Rafeet Et Al - Final
Rafeet Et Al - Final
Rafeet Et Al - Final
TITLE
Effects of slag substitution on physical and mechanical properties of fly ash-based alkali activated
binders (AABs)
AUTHORS
Rafeet, A; Vinai, R; Soutsos, M; et al.
JOURNAL
Cement and Concrete Research
DEPOSITED IN ORE
02 May 2019
http://hdl.handle.net/10871/36948
A NOTE ON VERSIONS
The version presented here may differ from the published version. If citing, you are advised to consult the published version for pagination, volume/issue and date of
publication
Effects of slag substitution on physical and mechanical properties of fly
School of Natural and Built Environment, Queen’s University Belfast, BT9 5AG, United Kingdom
*Corresponding author. Current address: College of Engineering, Mathematics and Physical Sciences,
Abstract
Neat fly ash-based alkali activated binders require high activator dosages and high temperature curing in order to
develop satisfactory mechanical properties. Blending ground granulated blast furnace slag (GGBS) with fly ash
can give medium to high strengths without the need for high temperature oven curing. An extensive investigation
was carried out for understanding the effects of GGBS substitution of fly ash in mortar. GGBS substitution in the
mix has an impact on mix proportions, fresh and hardened properties, and microstructure of reaction products.
The strength of fly ash/GGBS blends cured at room temperature increased with the increase of GGBS content,
whilst setting time showed an opposite trend. Fly ash/GGBS blends required lower activator dosages for obtaining
high compressive strength, which has cost and environmental benefits. XRD, FTIR, TGA, and SEM/EDX results
confirmed the presence of C-A-S-H gel as a reaction product with as low as 20% GGBS content.
Keywords: alkali activated cement (D), microstructure (B), mixture proportioning (A), fly ash (D), Granulated
1. Introduction
Alkali activated concrete (AAC) can be a potential alternative to ordinary Portland cement based concrete (OPC)
for reducing the CO2 emissions from the building sector, which account for around 8% of the worldwide carbon
emissions [1]. Numerous studies have been carried out worldwide on binders based on neat fly ash or neat slag.
Low calcium fly ash-based binders usually require high temperature curing and high activator dosages to achieve
good mechanical properties. Chemical activators are responsible for the majority of CO2 emissions and production
costs of AAC, as using high activator dosages leads to an increase in both of these [2]. This may hinder the
industrial uptake of this technology. Slag-based binders, on the other hand, require relatively lower activator
dosages but suffer from some technical problems such as rapid setting and low workability. Recently, blended
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binders have attracted a great deal of attention mainly due to their potential to mitigate some of the above
mentioned issues.
Blending fly ash and Ground Granulated Blast Furnace Slag (GGBS) enables curing at ambient temperature (20
°C) leading to a denser and more compact microstructure and therefore better mechanical properties [3]. However,
despite around 40 years of studying [4], relatively few investigations focused on the optimization of mix design
in terms of binder blends and their influence on activator dosage, fresh and hardened properties of the mix and
identification of the microstructure of reaction products. The majority of the studies focused on pastes [5, 6] and
only few data are available on the properties of blended fly ash/GGBS mortars and concrete [7-9]. The main
conclusions from these studies were that the substitution of GGBS increased the compressive strength but
decreased the setting time especially when higher percentages of GGBS and higher chemical dosages were used.
Understanding the chemistry of AAC can also help towards designing more robust and durable concrete.
However, the reaction mechanism of fly ash, despite having been studied for decades, is still not yet well
understood [1]. Blending fly ash with GGBS makes the reaction process more complex as different reaction
products can form. These reaction products depend on the ratio of slag and the activation dosages. Geopolymer
gel (N-A-S-H) was found to be the main reaction product in mixes with slag ratio up to 25%, with possible
This study aims to provide more insight into the influence of GGBS substitution on (a) the physical and
mechanical properties of fly ash/GGBS blends, (b) the required activator dosage and (c) heat output development.
