Construction and Building Materials 200 (2019) 502–513

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Chloride induced corrosion in different fly ash based geopolymer

concretes
Chamila Gunasekara a,⇑, David Law a, Shamir Bhuiyan a, Sujeeva Setunge a, Liam Ward b
a
Civil & Infrastructure Engineering, School of Engineering, RMIT University, Australia
b
Environmental & Chemical Engineering, School of Engineering, RMIT University, Australia

h i g h l i g h t s

Fly ash geopolymer shows higher corrosion rate than PC concrete with cast-in chlorides.

Higher corrosion rate in cast-in specimens is attributed to a lower pH in geopolymer.

Chloride diffusion rate is dependent on the reactivity of the precursor fly ash.

Chloride binding capacity of fly ash geopolymer is dependent on CaO in precursor.

Hematite, akageneite & lepidocrocite are main corrosion products of geopolymer.

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

Article history: This study investigates the corrosion of reinforcement in geopolymer concrete manufactured from three
Received 3 October 2018 different low calcium fly ashes from Australian power plants. The long term corrosion condition of
Received in revised form 21 December 2018 embedded rebar in fly ash geopolymer concretes containing cast in chlorides (0–5%) subjected to wet-
Accepted 22 December 2018
dry cycles, together with specimens exposed to ponding in 3% NaCl were examined. Half-cell potential
and linear polarisation resistance techniques were used to measure corrosion up to 540 days of age,
and compared with results of a similar binder content PC concrete. Increased levels of corrosion were
Keywords:
observed in the cast-in chloride geopolymer specimens compared with the equivalent PC concretes.
Fly ash
Geopolymer
However, in the case of the ponded specimens the reinforcement in the geopolymer concrete specimens
Corrosion rate displayed lower corrosion levels than the PC concrete. The higher corrosion rate in the cast-in specimens
Polarization is attributed to a lower pH in the geopolymer specimens resulting in a higher Cl/OH ratio. In the
Chloride concentration ponded specimens the formation of three-dimensional N-A-S-H and C-A-S-H cross linking in the gel
Chloride binding matrix reduces chloride diffusion to rebar depth, resulting in a lower corrosion rate being observed for
ponded geopolymer specimens compared to the PC concrete.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction
Portland Cement (PC) is the second most used product in the
world after water, and also the second largest source of anthro-
pogenic carbon dioxide (CO2) emissions, after power generation.
Current cement production contributes 4–7% of the CO2 emission
worldwide [1–3], with the production of 1 tonne of cement pro-
ducing from 600 to 800 kg of CO2 [4–6]. In the worst case scenario
rapid urban growth in developing countries may significantly
increase cement demand with estimates that cement production
could represent 10–15% of global CO2 emissions in next decade
[7]. Due to reduced carbon emission and low embodied energy,
⇑ Corresponding author.
E-mail address: chamila.gunasekara@rmit.edu.au (C. Gunasekara).
fly ash based geopolymer concrete has received significant atten-
tion in the last two decades as an alternative to PC concrete for pro-
duction of structural/non-structural elements. The most
emphasized advantage of geopolymer production is the potential
reduction of CO2 emission by 26–45% with the replacement of PC
with no associated adverse economic impact [8–10].
The durability of concrete is of great importance as it governs
the performance of reinforced concrete structures during their
operational life. Chloride induced corrosion in infrastructure is
one of the major durability concerns, causing billions of dollars
to be spent globally in repairs and maintenance of reinforced con-
crete structures [11]. Concrete provides an alkaline pH that pro-
motes the passivation of steel reinforcement. The ingress of
chloride ions results in the depassivation of steel and, once the
chloride ions have reached a critical concentration at the rebar,

