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Fly ash SiO2 Al2O3 SiO2/Al2O3 Fe2O3 CaO P2O5 TiO2 MgO K2O SO3 MnO Na2O LOI*
Gladstone 47.87 28.0 1.71 14.09 3.81 1.81 1.99 0.93 0.62 0.27 0.21 0.41 0.43
Pt. Augusta 49.37 31.25 1.58 4.47 4.80 1.65 2.94 1.28 2.21 0.24 0.04 1.30 0.51
Collie 53.82 29.95 1.80 9.24 1.03 1.28 2.19 0.58 0.79 0.34 0.04 0.75 0.63
Tarong 75.66 19.0 3.98 1.38 0.30 1.0 1.83 0.0 0.63 0.03 0.02 0.15 1.16
*
Loss on ignition (unburnt carbon content).
Mixture designs
The mixture design is an optimized concrete mixture
developed in previous research for each of the four fly
ashes.23 In this study, the Na2O dosage is fixed at 15%
while the total aggregate in the concrete was kept to 64%
of the entire mixture by volume for all mixtures. The ratio
of mixture components in Table 3 was calculated based on
the absolute volume method24; as a result, the total weight of
binder and water was varied to keep the volume of material
and water/solid ratio (0.37) constant.
The mass of water in the mixture was taken as the sum
of mass of water contained in the sodium silicate, sodium
hydroxide, and added water. The mass of solid is taken as the
sum of fly ash, the solids in the sodium silicate solution, and
the sodium oxide pellets.
Fig. 2—Long-term density development and workability.
Mixing, casting, and curing (Note: 1 kg/m3 = 0.0624 lb/ft3; 1 mm = 0.0394 in.)
The mixing of geopolymer concrete was carried out using reported test results in each specific test are an average of
a 120 L (4.238 ft3) concrete mixer. The dry materials (fly ash, three samples.
fine and coarse aggregates) were mixed first for 4 minutes. The microstructure development was observed using scan-
Then activator and water were added to the dry mix and ning electron microscopy (SEM) imaging employing back-
mixed continuously for another 8 minutes. The mixture scatter electron detector with 15 eV of energy. Energy-dis-
was then poured into molds and vibrated using a vibration persive X-ray spectroscopy (EDS) analysis was performed
table for 1 minute to remove air bubbles. After vibration, the using nano-analysis software (AZtec 2.1) to determine the
molds were kept at room temperature for 1 day and then heat chemical composition (Si/Al atomic ratio) of the reacted
cured in an oven for 24 hours at 80°C (176°F) temperature geopolymer concrete. Specimens were cut using a diamond
with 95% relative humidity. Molds were removed from the saw to a size of 2 to 4 mm (0.0788 to 0.1576 in.) in height
oven and left to cool to room temperature before demolding, and 5 to 10 mm (0.197 to 0.394 in.) in diameter. The samples
and then kept at room temperature until being tested. were subsequently carbon coated and then mounted on the
SEM sample stage with conductive, double-sided carbon
Testing tape. A total of three samples were investigated for each
The compressive strength test was performed by MTS geopolymer concrete.
machine with a loading rate of 20 MPa/min (2.9 ksi/min)
according to AS 1012.9.25 The flexural and splitting tensile EXPERIMENTAL RESULTS
strength tests were conducted in accordance with AS 1012.1126 Density and workability
and AS 1012.10,27 respectively. The flexural tensile strength The dry density of four geopolymer concretes ranged
test was carried out on a MTS machine with additional testing between 2074 and 2205 kg/m3 (129.42 and 137.59 lb/ft3)
apparatus under a four-point bending test with a loading rate (Fig. 2), all of which increased with age. The range of densi-
of 1 MPa/min (0.145 ksi/min). The splitting tensile strength ties observed is in agreement with the literature11,31 and is
test was performed on an MTS machine equipped with split- lower than PC concrete, which is characteristically cited
ting tensile strength test equipment under a loading rate of as 2400 kg/m3 (149.76 lb/ft3).19 In addition, all concretes
1.5 MPa/min (0.218 ksi/min). The elastic modulus and Pois- displayed a very high, collapsed slump. This is attributed
son’s ratio were determined using a concrete testing machine to the spherical shape of fly ash particles combined with the
coupled with the compressometer/extensometer with a lubricating effect of sodium silicate solution. Thus, work-
loading rate of 0.25 MPa/s (0.036 ksi/s) in accordance with ability is represented by the slump flow diameter (ϕ) and
AS 1012.17.28 Slump and dry density tests were conducted ranged between 350 and 735 mm (13.79 and 28.96 in.) for
in accordance with AS 1012.3.129 and AS 1012.12.2.30 All the four materials.