Furthermore, characterisation of reaction products was carried out using microstructural techniques in order to
The binders used in this study were based on fly ash and GGBS having chemical compositions (obtained by X-
ray fluorescence – XRF) as shown in Table 1. Fly ash was supplied by Power Minerals Ltd, United Kingdom. It
was class F according to ASTM C618 [11], and compliant to BS EN 450 standard [12], with Loss on Ignition
(LOI) falling into Category A. GGBS was supplied by Civil and Marine Ltd, United Kingdom. The slag was
defined as basic since its basicity coefficient Kb = (CaO+MgO) / (SiO2+Al2O3) was higher than 1. The physical
properties of the precursors are shown in Table 2. The grain size distribution is described by the parameters D50
and D90, i.e. the mesh sizes for 50% and 90% sample mass passing respectively.
Oven-dried natural siliceous sand having grain size in the range 0 to 4 mm and density 2.69 g/cm3 was used for
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Table 1. Main oxides determined by XRF analysis on precursor materials.
Other oxides
Oxide CaO SiO2 Al2O3 Fe2O3 Na2O K2O SO3 MgO TiO2 LOI
(minors)
Fly ash 2.2 46.8 22.5 9.2 0.9 4.1 0.9 1.3 1.1 7.4 3.6
GGBS 43.7 29.4 11.2 0.4 1.0 0.9 1.8 6.9 0.7 1.6 2.4
Alkali dosage (M+) and alkali modulus (AM) were the parameters adopted for determining the activator dosage
(i.e. mass of sodium hydroxide and sodium silicate solutions in the mix). M+ is the mass ratio of sodium oxide
(Na2O) to the total mass of the precursor, whilst AM is the mass ratio of Na2O to SiO2. The activators used in this
study were commercial grade (99% purity) sodium hydroxide (NaOH), and sodium silicate solution with
SiO2:Na2O mass ratio = 2:1 (mass composition: Na2O 12.8%, SiO2 25.5%, water 61.7%), provided by Fisher
Scientific UK. NaOH solutions with the required concentration were prepared by dissolving NaOH prills in tap
water, leaving the solution to cool down for at least 24 hours before use. Sodium hydroxide solution was used to
adjust the Na2O content in the activating solution in order to achieve the required M+. The water-to-solid ratio
(w/s) was defined as the mass ratio of water to the mass of binder including the solid chemicals (i.e. mass of
Mortars were mixed in a planetary mixer. The sand/binder ratio was kept constant at 2.75. Dry constituents (sand,
fly ash and GGBS) were first dry mixed for 2 minutes, then the liquid part was added and mixing continued for a
further 5 minutes. Typical mix proportions of mortars are shown in Tables 3a for production batches. These have
Table 3a. Typical mix proportions for mortar production batch (M+ 7.5%, AM 1.25, w/s ratio 0.37).
Label Fly ash (g) GGBS (g) NaOH solution Sodium silicate Water Sand (g)
@ 30% conc. (g) solution (g) (g)
100/0 500 0 97 118 70 1375
95/5 475 25 97 118 70 1375
80/20 400 100 97 118 70 1375
60/40 300 200 97 118 70 1375
30/70 150 350 97 118 70 1375
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Table 3b. Typical mix proportions for 1 litre of mortar (M+ 7.5%, AM 1.25, w/s ratio 0.37).