https://doi.org/10.1016/j.conbuildmat.2018.12.168
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
 C. Gunasekara et al. / Construction and Building Materials 200 (2019) 502–513
the initiation of corrosion. The Cl/OH ratio has been identified as
one of the principal factors determining the onset of corrosion,
with the OH ion concentration being dependant on the pH [12].
Badar et al. [13] noted that due to the high pH of the pore system,
fly ash geopolymer concrete can passivate reinforcement similar to
PC concrete. However, Lloyd et al. [14] showed that the presence of
CaO is important in lowering the permeability and inhibiting a
drop in the pH due to leaching of alkali ions, which may result in
depassivation of the reinforcement in geopolymer concrete.
It has been reported that fly ash geopolymer concrete has a high
resistance to chloride ingress due to low chloride ion permeability
[15,16]. However, Ganesan et al. [17] stated that chloride penetra-
tion of both PC and fly ash geopolymer concretes are identical.
Babaee and Castel [18] also noted that low-calcium fly ash-based
GPC exhibit comparable electrochemical performance to similar
strength PCC during the propagation phase of corrosion. However,
Olivia et al. [19] observed a higher chloride penetration than PC
concrete and Pasupathy et al. [20] reported significantly higher
chloride ingress in low Calcium fly ash based geopolymer concrete
following 6 years exposure in a saline environment, while Munt-
ingh [21] concluded that the precursor fly ash used and mix design
may result in varying long term performance in geopolymer con-
crete. Monticelli et al. [22] studied chloride induced corrosion in
contaminated fly ash geopolymer concrete when adding 2% chlo-
ride by mass of binder in the mixing process. Test results indicated
that silicate ions in the pore solution in geopolymer concrete pro-
vide extra protection for the passivation of the reinforcement.
However, Miranda et al. [23] reported that embedded steel did
not have a steel shielding passive layer and showed an identical
level of corrosion to PC concrete. Bastidas et al. [24] worked with
three different fly ash based mortars and investigated the corrosion
stability of the passive state with 0%, 0.2%, 0.4% and 2% chloride
additions in relation to the binder material. The authors reported
that the addition of 2% (by binder weight) chlorides increases the
reinforcement corrosion rate by 100 times. Hence, the corrosion
resistance performance of steel in geopolymer concrete is not
clearly understood. One of the reasons for the differences in
reported literature is due to the varied composition of fly ash from
different sources which affects the material properties of the
geopolymer concrete produced [25]. The question of whether rein-
forcing steel can be protected in different fly ash based geopolymer
concretes, as effectively as with PC concrete, is examined in this
study. To that end, a range of geopolymer specimens were pre-
pared using three different low calcium fly ashes containing a
range of cast in chloride contents, varying from 0% to 5%. The cor-
rosion state of embedded rebar was evaluated using electrochem-
ical techniques, namely half-cell potential and corrosion rate
(linear polarisation resistance technique), and then compared with
results of a similar binder content PC concrete. The study further
evaluates the long-term corrosion state of the embedded rebar in
fly ash geopolymer and PC concretes while being subjected to
wet-dry cycles and chloride ponding, which was adopted to simu-
late natural chloride induced corrosion. A detailed microstructural
and chemical analysis was also conducted to determine the effects
of cast in chloride and chloride ponding corrosion rate, pH and the
condition of the rebar. The observed test results up to 540 days of
age are reported.
2. Significance of research
To date, few studies have been conducted in examining the
long-term durability of 100% fly ash geopolymer concrete subject
to chloride induced reinforcement corrosion. This lack of knowl-
edge is one of the main limitations associated with the confident
adoption of this concrete for industrial applications. This research,
503
examining the performance of geopolymer concrete up to 540 days
using three different low calcium fly ashes with the same mixing
process, provides a systematic long term durability study of a
range of geopolymer concretes. The reported geopolymer research
data can thus provide a clearer understanding of the behaviour of
this novel concrete against chloride ingress, made with a range of
low calcium fly ashes, representative of those that are available
worldwide.
3. Experimental procedure
3.1. Materials used
Low calcium, Class F fly ash for this study was provided from
Gladstone, Pt.Augusta and Collie power plants in Australia [26].
Tables 1 and 2 report the chemical composition and physical and
mineralogical properties of the three fly ashes. X-ray fluorescence
and X-ray diffraction techniques were used to measure the chem-
ical oxide composition and crystallinity of the material. Commer-
cially available liquid Na2SiO3 (Grade D, Na2O = 14.7% and
SiO2 = 29.4% by mass) and 15 M liquid NaOH were used as alkaline
activator. River sand was used as fine aggregate (2600 kg/m3 of
density) and crushed granite aggregate used as coarse aggregate
(2650 kg/m3 of density). The coarse aggregate was prepared in a
saturated surface dry aggregates condition. The coarse aggregate
consists of 7 and 10 mm grain sizes. Demineralized water was used
in the concrete production.
3.2. Mix designs
The mix design used is an optimised concrete mix developed in
previous research for each of the three fly ash [27], Table 3. The
mix proportions were calculated based on the absolute volume
method [28] and water to solid (w/s) ratio (Eq. (1)) is fixed at 0.37.
w mass of water in alakline activatorþmass of added water
ratio ¼
s mass of solid in alkaline activatorþmass of fly ash
ð1Þ
3.3. Mixing, casting and curing
A 120 L concrete mixer was used to mix the geopolymer and PC
concrete. For the geopolymer concrete mix, the fly ash, sand and
coarse aggregates were mixed initially for 4 min. The activator,
which was pre-mixed, and water were added to the dry mix and
mixed another 8 min. A similar mixing procedure was conducted
for PC concrete, except for the addition of the alkaline activator
to the dry materials (i.e. PC, fine and coarse aggregates). For each
concrete type, a total of 7 cubes (150 mm3) were cast with ribbed
bars (10 mm diameter and 120 mm length). For the ‘‘cast in chlo-
ride” specimen, the percentages of admixed NaCl percentage are
0, 0.25, 0.5, 1, 2, 3 and 5% of NaCl by weight of binder. An additional
set of concrete cubes of 150 mm3 were cast with ribbed bars
(10 mm diameter and 120 mm length) without chloride additions
for the ponding tests. A copper wire was welded to each bar prior
to casting to enable the steel to be used as the working electrode.
The weld was sealed with epoxy to prevent the onset of unin-
tended corrosion.
Specimens were placed on a vibration table and vibrated to
remove air bubbles. All geopolymer specimens were initially
stored at room temperature for 1 day and then heat cured in a
dry oven for 24 h at 80 °C temperature. After heat curing, the
geopolymer specimens were removed from the oven and left to
cool to room temperature before demoulding. Following casting
all PC concrete specimens were demoulded and kept at room
504 C. Gunasekara et al. / Construction and Building Materials 200 (2019) 502–513

Table 1
Chemical composition.

Fly ash By weight (%)

SiO2 Al2O3 Fe2O3 CaO K2O TiO2 P2O5 MgO Na2O SO3 MnO
Gladstone 47.87 28.0 14.09 3.81 1.81 1.99 0.93 0.62 0.27 0.21 0.41
Pt.Augusta 49.37 31.25 4.47 4.80 1.65 2.94 1.28 2.21 0.24 0.04 1.30
Collie 52.67 29.60 11.27 0.64 0.65 1.83 1.13 0.72 0 0.48 0.05
PC 22.5 4.5 0.4 66.3 0.15 0.20 0.67 0.51 0.17 2.8 0.10