tests were conducted at 28, 90, and 365 days of casting. The
Flexural strength
Figure 4 shows long-term flexural strength development
of four fly ash geopolymer concretes. It ranged from 3.36
to 6.30 MPa (0.487 to 0.914 ksi) between 28 and 365 days.
Similar to compressive strength development, the flexural
strength of all concretes tended to increase with time. The
highest and lowest flexural strengths were displayed by
Gladstone and Collie geopolymers, while the Pt. Augusta and
Tarong again fell in between the Gladstone and Collie. While
Fig. 4—Long-term flexural strength development. (Note: Tarong showed a lower compressive strength, it achieved a
1 MPa = 0.145 ksi.) slightly higher flexural strength than Pt. Augusta. Tarong
had the highest increase both from 28 to 90 days (0.77 MPa
Compressive strength
[0.112 ksi]) and from 90 to 365 days (1.59 MPa [0.231 ksi]),
Figure 3 shows long-term compressive strength develop-
while Collie had the lowest increase in both periods. Overall,
ment of the four different fly ash geopolymer concretes. It is
the flexural strength of the four geopolymers ranged from 7
observed that the compressive strength of all geopolymers
to 14% of the compressive strength, compared to a range of
tended to increase with time, but in different increment ratios,
9 to 12% typically cited for PC concrete.11,24 Diaz-Loya et
depending on the fly ash properties. Gladstone geopolymer
al.11 reported a similar trend but over a wider range, noting
displayed the highest strength while Collie the lowest at all
that the flexural strength of the geopolymers are between 9
ages, with the strengths of Pt. Augusta and Tarong geopoly-
and 26% of the compressive strength.
mers falling between the two. The compressive strength
of Gladstone ranged from 82.5 to 87.4 MPa (11.963 to
Splitting tensile strength
12.673 ksi) while the Collie varied from 24.9 to 28.7 MPa
Figure 5 shows long-term splitting tensile strength devel-
(3.611 to 4.162 ksi) between 28 and 365 days. It was noted
opment of four fly ash geopolymer concretes. The splitting
that Gladstone obtained 95% of its ultimate strength in first
tensile strength ranged from 1.15 to 4.72 MPa (0.167 to
28 days, showing a lowest percentage increase in strength
0.684 ksi) between 28 and 365 days, and ranged from 4 to
between 28 and 365 days. Collie geopolymer demonstrated
8% of the compressive strength. The splitting tensile strength
a higher strength gain: 15.3% between 28 and 365 days.
of all geopolymer concretes increased with time. Gladstone
However, the actual increase in strength is only by 3.8 MPa
and Collie achieved the highest and lowest splitting tensile
(0.551 ksi), which is lower than 4.9 MPa (0.711 ksi) increase
strength, respectively, with Pt. Augusta and Tarong geopoly-
observed for Gladstone. Tarong and Pt. Augusta geopolymers
mers once more falling between the two. It is interesting to
displayed a high compressive strength development: 44.6%
note that Pt. Augusta showed higher splitting tensile strength
(13.2 MPa [1.914 ksi]) and 27.4% (10.1 MPa [1.465 ksi]),
than Tarong, though it had lower flexural strength of the two.
respectively, between 28 and 365 days. Pt. Augusta had
significant strength development: 8.7 MPa (1.262 ksi) by 90
Elastic modulus
days, but little further increase (1.4 MPa [0.203 ksi]) in the
The elastic modulus of concrete is defined as the stress
period between 90 and 365 days. Tarong, however, had a
required to induce a unit strain within the elastic limit. The
similar increase both from 28 to 90 days (6.9 MPa [1.0 ksi])
DISCUSSION
In the geopolymerization process, alumina and silica
species in fly ash rapidly react with highly alkaline activator
solution and produce a three-dimensional polymeric chain
and ring structure consisting of Si-O-Al-O bonds (Eq. (1)),33
Fig. 6—(a) Stress-strain curve; and (b) elastic modulus where z is the type of bond presence (1, 2, or 3), and n is
development. (Note: 1 MPa = 0.145 ksi.) the degree of polymerization. The schematic formation of
stress-strain curves shown in Fig. 6(a) presents the range of the resultant geopolymer product is generally represented by
elastic modulus measured in this study. As the geopolymer Eq. (2) and (3).