Label Fly ash (g) GGBS (g) NaOH solution Sodium silicate Water Sand (g)
@ 30% conc. (g) solution (g) (g)
100/0 530 0 102 125 74 1456
95/5 504 26 102 125 74 1459
80/20 427 107 103 126 74 1467
60/40 323 215 104 127 75 1478
30/70 163 381 105 128 76 1495
Setting time was measured with a manual Vicat apparatus. The paste consistency required for this method
was not achievable with geopolymer pastes due to the need of higher water contents for preventing quick
reaction as discussed by Vinai et al. [13]. The Vicat method was instead used with mortars for comparing
The consistency of mortars was assessed using the flow table in accordance with British Standard BS
EN 1015-3: 1999. The conical frustum available in the laboratory had different dimensions than the
standard (90 mm instead of 60 mm in height, internal diameter 65 mm instead of 100 mm at the base and
50-mm mortar cube specimens were cast in PVC moulds and compacted on a vibrating table. Moulds
were then wrapped in a plastic film and stored for curing. Neat fly ash samples were oven cured at 70 °C
whereas fly ash/GGBS blends were cured at a constant room temperature of 20 °C ± 2 °C and a relative
humidity of 55% ± 5% until the day of testing. Samples were demoulded after 24 hours and tested for
compressive strength at 1, 7 and 28 days using a 2000 kN capacity compression testing machine with a
loading rate of 1.5 kN/s, which is within the range specified in BS 12390-3: 2009.
A TAM Air Isothermal Calorimetre (IC) was used for determining the heat of reaction of fly ash/GGBS
paste blends. Ex-situ (i.e. sample mixed outside the machine and then lowered into the measuring
chamber) and in-situ (i.e. sample mixed directly in the measuring chamber) methods were adopted. Ex-
situ measurements were carried out at two temperatures, i.e. 20 and 70 °C, whilst for in-situ measurement
X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermo-gravimetric analysis (TGA)
and scanning electron microscopy (SEM) coupled with Energy Dispersive X-ray analysis (EDX) techniques were
XRD was used to detect the crystal phases of both the raw materials and the reacted samples. Tests were
carried out with a PANalytical X’Pert PRO diffractometer using pure copper-K-Alpha 1 radiation with
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wavelength 1.54 Å. The X-ray generator was set to 40 kV and 40 mA, the recorded angular range was 5
to 60° (2θ) with a step close to 0.017°. Malvern PANalytical X’Pert Highscore Plus software was used
for pattern interpretation. An internal standard (corundum) was used with raw fly ash for the
FTIR spectra were obtained using a Jasco 4100 series FTIR Spectrometer to determine the chemical
functional groups of raw materials and reacted samples. Jasco software was used for data interpretation.
Attenuated Total Reflectance (ATR) attachment (germanium crystal) in the range 3960 – 650 cm-1 was
TGA was performed using a thermobalance Netzsch TG 209 F1 Libra. Powder was obtained from the
samples with the use of a mortar and pestle. The powder was placed in an alumina crucible and then
heated from 25 to 1000 °C at 20 °C/min in an inert environment. The thermobalance was coupled with a
Pfeiffer mass spectrometer Vacuum Thermostat for the analysis of gases emitted during the heating
process.
SEM images and EDX data were obtained on gold-palladium coated cubes of 1x1x1 cm with a FEI
QUANTA 200 scanning electron microscope. The accelerating voltage was set at 20 kV. Six samples
The effect of partially replacing fly ash with GGBS on the (a) fresh and hardened properties of mortars, (b) reaction
heat development and (c) microstructure of pastes was investigated. A detailed study was carried out for evaluating
the effect of activator dosage on neat fly ash mortars and fly ash/GGBS blends with high level of GGBS
substitution (70% in mass), in order to determine ranges of dosage giving high compressive strengths. Several
microstructural analysis techniques were used to assess the properties of the reaction products and relate these to
the compressive strengths of mortars. The chemical composition of reaction products was determined which gave
3.1. Fresh and hardened properties of mixes with neat fly ash and fly ash/GGBS blends
A first series of mixes aimed at assessing the effects of the GGBS inclusion in fly ash-based mortars cured at
ambient temperature. This included tests for consistency, setting time and compressive strength. Samples were
mixed with GGBS contents ranging from 5% by mass (5% GGBS and 95% fly ash, referred as to 95/5, where the
first number corresponds to the fly ash content and the second to the GGBS content) to 70% (i.e. 30/70). Mixes
with higher GGBS content exhibited setting within a very short time (i.e. less than 5 minutes) and therefore were
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not investigated. Water-to-solid ratio (w/s) was kept constant at 0.37. Activator dosages were kept constant at M+
Results from the investigation on consistency and setting time of mortars with different GGBS contents are shown
in Figure 1. Mortar consistency seemed to be moderately affected by the GGBS substitution, although no clear
trend could be observed. An increase of GGBS content seemed to lead to a reduction of the flow, but this reduction
was not significant. Similar findings have also been reported in the literature [3, 15].