Table 2 of the reference electrode housing, coated with a permeable foam

Physical and mineralogical properties. material (moistened prior to test) to ensure good contact with the
Properties investigated Gladstone Pt.Augusta Collie concrete. The corrosion current, Icorr, is then calculated [30]. Tafel
Specific Gravity 2.26 2.23 2.42
constants were not directly determined as this can cause irre-
BET Surface Area, (kg/m2) 2363 1228 1095 versible damage to the system due to the large applied overpoten-
Fineness (%) at 10 mm 43.1 46.7 40.9 tials. A value of 26 mV for active steel and 52 mV for passive steel
at 20 mm 61.9 62.1 54.6 were used for the Stern-Geary constant calculations, B based upon
at 45 mm 82.7 80.2 70.0
the values derived for PC concrete [30–32].
Amorphous (%) 71.8 59.5 72.5
Crystalline (%) Quartz 6.8 29.2 18.2 The suspension method was used to obtain the pH profile of the
Mullite 17.9 7.5 8.7 concrete [33]. Concrete powder samples were taken at rebar depth
Others 3.5 3.8 0.6 and mixed in de-ionised water at a 1:1 ratio. The suspensions were
Al coordination Tetrahedral (AlIV) 54.3 40.2 50.7 stirred using a magnetic stirrer for 6 min. A pH meter was used to
Octahedral (AlIV) 45.7 59.8 49.3
Unburnt carbon content (%) 0.42 0.53 0.61
obtain pH readings. In order to verify the pH values, the pore solu-
tion from a respective mortar sample (similar mix design as Table 3,
without coarse aggregate) was extracted and the pH measured. A
pressure of 500 MPa was applied with the loading rate of 1 MPa/
temperature. All chloride contaminated concrete specimens (PC &
s [34]. The measured pH difference was 0.68 (correction) and this
geopolymer) were kept in a spray cabinet which was set to spray
was subtracted from each data point along the profile in order to
water twice a day (every 12 h), with each spray cycle lasting
obtain the calibrated profile.
30 min. The non-chloride contaminated concrete specimens were
Powder samples taken from 540-day matured concrete speci-
stored under laboratory condition for 14 days (24 °C temperature
mens, close to the reinforcement bar, were used for the chloride
and 50% Relative Humidity), prior to ponding in 3% NaCl solution
analysis, Fourier transform infrared (FT-IR) and X-ray diffraction
for one week. After ponding, all specimens were subjected to a
(XRD) tests. Samples were sent to a NATA accredited laboratory
two-week dry cycle. This one-week ponding and two-week drying
to determine the total and free chloride content. FT-IR absorption
cycle process was continued up to 540 days.
spectrometry was used to identify bond formations within the
range 4000–450 cm1. X-ray diffraction (XRD) data was obtained
3.4. Testing using a Bruker AXS D4 Endeavor wide angle X-ray diffractometer
with copper anode at 40 kV and 35 mA.
Compressive strength testing was performed at 28 and 540 days Scanning electron microscopy in backscattered electron (BSE)
using a MTS machine with a loading rate of 20 MPa/min according imaging mode (BSE detector energy setting of 15 eV) was used to
to AS 1012.9 [29]. Four standard cylindrical specimens were tested examine the microstructure of the geopolymer concretes. Speci-
for each data point and the mean value reported. The corrosion men with dimensions 10 mm diameter and 5 mm thickness, were
rates were measured using linear polarisation resistance (LPR), carbon coated prior to insertion in the microscope chamber. A mer-
utilising a 3-electrode arrangement [30]. LPR measurements were cury intrusion porosimeter (V1.09 of Auto pore IV 9500) was used
taken potentiostatically by applying a  10/+10 mv shift, DE, to to measure pore-structure development in the geopolymer con-
the steel (working electrode) using an ACM Field machine. This crete. Geopolymer monoliths were initially dried in an oven at
result is a current, DI, passing between the working electrode 105 °C for 48 h and then vacuum saturated before testing.
and auxiliary electrode, which is measured after a 30 s delay time,
tequilib, to allow equilibrium to be established. The solution resis-
tance, Rs, is automatically measured by applying a high frequency 4. Experimental results
300 Hz input signal between the auxiliary electrode and reinforc-
ing bar and measuring the resulting current. The polarisation resis- Fig. 1 shows the compressive strength development for the dif-
tance, Rp is determined from the potential to current density slope ferent low calcium fly ash based geopolymer and PC concretes after
obtained. A Cu/CuSO4 electrode (CSE) was used as the reference 28 and 540 days with 0%, 2% and 5% NaCl. The Gladstone geopoly-
electrode and the auxiliary electrode was a brass ring on the base mer achieved the highest strength, with the Pt August and PC

Table 3
Optimum mix design (kg/m3).
*
Concrete Fly ash (kg) Cement (kg) Aggregates (kg) Activator (kg) Added Water (kg) Water/solid ratio
Sand 7 mm 10 mm Na2SiO3 (Liquid) NaOH (15 M)
Gladstone 417 – 698 308 619 293 66 7 0.37
Pt.Augusta 417 – 698 308 619 293 66 7 0.37
Collie 420 – 706 312 624 241 92 15 0.37
PC – 410 615 550 550 – – 220 –
*
Water/Cement ratio of 0.54 is used for PC concrete.
 C. Gunasekara et al. / Construction and Building Materials 200 (2019) 502–513 505

concretes having a similar strength, whilst the Collie was signifi- geopolymers, the only mix that achieved this condition was the
cantly lower (approx. 50% less than the PC concrete). All mixes control mix, i.e. concrete with no chloride.
increased by a similar percentage from 28 to 540 days. The addi- It is noted that the larger negative readings are not indicative of
tion of NaCl had no observable effect on the 28 day strength of increased susceptibility to corrosion due to many reasons. These
any of the mixes. In contrast, all geopolymer and PC concretes with can include factors such as a lower pH in the geopolymer than
‘‘cast-in chloride” recorded a loss in strength between 28 and the PC concrete, binding of the chloride ions or oxygen reduction
540 days. The loss in strength increased with increasing chloride at the reinforcement area due to oxygen depletion. Oxygen deple-
concentration. Strength reductions were of similar magnitude, tion may occur due to (i) saturation of the concrete associated with
13.2–17.7% for the 2% chloride and 19.8–23.2% for the 5% chloride the wet/drying cycle or (ii) decreased permeability of the concrete
specimens. The Gladstone again yielded the highest strength while due to the fineness of the fly ash. Such factors could limit oxygen
the Collie provided the lowest strength. It is well established that diffusion to cathodic areas on the rebar and result in more negative
additions of CaCl2 can increase initial strength development in PC corrosion potential values [24,36,37].
concrete, being a common set accelerator through the 1960’s and The alkalinity of concrete the pore solution is critical for pro-
1970’s, but that it can have a negative impact on the long term tecting the reinforcement against chloride induced corrosion.
strength gain due to the formation of chloroaluminate hydrates. Hence, the pH profile of each concrete was measured using the sus-
These results show a similar long term reduction in strength for pension method [33] and calibrated by direct measurement of the
geopolymer concretes with cast in chloride. extracted pore solution. The calibrated pH profiles for geopolymer
Corrosion potential (Ecorr) measurements of the rebars in the and PC concretes at different chloride concentrations are shown in
geopolymer and PC concrete specimens are shown in Fig. 2. As Fig. 4. The pH of Gladstone, Pt.Augusta and Collie fly ash based
expected, the potential became more negative as the chloride per- geopolymer concretes varied between 11.58 and 10.72, 11.62–
centage increased in the concrete specimen [35]. The PC concrete 10.88 and 11.58–10.95, respectively, compared to a pH variation
potential was generally more positive than for the geopolymer of 12.48–11.67 for PC concrete. It was noted that all geopolymer
concretes. Although there was no clear pattern within the geopoly- concretes containing no chloride displayed significantly lower pH
mer concretes themselves, the Gladstone samples were the most values (11.6) than PC concrete (12.5) at 28 days, and this was
negative, especially at NaCl concentrations greater than 1%. Based further reduced to  11.3 at 540 days, compared to the pH
on the van der Veer criteria, the 2, 3 and 5% data all showed a of  11.9 for PC concrete. All three geopolymer concretes showed
90% chance of corrosion for all three geopolymer concretes at all a pH drop between 28 and 540 days with increasing chloride con-
ages, while only the 5% PC concrete had a potential consistently centration, in particular in the 2–5% sodium chloride concentra-
more negative than  350 mV CSE. It was noted that PC concrete tions. Gladstone showed the largest pH reduction, followed by Pt.
mixes containing less than 1% of sodium chloride showed corro- Augusta and Collie. The PC concrete followed a similar trend to
sion potentials more positive than  200 mV CSE throughout the the geopolymer concrete at the higher chloride concentrations,
entire testing period. However, from all of the three fly ash but showed a lower pH reduction than the fly ash geopolymer. It