concretes demonstrated brittle failure,11 the descending
branch of the stress-strain curve could not be determined in
any of the tests. Each curve represents the tangent modulus
of elasticity and ranged from 8.2 to 22.7 GPa (1160 to
3291.5 ksi) between Collie and Gladstone geopolymers at
28 days. Figure 6(b) further shows elastic modulus devel-
opment at 90 and 365 days. Similar to the strength proper-
ties discussed, the elastic modulus also tended to increase
with time in all concretes with different increment ratios.
Gladstone showed the highest value while Collie gave the
lowest at all ages. A substantial increase of elastic modulus
was noted between 90 and 365 days compared to the initial The Si/Al (atomic) ratio determines the structure of
28- to 90-day period for all geopolymers, except Collie, the geopolymer backbone. In this study, Si/Al ratio of
which displayed the opposite trend. Moreover, in the first geopolymer concrete ranged between 2.69 and 2.84, 2.55
90 days, Tarong had a very low elastic modulus, similar to and 2.64, and 2.48 and 2.58 for Gladstone, Pt. Augusta,
Collie and lower than Pt. Augusta. However, by 365 days, it and Collie at 28, 90, and 365 days, respectively. As such,
had achieved the second-highest elastic modulus, having a the geopolymer structure was inferred to be polysialat-si-
twofold increase between 90 and 365 days. loxo (Si-O-Al-O-Si-O). In Tarong geopolymer, the Si/Al
ratio ranged 4.05 to 3.65, and the corresponding gel struc-
Poisson’s ratio ture is identified as polysialate-disiloxo (Si-O-Al-O-Si-O-
Figure 7 shows long-term Poison’s ratio changes of the Si-O). In all geopolymers, the Si/Al ratio decreased with age
four geopolymer concretes. The Poisson ratio varied from (Fig. 8 and 9). This indicates an ongoing geopolymerization
Fig. 9—SEM images of gel-microstructure in: (a) to (c) Pt. Augusta; and (d) to (f) Tarong geopolymer concretes.
process, with continuous gel formation along with incor- (3.94 × 10–4 and 7.88 × 10–4 in.) size, coupled with the larger
poration of alumina into the silicate backbone. The Si/Al surface area, increased the fly ash reactivity. Gladstone fly
ratio of all geopolymer concretes, other than Tarong, varied ash has the highest surface area with a large amount of finer
over a small range, but their mechanical properties differed particles, especially a higher percentage passing at 10, 20,
significantly. Hence, although the Si/Al ratio indicated that and 45 micron sieves. It also consists of a high amount of
the geopolymer bond structure should be similar, the nature reactive alumina-silica amorphous phase. The very fine
of the geopolymer gel matrix formed, in terms of uniformity particles of amorphous phase in Gladstone rapidly react with
and compactness, is significantly different, which is hypoth- the alkali activator and precipitates geopolymeric gel on the
esized as the reason for the mechanical properties observed. surface of the fly ash particles. This is because alumina-silica
The matrix formed and its development with the time in species are primarily leached by dissolution of the amor-
Gladstone and Collie geopolymer concretes are displayed in phous phase, not the crystalline phases of fly ash,4 with the
Fig. 8. Gladstone produced a uniformly distributed geopoly- significant part of the alkali-fly ash reaction occurring at the
meric gel-microstructure at all ages. The degree of reac- particle-liquid interface.35 This gel then diffuses through the
tivity of fly ash governs the dissolution, coagulation, and surface, covering and coalescing unreacted fly ash spheres
gel formation, which is itself dependent on the properties together. Continuous gel precipitation further fills the inte-
of source material. Gunasekara et al.23 reported that a higher rior spaces and forms a uniform, strongly compacted, and
quantity of fly ash particles with the range of 10 and 20 µm well-condensed gel-microstructure.