The initial setting times were however significantly affected with increasing content of GGBS. The initial setting
time decreased from above 3 hours for 95/5 mix to as low as 10 minutes in the case of 30/70 mix. The reduction
in the initial setting time was found to be bilinear, with a more pronounced variation in the range 5% to 20%
GGBS content (i.e. 95/5 to 80/20 mixes), in which the setting times were reduced from 3 hours to 1 and a half
hour. The effect of GGBS inclusion on setting time had a lower slope in the GGBS range 20% to 70%, in which
the initial setting time varied from one and a half hours to about 10 minutes.
Figure 1. Consistency and setting time of fly ash/GGBS mortar mixes. Legend: ×: initial setting time (minutes).
○: flow (mm).
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3.1.2. Cube compressive strength
Compressive strength of ambient temperature cured mortar cubes was found to increase with increasing GGBS
content, see Figure 2. 28-day compressive strength varied from about 20 to 30 MPa for GGBS contents up to 20%
to about 75 MPa for GGBS substitution of 70%. The increase in the strength with increasing GGBS has also been
reported by others [3, 15, 16] and it is attributed to the densification of the matrix due to the formation of calcium
silicate hydrate binding gel [15]. The increase in the compressive strength observed with increasing GGBS in the
mix blend was also attributed to the coexistence of the geopolymeric gel (N-A-S-H) along with C-A-S-H type gel,
which can lead to a denser and more homogeneous matrix and eventually to better mechanical properties [17].
Increasing GGBS allowed high compressive strengths to be obtained for samples cured at room temperature at a
specific combination of activator dosages, i.e. M+ 7.5% and AM = 1.25. However, neat fly ash mortars have been
shown to be capable of achieving compressive strengths as high as 60 MPa, when other activator dosages are used
[14]. It is therefore of interest to understand how the activator dosages influence neat fly ash and fly ash/GGBS
The mechanical strength of alkali activated binders is significantly influenced by the activator dosage, and a range
of dosages resulting in high compressive strengths have been suggested [2, 14, 18-20, 65, 66].
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3.2.1. Effect of activator dosage on the compressive strength of 100% fly ash mortar cubes
The effect of M+, which is a proxy for the concentration of the alkali activator solution, and AM, which is a proxy
for the amount of added silica in the activator solution, on compressive strength was first investigated for neat fly
ash mortar cubes. M+ was in the range 7.5 to 13.5%, whilst AM was from 0.5 (corresponding to all sodium
silicate) to ∞ (i.e. all sodium hydroxide). Figure 3 shows the combined effect of AM and M+ on the compressive
strength of mortar cubes produced with 100% fly ash. Mix proportions of mortars are shown in Appendix A (Table
A1 for production batches information, Table A2 for grams/litre conversion). The structure of sample labels is
“precursor-M+-AM”. In order to maintain the required w/s ratio, samples with M+ equal to 12.5% and 13.5%
Figure 3. Combined effect of M+ and AM on 28-day compressive strength for neat fly ash mortar mixes.
The “sweet spot” for compressive strength was found to be with an AM in the range 0.7 to 1.0 and an M+ in the
range 11.5% to 13%, where compressive strengths in excess of 60 MPa were obtained.