60 60
(a) 28-day 540-day (b) 28-day 540-day
+14.1%a 50
Compressive Strength (MPa)

50
Compressive Strength (MPa)

(+6.7MPa) b
-19.8%
-17.7%
(-9.5MPa) 40
40 (-8.0MPa)
+20.3%
(+6.4MPa) -16.9%
30 30 -23.0%
54.3 (-5.4MPa) (-7.3MPa)
47.6 45.3 48.1
20 38.6 20 37.9
37.3
31.5 31.9 31.7
26.5 24.4
10 10

0 0
Gladstone 0 Gladstone 2 Gladstone 5 Pt.Augusta 0 Pt.Augusta 2 Pt.Augusta 5
60 60
(c) 28-day 540-day (d) 28-day 540-day
50
Compressive Strength (MPa)

50
Compressive Strength (MPa)

40 +20.2%
40
(+7.4MPa)
-13.2%
-19.8%
(-4.7MPa)
30 30 (-7.0MPa)

+16.4% 44.1
20 -23.2% 20
(+3.0MPa) -15.7% 36.7 35.5 35.4
(-2.8MPa) (-4.2MPa) 30.8 28.4
10 21.3 10
18.3 17.8 18.1
15.0 13.9

0 0
Collie 0 Collie 2 Collie 5 PC 0 PC 2 PC 5

a
Fig. 1. Compressive strength development of geopolymer and PC concretes, contained with different percentages of chlorides. Percentage of strength gain/loss
[(540 day  28 day)/28 day]. bAbsolute value of strength gain/loss (MPa).
506 C. Gunasekara et al. / Construction and Building Materials 200 (2019) 502–513

Duraon (Days) Duraon (Days)

0 100 200 300 400 500 600 0 100 200 300 400 500 600
0 0

-100 -100

-200 -200

Ecorr (mV)
Ecorr (mV)

-300 -300

-400 -400

-500 -500

High Corrosion probability Zone High Corrosion probability Zone

-600 -600
Gladstone 0 Gladstone 0.25 Gladstone 0.5 Gladstone 1 Pt.Augusta 0 Pt.Augusta 0.25 Pt.Augusta 0.5 Pt.Augusta 1
Gladstone 2 Gladstone 3 Gladstone 5 Pt.Augusta 2 Pt.Augusta 3 Pt.Augusta 5

Duraon (Days) Duraon (Days)

0 100 200 300 400 500 600 0 100 200 300 400 500 600
0 0

-100 -100

-200 -200
Ecorr (mV)
Ecorr (mV)

-300 -300

-400 -400

-500 -500

High Corrosion probability Zone High Corrosion probability Zone

-600 -600
Collie 0 Collie 0.25 Collie 0.5 Collie 1
PC 0 PC 0.25 PC 0.5 PC 1 PC 2 PC 3 PC 5
Collie 2 Collie 3 Collie 5

Fig. 2. Corrosion potential vs. Cl concentration in geopolymer and PC concretes.

is hypothesized that the reduction in pH can be attributed to a
number of factors. Firstly, continuing geopolymerisation results
in the consumption of hydroxyl ions which results in a lowering
of the pH. Secondly, the pH will be reduced by the formation of
acid within in the pits due to corrosion of the steel. Finally there
may be some leaching of excess activator during the wet/dry
cycles. Further it is hypothesized that the more negative corrosion
potential values obtained by fly ash geopolymer concretes can be
attributed to the lower pH in the geopolymer concretes compared
to the PC concrete.
The corrosion potential (Ecorr) should be considered more as a
qualitative parameter and cannot be used to determine corrosion
rates alone, as there is no direct correlation between Ecorr and Icorr
(corrosion current density) [23,38,39]. Thus, corrosion current den-
sity (Icorr) was measured to provide an indication of the corrosion
rate. The Icorr for the rebars in the four concretes is shown in
Fig. 3. As a guide the Icorr values are quantified as low, medium
or high as defined elsewhere for PC concrete [30]. Fluctuations in
Icorr were observed over the first 90 days, with most samples show-
ing a decrease in corrosion rate, although a small number showed
an increase. This is attributed to the activation and hydration reac-
tions and the passivation of the rebars, during this period. These
are dependent upon the materials (FA or PC) and the chloride con-
centration. However, beyond 90 days almost all the specimens dis-
played an overall increase in corrosion rates with time, though
some fluctuation was observed.
All concretes with 0% chlorides had a corrosion rate of less than
1 lA/cm2 during the entire test period, which correlates well with
the corrosion potential readings. The Gladstone concrete consis-
tently displayed the highest Icorr for 5% sodium chloride concentra-
tions compared with the other concretes. The Pt Augusta generally
had a higher Icorr than the Collie for all chloride concentrations
except 1%, which was considerably lower than Collie geopolymer
concrete. The Icorr values of the fly ash geopolymer concretes were
significantly greater than the PC concrete, apart from the low chlo-
ride concentration samples (0–0.5%) where a minimal difference
was observed. The Icorr values for fly ash geopolymer concrete spec-
imens ranged from 0.5 to 3.5 lA/cm2, whereas values of 0.5–
2.0 lA/cm2 were recorded for PC concrete. Based on Icorr values,
two distinct groupings can be identified for fly ash geopolymer
and PC concretes in regard to chloride concentration. After 90 days,
all the 0% and 0.25% chloride samples (except 0.25% Pt Augusta)
displayed corrosion rates in the moderate range. All the other spec-
imens, i.e. 0.5% chloride and above, had corrosion rates classified in
the high range [30]. However, in the geopolymer specimens there
are two distinct groupings evident between the 0 to 0.5% chloride
specimens and those with a chloride concentration above 0.5%.
Given that the control specimens with no chloride present display
moderate corrosion rates, this would suggest that the calculated
corrosion rates are overestimated.
As stated, B values of 26 mV for active and 52 mV for passive
steel were adopted based upon the values derived for PC concrete.
However, Babaee and Castel have reported values of 13 to 20 mV
for passive steel and 43 to 65 mV for active steel in geopolymer
concrete [18] attributing this to the formation of iron oxide layers
around the rebar. Adopting these values for the geopolymer
 C. Gunasekara et al. / Construction and Building Materials 200 (2019) 502–513 507

