625 BAG concrete after immersion in H2SO4
3555 670 600
Weight (%)

3405 1145
BAG concrete before immersion in H 2SO4 90
1650 88 BAG concrete before immersion in H2SO4
3465 1425 780
1040
86 OPC concrete before immersion in H2SO4
BAG concrete after immersion in H 2 SO4
84
1650
1425 780
82
3465
1040 80
OPC concrete after immersion in H2SO4
4000 3500 3000 2500 2000 1500 1000 500 78
76
wavenumber (cm-1)
0 200 400 600 800
Fig. 8. FTIR spectra of OPC and BAG concrete samples.
Temperature (°C)
(a) Themogravimetric data (TGA)

phase was poorly observable in Fig. 7, and it was present at a opc concrete before immersion in H 2 SO4
greatly reduced intensity compared to the unexposed samples.
This suggested that decomposition of the C–S–H phase in the con-
crete had supplied the calcium required for the formation of gyp- opc concrete after immersion in H 2SO4
sum [28,29]. Based on the analysis, BAG concrete has high
resistance of sulfuric acid compared to OPC concrete.

3.5.3. Thermogravimetry (TGA/DTG) BA concrete before immersion in H 2SO4

Fig. 9 shows the TGA and DTG data respectively, for the samples
after 18 months sulfuric acid exposure. The mass loss values BA concrete after immersion in H 2 SO4
shown in the BAG samples were between 9% and 10%, no signifi-
cant change between the unexposed and exposed samples. Con-
versely, the mass loss observed was much higher in OPC samples
after exposure to sulfuric acid which the total mass loss of the sam- 0 100 200 300 400 500 600 700 800
ple falls in the range of 18–22%, which was higher than the unex- Temperature (°C)
posed samples. This is similar to the value in Fig. 4 as discussed
(b) Differential thermograms (DTG)
before. Decomposition of phases is shown in the DTG plot, showing
the release of water between 140 °C (OPC) and 122 °C (BAG), which Fig. 9. Thermogravimetry (TGA–DTG) curves for OPC and BAG concretes. (a)
was much higher compared to the unexposed samples. From XRD Themogravimetric data (TGA). (b) Differential thermograms (DTG).
and FTIR as discussed above, it was evident that gypsum was the
dominant product in the samples exposed to sulfuric acid. Gypsum
started to decompose between 110 and 150 °C. Gypsum was 3.5.4. Scanning electron microscopy
known to dehydrate via an intermediate calcium sulphate hemihy- SEM and EDX spectrum of both samples are shown in Fig. 10.
drate (CaSO4
5H2O) phase, to anhydrite (CaSO4) at 150–200 °C The EDX spectrum in Fig. 10a showed the presence of extended
[28,29]. crystalline structures of gypsum (CaSO4
2H2O) as shown by the
 M.A.M. Ariffin et al. / Construction and Building Materials 43 (2013) 80–86 85

Element wt%
--------------------
OK 36.25
NaK 8.30
MgK 6.06
AlK 8.44
SiK 20.30
SK 5.96
CaK 14.70

(a) OPC concrete

Element wt%
--------------------
O K 31.73
NaK 13.59
MgK 9.76
AlK 13.05
SiK 29.43
S K 1.18
CaK 1.25
Total 100.00

(b) BAG concrete

Fig. 10. SEM images and EDX spectrum of OPC and BAG samples. (a) OPC concrete. (b) BAG concrete.

Table 4
Mean Ca/Si atomic ratio before and after sulfuric acid exposure.
Type of sample Ca/Si ratio
Before immersion
OPC 2.24
BAG 0.25
large presences of Ca, O and S. However, the situation following
BAG samples exposure after 18 months was quite different. The
SEM images of BAG samples after exposure to sulfuric acid showed
no significant formation of any new distinct phases. Conversely,
the OPC concrete had soft white depositions on the surface and be-
came very porous after exposure to sulfuric acid for up to
18 months. The BAG concrete exhibited better performance than
the OPC concrete when exposed to sulfuric due to difference in
chemical and phase composition. The major components of the
EDX spectrum of BAG concrete were O, Si, Na, and Al. This result
complied to the work of other researchers who found that geopoly-
mer materials had better resistance than cement based specimens
[3,9].
In general, as the sulfuric acid attack progresses, the C–S–H and
N–A–S–H decalcifies, and therefore the Ca/Si molar ratio decreases.
Table 4 shows the elemental ratio (Ca/Si) calculated from SEM/EDX
data for OPC and BAG concrete samples collected before and after
sulfuric acid exposure. In OPC concrete the Ca/Si ratio tended to be
higher because of the high content of CaO in the concrete com-
pared to BAG concrete. This showed that the Ca rich gel such as
C–S–H could have more deleterious effects compared to a lower
Ca/Si ratio in the binder system like N–A–S–H when the concrete
samples were exposed to sulfuric acid.
4. Conclusions
Based on the results of this study, the following conclusions can
be drawn:
After immersion
1. BAG concrete specimens were seen to remain structurally intact
0.72
0.04 though surface turned a little softer, while visual observation of
OPC concrete specimens showed severe deterioration after
18 months sulfuric acid exposure. The mass loss for BAG con-
crete specimens was 8% that is considerably smaller than the
mass loss of OPC concrete specimens which exhibited 20% after
18 months sulfuric acid exposure.
2. The BAG concrete specimens had 35% compressive strength loss
while the OPC concrete specimens started deteriorating in the
first month of the exposure and had 68% strength loss and were
severely deteriorated after 18 months of sulfuric acid exposure.
3. The presence of the Ca-rich gel phases present in the OPC, caus-
ing degradation of the binder system and the precipitation of
gypsum. The products of sulfuric attack were poorly cohesive
and expansive, leading to dimensional instability and a loss of
mechanical performance.
4. Conversely, exposure of BAG concrete to sulfuric acid did not
lead to any apparent degradation of the binder, and no conver-
sion of the binder phase components into sulphate-containing
precipitates was observable.
5. The results obtained here provided strong indications that the
key factor which determined the rate and effects of the pro-
cesses commonly described as ‘sulfuric attack’ in concrete was
actually the nature of the binder gel system. The Ca-rich gel
such as C–S–H like OPC could have severely deleterious effects
on these materials, while N–A–S–H gel systems at the same
concentration appeared to have little or no effect on the struc-
ture of the material.
86 M.A.M. Ariffin et al. / Construction and Building Materials 43 (2013) 80–86
Acknowledgments
The authors are grateful to the Ministry of Higher Education,
Malaysia (Mohe) and Research Management Centre (RMC), Univer-
siti Teknologi Malaysia (UTM) for financial support under grant:
Q.J130000.2522.00H96. The authors are also thankful to the staff
of Materials & Structures Laboratory, Faculty of Civil Engineering
for the facilities and support for experimental work.
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