The AM was found to have a strong effect on the compressive strength development, as compressive strengths
higher than 50 MPa were obtained with an AM in the range 0.7-1.0 regardless of the value of M+. Similar ranges
have been reported in the literature [21-23]. This can be attributed to the enhancement of the degree of
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polymerisation of the dissolved species, leading to better mechanical properties. Hajimohammadi et al. [24]
observed that high Si availability led to multiple aluminosilicate nucleation point opportunities, enhancing also
the Al dissolution and the geopolymer gel formation. Compressive strength decreased as AM increased over 1.0,
being in the range of about 10 MPa when AM = ∞ (i.e. when only NaOH solution was used as activator). This
can be due to the non-availability of soluble silicates which affected the geopolymerisation process and, thus
resulted in lower compressive strength. A decrease in compressive strength was also observed when the AM was
This strength reduction (around 50%) can be attributed to the decrease in the pH of the system with the increase
in sodium silicate solution. A drop in the pH from 14 to 12 when AM decreased from 1.25 to 0.5 has been observed
in the literature [25]. The decrease in the pH affects the dissolution of the glassy aluminosilicate species from the
precursor [26], which in turn affects the geopolymerization process and thus results in lower compressive strength.
The amount of SiO2 in the activating solution (i.e. high soluble silicates) seemed to correlate well with the
compressive strengths, confirming that the increase in SiO2 results in an increase in compressive strength until a
SiO2/binder mass ratio of about 15%. Higher amounts of SiO2 did not increase the strength further. Data points
corresponding to AMs at the two ends of the investigated range did not follow the trend, see Figure 4. As
previously discussed, when the silicate contents were very low (i.e. AM > 30 in Figure 4) the geopolymerisation
process was hindered, whilst excess of silicate (i.e. AM 0.5 in Figure 4) lowered the pH of the pore solution,
reducing the dissolution of reactive species and thus negatively affecting the strength development.
The effect of M+ on strength was also assessed. Within the optimum range of AM previously determined,
compressive strength increased from 50 to 60 MPa when M+ of 8% increased to 12.5%. The increases in
compressive strength were more pronounced (i.e. from about 35 – 40 MPa to about 55 to 60 MPa) when M+
increased from 7.5% to 9.5%. The strength increase was not significant for M+ higher than 12.5%. This was
attributed to the saturation of the gel with alkali ions, i.e. less free water is available for speciation of silica and
3.2.2. Effect of activator dosage on the compressive strength of fly ash/GGBS mortar cubes
The effect of activator dosage on compressive strength of blended binder was investigated on mixes with a GGBS
content as high as 70% (i.e. 30/70). Higher than 70% GGBS substitution was not investigated as it resulted in
quick setting times which did not allow proper casting of samples, for the M+ and AM used in this series of mixes.
Preliminary trials with 30/70 mixes showed satisfactory workability and reasonable working time. Neat GGBS-
based binder typically requires lower M+ dosages than neat fly ash [6, 23, 27, 28] and therefore the M+ range
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selected was from 4.5 to 10.5%, and the AM was in the range 0.75 to ∞ (i.e. NaOH solution only). Water-to-solid
ratio (w/s) of 0.4 was adopted to ensure proper consistency of mixes. This value was slightly higher than the 0.37
used for neat fly ash mixes. Results are shown in Figure 5. Mix proportions of mortars are shown in Appendix A
Figure 4. Relationship between mass ratio of SiO2 in the activating solution to the binder and 28-day compressive
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Figure 5. Effect of alkali dosage M+ and alkali modulus AM on 28-day compressive strength of 30/70 blend
GGBS substitution had a significant effect on activator dosages required for achieving highest possible strength.
28-day strength higher than 60 MPa was obtained with AM in the range 0.7 to 1.7 and M+ in the range 6 to 10.5%.