Gladstone 0 Gladstone 0.25 Gladstone 0.5 Gladstone 1 Pt.Augusta 0 Pt.Augusta 0.25 Pt.Augusta 0.5
Gladstone 2 Gladstone 3 Gladstone 5 Pt.Augusta 1 Pt.Augusta 2 Pt.Augusta 3
3.5 3.5
(a) (b)
3.0 3.0
Icorr (μA/cm2)

Icorr (μA/cm2)
2.5 2.5

2.0 2.0

1.5 1.5

High High
1.0 1.0

Moderate Moderate
0.5 0.5
Low Low
0.0 0.0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Duraon (Days) Duraon (Days)

Collie 0 Collie 0.25 Collie 0.5 Collie 1

PC 0 PC 0.25 PC 0.5 PC 1 PC 2 PC 3 PC 5
Collie 2 Collie 3 Collie 5
3.5 3.5
(c) (d)
3.0 3.0

Icorr (μA/cm2)
Icorr (μA/cm2)

2.5 2.5

2.0 2.0

1.5 1.5

High High
1.0 1.0

Moderate Moderate
0.5 0.5
Low Low
0.0 0.0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Duraon (Days) Duraon (Days)

Fig. 3. Corrosion current density (Icorr) vs. Cl concentration in geopolymer and PC concretes.

12.6 12.6
Gladstone 0 Gladstone 1 Gladstone 2 (a) Pt.Augusta 0 Pt.Augusta 1 Pt.Augusta 2 (b)
12.4 12.4
Gladstone 3 Gladstone 5 Pt.Augusta 3 Pt.Augusta 5
12.2 12.2

12.0 12.0
pH

pH

11.8 11.8

11.6 11.6

11.4 11.4

11.2 11.2

11.0 11.0
pH range: 11.58 10.72 pH range: 11.62 10.88
10.8 10.8

10.6 10.6
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Duraon (Days) Duraon (Days)
12.6 12.6
Collie 0 Collie 1 Collie 2 (c) (d)
12.4 12.4
Collie 3 Collie 5
12.2 12.2

12.0 12.0
pH

pH

11.8 11.8
pH range: 12.48 11.67
11.6 11.6

11.4 11.4

11.2 11.2

11.0 11.0
pH range: 11.58 10.95 PC 0 PC 1 PC 2 PC 3 PC 5
10.8 10.8

10.6 10.6
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Duraon (Days) Duraon (Days)

Fig. 4. pH vs. Cl concentration in geopolymer and PC concretes.

508 C. Gunasekara et al. / Construction and Building Materials 200 (2019) 502–513
concretes would increase the corrosion rates for the active speci-
mens (1% chloride and above) and reduce the corrosion rates for
the passive specimens (0.5% chloride and below).
Images of the steel rebars after 540 days of exposure are shown
in Fig. 5. No corrosion induced cracking was noted around the steel
reinforcement, but uniform and pitting corrosion can be observed
on the bars. The pitting attack is concentrated on the rebar surface
and is more prevalent for the higher chloride concentrations (2–
5%). It is evident that there is a substantial degree of corrosion of
the reinforcement embedded in Gladstone and Pt.Augusta fly ash
based geopolymer concretes. Conversely in the Collie fly ash
geopolymer concrete, less rust formation on the surface of the steel
rebars can be observed compared to the other two geopolymers. In
the PC concrete, minimal deposition of steel corrosion products is
identifiable at 2–5% chloride. These observations correlate well
with the observed potentials and corrosion rate measurements,
which indicate a higher level of corrosion in the Gladstone and
Pt. Augusta specimens containing high chloride concentrations,
and little corrosion evident on the specimens containing 0.5% chlo-
ride and below, further suggesting that these are in a passive state.
The corrosion rates (Icorr) of the geopolymer and PC concretes
immersed in 3% sodium chloride solution are shown in Fig. 6.
The trends observed were similar to those for the cast-in speci-
mens. The Gladstone, Pt Augusta and PC specimens showed a
decrease in Icorr values in the first 90 days, indicative of passivation,
though the Collie showed an increase in corrosion rate throughout
having an Icorr above 1.0 lA/cm2 by day 90. All four concretes dis-
played a consistent increase between 90 and 540 days, but of dif-
ferent proportions, indicating corrosion had been initiated. The
Icorr values for Gladstone, Pt.Augusta and Collie geopolymer con-
cretes ranged from 0.55 to 1.05 lA/cm2, 0.65–1.10 lA/cm2 and
0.85–1.65 lA/cm2, respectively, whereas Icorr of PC concrete varied
between 0.65 and 1.20 lA/cm2. Gladstone geopolymer had the
lowest corrosion rate while Collie displayed the highest across
the entire testing period. The PC concrete displayed higher corro-
sion rates than the Gladstone and Pt.Augusta geopolymers.
The alkalinity of the four concretes was measured at 28 and
540 days. The data confirmed that fly ash geopolymer concretes
had a lower initial pH (pH = 12.05) than PC concrete (pH = 12.62).
The alkalinity of all concretes reduced with time. The measured
Fig. 5. Corrosion pattern of rebar vs. Cl concentration in geopolymer and PC concretes.
pH value of Gladstone, Pt.Augusta, Collie and PC concretes at
540 days were 11.57, 11.51, 10.92 and 11.42, respectively. Collie
geopolymer had a significant pH drop between 28 and 540 days,
compared to the other two geopolymer concretes. Both Gladstone
and Pt.Augusta exhibited slightly higher pH than PC concrete at
540 days. Again, the drop in pH observed can be attributed to fur-
ther geopolymerisation and to acid formation in the pits due to
corrosion. The magnitude of the pH reductions suggest that acid
formation may be the more influential, with a greater drop in pH
observed for the specimens with higher rates of corrosion and
more corrosion evident on the rebar.
Fig. 7 illustrates the corroded surface of the rebars of fly ash
geopolymer and PC concretes immersed in 3% sodium chloride
solution. It was observed that there was a significant amount of
rust formed on the surface of reinforcement in the Collie geopoly-
mer and PC concretes. Both concretes showed uniform and local-
ized corrosion throughout their rebar surface. On the other hand,
Gladstone and Pt.Augusta geopolymer displayed more isolated
regions of corrosion and overall, less rust formation on the rebar
surface. This again correlates well with the corrosion rate
measurements.
The chloride binding capacity in ponded concrete specimens at
rebar level (i.e. 20–30 mm depth) is calculated by subtracting the
measured free chloride content from measured total chloride con-
tent. The calculated chloride binding capacity using Eq. (2)
together with the measured total/free chloride contents in each
fly ash geopolymer and PC concrete is tabulated in Table 4.
 
 ðTotal Cl  Free Cl Þ
Cl binding capacity ¼   100 ð2Þ
Total Cl
In PC concrete, the chemical binding occurs due to hydrated cal-
cium aluminate derived from C3A, which produces Friedel’s salt.
Moreover, chloride ions physically bond with cement hydration
products, C-S-H and C-A-H gel [40]. In geopolymer concrete the
chloride ions can react with alumina and calcium oxide in undis-
solved fly ash grains, and form Friedel’s salt (3CaOAl2O3CaCl2-
10H2O) [41]. The PC concrete displayed the highest chloride
binding capacity, consistent with the chemical composition of
the PC and formation of Friedel’s salt. As expected, the highest total
chloride content together with the lowest chloride binding
 C. Gunasekara et al. / Construction and Building Materials 200 (2019) 502–513 509

1.75 geopolymers (i.e. G0, PA0, C0), the number of unreacted grains
had reduced in all specimens. This was attributed to additional
1.50
High alkali-fly ash reactivity over this period which results in the gel
1.25 produced filling the cracks and voids visible at 28 days, thus
increasing the compressive strength.
Icorr (μA/cm2)

1.00
0.75
0.50
Gladstone PC
0.25
Collie Pt.Augusta
0.00
0 100 200 300 400 500
Duraon (Days)
Fig. 6. Corrosion rate of geopolymer and PC concrete specimens, immersed in 3%
NaCl solution.
Fig. 7. Corrosion pattern of rebar in geopolymer and PC concrete specimens,
immersed in 3% sodium chloride solution.
capacity was observed for the Collie specimen, given the low, 0.3%
calcium oxide content in the ash. The Gladstone and Pt.Augusta
samples had similar calcium oxide contents and displayed similar
binding capacities. This is attributed to the calcium–aluminosili-
cate (C–A–S–H) gel formed during geopolymerisation physically
adsorbing chlorides on the surface of the C–A–S–H gel.
Fig. 8 shows the microstructure observed in the fly ash geopoly-
mer concretes at 28 and 540 days at 0%, 2% and 5% sodium chloride
concentrations. At 0% all geopolymer concretes showed an increase
in the packing density in the microstructure from 28 to 540 days.
Gladstone has a well compacted, uniform, dense microstructure
with a small number of unreacted/partially reacted fly ash spheres
and micro-cracks. Pt.Augusta has a similar microstructure to Glad-
stone, but is heterogeneous in nature, with an increased number of
micro-cracks and unreacted grains. At 28 days, the Collie geopoly-
mer has a loosely packed microstructure with a large quantity of
unreacted fly ash particles. At 540 days in non-chloride
However, propagated cracks can still be observed after 540 days
for the geopolymers containing chlorides, with the width of these
Moderate
cracks in Collie being visibly larger than those in the Gladstone and
Pt.Augusta matrices. Further inspection of the microstructure
reveals that the number of cracks and the width of the cracks in
Low
the geopolymer matrix increased with an increase of chloride con-
centration in all geopolymer concretes, consistent with the
600 reduced compressive strengths observed. It is hypothesized that
an increase in the corrosion products in rebar would increase the
internal stresses in the adjacent concrete, resulting in formation
of cracks in the gel matrix and the widening of existing cracks.
Fig. 9 illustrates the cumulative macropore volume changes of
the fly ash geopolymer and PC concrete between 50 nm and
25 mm. All concretes showed a porosity reduction between 28
and 365 days, but by different percentages. The degree of geopoly-
merization determines the quantity of gel formation, and this gel
fills the gaps between unreacted fly ash particles and pore spaces,
thus refining the size of these pores. Two major zones were iden-
tified in the examined macropore region, i.e. pore size ranging from
50 nm to 1 mm and 1 mm–25 mm. Collie and Gladstone geopolymer
concretes displayed the highest and lowest macroporosity, respec-
tively, at both 28 and 365 days. Both Gladstone and Pt.Augusta dis-
played a substantial porosity reduction in the range of 50 nm–1 mm
over this period. PC concrete also showed a porosity reduction dur-
ing this period, which was significant in the range of 1 mm–25 mm.
The pore size distribution in Collie varied significantly compared to
the other two fly ash geopolymers, having the lowest and highest
pore volume reduction at 50 nm–1 mm and 1 mm–25 mm regions,
respectively between 28 and 365 days. This variation in pore size
distribution is consistent with the lower compressive strength
and higher chloride ingress observed for the Collie geopolymer
concrete.
FTIR analysis of three different fly ash based geopolymer con-
cretes at reinforcement-geopolymer binder interface (at 540 days)
is shown in Fig. 10. The corrosion products were examined at the
rebar/binder interface of 3% cast in chloride geopolymer specimens
and compared to the ponding specimens. FTIR analysis identified a
strong peak of hematite (Fe2O3) and akageneite (FeO(OH)) between
770 cm1 and 690 cm1 in all three geopolymers with cast-in chlo-
rides, whereas a small peak of lepidocrocite [c-FeO(OH)] is noted
at 1155 cm1. However, for ponded specimens, FTIR analysis did
not detect this lepidocrocite peak, and only detected a small peak
identified with hematite and akageneite.
Peaks associated with A–O–Al/Al–OH and Si–O–Si/Si–OH bonds
were observed for all geopolymer concretes at 1030 cm1 and
580 cm1, respectively. These bonds are indicators of N–A–S–H
gel [42], which is formed during the formation of the three dimen-
sional geopolymer network. It was interesting to note that a broad
peak with a small hump occurred at 1030 cm1 for cast-in chloride
specimens, compared to the narrow, sharp peak observed for the

Table 4
Chloride binding capacity in geopolymer and PC concretes.

Concrete Type Cl (% w/w of Cement) Cl binding Capacity (%)

Total Cl Free Cl Bound Cl
Gladstone GP 0.80166 0.30715 0.49451 61.7
Pt.Augusta GP 0.82659 0.30001 0.52658 63.7
Collie GP 1.33667 0.65001 0.68666 51.4
PC Concrete 1.21260 0.42716 0.78544 64.8
510 C. Gunasekara et al. / Construction and Building Materials 200 (2019) 502–513

Fig. 8. Microstructure development of different fly ash based geopolymer concretes.

0.105
50nm < < 1μm
is shown in Fig. 11. All fly ash geopolymer concretes exhibited
Gladstone-28d
Pt.Augusta-28d
peaks of quartz (SiO2) and mullite (Al6SiO2O13), which are indica-
0.095
Collie-28d tive of the formation of zeolytes during geopolymerisation [43].
Cumulave Pore Volume (ml/g)

0.085 PC-28d In addition to these phases, all geopolymers displayed peaks of cor-
Gladstone-365d rosion products in the form of hematite (Fe2O3) and akageneite
0.075
Pt.Augusta-365d (FeO(OH)), as noted in the FTIR spectra. Both Gladstone and Pt.
0.065 Collie-365d Augusta geopolymer concretes showed a higher intensity of hema-
PC-365d tite and akageneite in the 3% cast-in chloride specimens, compared
0.055
to chloride immersion specimens. However, Collie displayed a
0.045 higher quantity of corrosion products in the immersion specimens.
The XRD results are consistent with the observed corrosion levels
0.035
on the rebar in the specific geopolymer concrete. It is hypothesized
0.025 that with an increase in the formation of three dimensional N–A–
S–H and C–A–S–H cross linking phases in the gel matrix reduces
0.015
the porosity and increases the resistance of the hardened matrix
0.005 to chloride ingress. Hence, the lower ingress of chloride observed
10 100 1000 10000 100000
in the Gladstone and Pt. Augusta concretes.
Pore Diameter, (nm)

Fig. 9. Pore size distribution of geopolymer and PC concretes between 28 and 5. Discussion
365 days.

PC concrete develops compressive strength through the forma-

ponding specimens, in particular for Gladstone and Pt.Augusta.
With increasing degree of geopolymerisation, the A–O–Al/Al–OH
bonds tend to become sharper and have an increase in peak height
[42]. Hence, the observed FTIR data correlate well with the
observed higher degree of geopolymerisation in the ponded
geopolymer specimens compared with the cast-in chloride
specimens.
The XRD analysis of the different fly ash based geopolymer con-
crete specimens at the reinforcement-geopolymer binder interface
tion of calcium silicate hydrates, which are produced by the hydra-
tion process of water, reacting with the PC [28,44]. However, fly
ash based geopolymer concrete follows a different reaction path-
way and gain compressive strength through the formation of alu-
minosilicate gel. The gel is produced by dissolving alumina and
silica oxides of the fly ash in a highly alkaline medium, typically
provided by the sodium hydroxide and sodium silicate solutions.
The rapid reaction of Gladstone fly ash in alkaline solution, due
to the higher surface area coupled with a large quantity of reactive
amorphous Al2O3 and SiO2 in the range of 10–45 mm, is expected to
 C. Gunasekara et al. / Construction and Building Materials 200 (2019) 502–513 511

1 [Lepidocrocite] 2 [N-A-S-H /Al-OH gel] 3 [Akaganeite/FeO(OH)] 4 [Hemate /Fe2O3] 5 [N-A-S-H /Si-OH gel]

(a) 3% cast in Chloride specimes (b) Ponded specimes

1 2 3 4 5 2 3 4 5

Collie Collie
Pt.Augusta

Pt.Augusta
Gladstone
Gladstone

1400 1300 1200 1100 1000 900 800 700 600 500 1400 1300 1200 1100 1000 900 800 700 600 500
Wave number (cm-1) Wave number (cm-1)

Fig. 10. FTIR analysis of three different fly ash geopolymer concretes at 540 days.

60 60 60
G3 Q : Quartz (siO2) PA3 Q : Quartz (siO2) C3 Q : Quartz (siO2)
50 M : Mullite (Al6SiO2O13) 50 M : Mullite (Al6SiO2O13) 50 M : Mullite (Al6SiO2O13)
H : Hemate (Fe2O3) H : Hemate (Fe2O3) H : Hemate (Fe2O3)
Q Q A : Akaganeite [FeO(OH)]
Intensity

40 A : Akaganeite [FeO(OH)] 40 A : Akaganeite [FeO(OH)] 40

Q
30 30 30

20 20 20
Q M M Q
A
10 H 10 Q M H 10 H
H M A H H M M
M Q A A A H A M H A H A
H M H Q H A Q
0 0 0
20 30 40 50 60 70 20 30 40 50 60 70 20 30 40 50 60 70
60 60 60
Q : Quartz (siO2) Q Q : Quartz (siO2) Q
Gimm PAimm Cimm Q : Quartz (siO2)
50 M : Mullite (Al6SiO2O13) 50 M : Mullite (Al6SiO2O13) 50 M : Mullite (Al6SiO2O13)
H : Hemate (Fe2O3) H : Hemate (Fe2O3) H : Hemate (Fe2O3)
Q A : Akaganeite [FeO(OH)] A : Akaganeite [FeO(OH)]
Intensity

40 40 40 A : Akaganeite [FeO(OH)]

30 30 30

20 20 20

Q Q A
10 Q M 10 10 H
M H M
H A H Q A M M H M
A H A M H M
A H A Q M A H Q A
0 0 0
20 30 40 50 60 70 20 30 40 50 60 70 20 30 40 50 60 70
2 Theta (degrees) 2 Theta (degrees) 2 Theta (degrees)

Fig. 11. XRD analysis of three different fly ash geopolymer concretes at 540 days.

produce large quantities of sodium–aluminosilicate (N–A–S–H) meric reaction because of its high reactivity, thus, the minimal
and calcium–aluminosilicate (C–A–S–H) gel [45] and form a uni- strength development (14.1%) observed between 28 and 540 days.
form condensed gel matrix at an early age, Fig. 8. This dense Pt.Augusta contains a higher calcium oxide percentage, which
microstructure together with a lower macroporosity, Fig. 9, results in addition to the reactive amorphous Al2O3 and SiO2 in 10–
in the high strength of Gladstone at 28 days compared to the PC 20 mm range, produces additional C–A–S–H gel as well as the N–
concrete. However, little fly ash remains for subsequent geopoly- A–S–H gel. The combination of the N–A–S–H and increased
512 C. Gunasekara et al. / Construction and Building Materials 200 (2019) 502–513
amounts of C–A–S–H gels provides additional rigidity to the three-
dimensional geopolymeric matrix. However, due to the lower sur-
face area, the alkali–fly ash dissolution rate is expected to be lower
than Gladstone fly ash. This resulted in the formation of a non-
uniform, heterogeneous geopolymer gel matrix which in turn
accounts for the lower compressive strength displayed by Pt
Augusta. Collie has a lower degree of alkali–fly ash reactivity due
to its lower surface area and small quantity of reactive amorphous
Al2O3 and SiO2 available in the range of 10–45 mm. This is hypoth-
esised as the reason that the Collie demonstrated a less compact,
non-uniform cracked microstructure, which was observed to be a
significantly different microstructure compared to the other two
geopolymers. Hence, the higher macroporosity and lower com-
pressive strength of the Collie geopolymer concrete.
During geopolymerization, the glassy Al2O3 and SiO2 in the pre-
cursor fly ash react with the strong alkalis and produces a complex
three-dimensional polymeric aluminosilicate gel network. Hence,
the greater the geopolymerisation and gel formation, the higher
the OH agglomeration into the geopolymeric backbone is to be
expected. This would result in reduction of pH in the pore solution
as the activator is consumed by the geopolymerisation reaction. It
has been noted that the relative concentrations of the Cl/OH ions
in the pore electrolyte govern the risk of chloride-induced corro-
sion in cement matrices [28]. Hence, the increase of Cl/OH ratio
due to reduction of alkalinity in Gladstone geopolymer results in
the highest corrosion rate being observed in the cast in chlorides
specimens. The increase in the corrosion rates for the Pt.Augusta
and Collie geopolymer concretes is attributed to the on-going
geopolymerisation lowering the OH concentration in the respec-
tive pore solutions and thus an increase in the Cl/OH ions in
the pore solution.
Conversely both Gladstone and Pt.Augusta had lower corrosion
rates than the PC concrete for the ponded specimens. Kupwade-
Patil et al. [46] observed similar corrosion behavior for ponded
fly ash geopolymer concrete specimens, with Icorr = 0.166 lA/cm2
and Icorr = 2.38 lA/cm2 for geopolymer and PC concrete respec-
tively. This is attributed to the lower rate of ingress of chloride, cor-
responding to a lower chloride diffusion coefficient for the
geopolymer concrete. The availability of free chlorides in the con-
crete is also a governing factor. Furthermore, these two geopoly-
mers showed similar chloride binding capacity compared to PC
concrete. On the other hand, Collie had the highest chloride con-
tent, the higher free chloride content in the pore solution and the
lowest chloride binding capacity. This resulted in the highest cor-
rosion rate being observed for the Collie geopolymer specimens
under ponded conditions. The cast-in data would indicate that
for an equivalent chloride concentration at the rebar a higher cor-
rosion rate can be expected for the Gladstone and Pt.Augusta
geopolymers, due to their lower pH. However, due to the low chlo-
ride diffusion coefficients of these geopolymers the rate of ingress
will be slower and thus the time until the critical chloride value
required to initiate corrosion will be extended. Understanding
the relationship between diffusion rate and critical chloride con-
centration for geopolymer concretes will be critical in determining
their long term durability.
6. Summary and conclusion
The key findings of this research study can be summarized as
follows:
1. Fly ash geopolymer concretes showed significantly higher cor-
rosion rates than PC concrete with the same concentration of
cast-in chlorides. This is attributed to geopolymerisation and
aluminosilicate gel formation leading to OH agglomeration
into the geopolymeric backbone, resulting in a reduction of
pH in the pore solution compared to PC concrete. This leads
to an increase in the Cl/OH ratio in the geopolymer concrete
and hence higher rates of corrosion.
2. Gladstone and Pt.Augusta geopolymer concretes displayed con-
tradictory corrosion behaviour when specimens were ponded
as compared with cast-in chlorides, showing a lower corrosion
rate than PC concrete. This is attributed to formation of three
dimensional N–A–S–H and C–A–S–H cross linking in the gel
matrix which decreases the diffusion of chlorides in the Glad-
stone and Pt.Augusta geopolymer.
3. The chloride diffusion rate in geopolymer concrete is dependent
on the porosity of the geopolymer matrix, which is governed by
the reactivity of the precursor fly ash. The reactivity is depen-
dent upon surface area, amorphous Al2O3 and SiO2 content
and CaO content. Higher surface area and amorphous Al2O3
and SiO2 increase aluminosilicate gel formation and produce a
stronger, less porous geopolymer matrix which reduces the rate
of chloride ingress.
4. The chloride binding capacity of low calcium fly ash based
geopolymer concrete is dependent on the CaO content in pre-
cursor, which produces C–A–S–H gel in the geopolymerisation,
resulting in the physical adsorption of chloride ions on the gel
surface, reducing the rate of chloride ingress.
5. Corrosion products in the form of hematite [Fe2O3], akageneite
[FeO(OH)] and lepidocrocite [c-FeO(OH)] are identified.
Conflict of interest
None.
Acknowledgements
Flyash Australia Pty Ltd and Cement Australia Pty Ltd are acknowl-
edged for providing fly ash for this research. RMIT University pro-
vided the microscopy facility, X-ray facility and microanalysis
facility for this study also acknowledged. Australian Research
Council Industrial Transformation Research Hub for Nano-science
based construction material manufacturing (IH150100006) is
funded for this work.
Compliance with Ethical Standards
The authors declare that they have no conflict of interest.
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