AM values in the range 1.0 to 1.25 achieved mortar compressive strengths higher than 60 MPa with M+ as low
as 6%. Neat fly ash mixes, as reported previously, required an AM in the range 0.7 to 1 and M+ in the range
11.5% to 12.5%. The inclusion of GGBS in the mix allowed an increase of the AM and a decrease of the M+ for
obtaining comparable strengths. This is a reduction of the amount of chemical activators required and therefore a
When only NaOH was used in the mix (i.e. AM infinite), a strength equal to 30 MPa was obtained regardless of
the M+ value. This can be attributed to the fact that the reaction in this case is mainly the hydration of calcium
species of GGBS. This kind of reaction requires a pore solution with a pH high enough for breaking down the
slag grain layer, allowing the water to reach the slag and the hydration to take place [29]. An M+ of 4.5% has
been reported to be sufficient for neat GGBS systems, although inadequate for neat fly ash systems [30]. M+ of
4.5% gave the same 28-day compressive strength of around 30 MPa for all the investigated AM i.e. 0.75, 0.95,
1.15 and 1.25. This confirms that the reaction at this AM dosage is mainly due to the GGBS. The aluminosilicates
from the fly ash do not contribute as this AM dosage is not sufficient for triggering the dissolution of fly ash
particles.
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For higher alkali dosages (M+) of 6%, 7.5%, 8.5% and 10.5%, the ‘optimum’ AM was found to be 1.25 (1/AM
of 0.8). Mixes with M+ of 8.5% and 10.5% gave compressive strengths of around 74 MPa, similar to those with
M+ of 7.5%.
Higher chemical dosages have adverse effects on the mix, i.e. they cause reduction in the setting time, an increase
of the CO2 footprint and an increase of the cost of AAC. Activator dosages of M+ = 7.5% and AM = 1.25 were
Heat output rate was determined with an isothermal calorimeter technique in order to understand the effects of
GGBS inclusion and curing temperature on the reaction. Ex-situ tests (i.e. samples prepared outside the
calorimeter) simulating curing temperatures 20 °C and 70 °C respectively were carried out on paste samples with
different GGBS percentage substitution (100/0, 95/5, 82/20, 60/40, 30/70 and 0/100). Furthermore, in-situ tests
(i.e. samples mixed directly in the calorimeter after temperature stabilisation) simulating room temperature
conditions (i.e., 20 °C) were carried out on 4 paste samples, namely 30/70, 60/40, 80/20 and 100/0 in order to
investigate the very early reaction which could not be investigated with the ex-situ method.
The solid powder was mixed with the liquid activator outside the isothermal calorimeter, and then the sample was
placed in the testing chamber. Some time was then allowed for temperature stabilisation and only after this
recording of the heat output started. The first 40 to 45 minutes of reaction could not be investigated.
Tests carried out at 20 °C aimed at assessing the heat of reaction simulating room temperature curing. Mixes with
significant content of GGBS (mixes 60/40 and above) showed one prominent peak, attributed to the dissolution
and precipitation reaction leading to the formation of C-A-S-H type binding gel [3], see Figure 6(a). The peak
appeared earlier and was higher as GGBS content increased. The peak occurred at around 10, 6, and 4 hours for
60/40, 30/70 and 0/100 samples respectively, whilst it was not observed in samples with GGBS content lower
than 40%. Similar peak but at longer reaction time i.e. 24 hours has been reported in the literature [31] for 50/50
fly ash/GGBS blend. The occurrence, magnitude and location of the peaks depend on various parameters such as
the type and concentration of the activator, reaction temperature [32] and the nature and the reactivity of the raw
materials.
The cumulative heat output increased with the increase in GGBS content, see Figure 6(b), which is consistent
with what has been reported by others [31]. Values recorded up to 120 hours were in the range of 140, 130, and
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90 J/g for mixes 0/100, 30/70, and 60/40 respectively. Mixes with low GGBS content such as 80/20, 95/5 and
100/0 showed low to very low cumulative heat outputs, with values of about 55, 20, and 10 J/g respectively.
Tests carried out at 70 °C investigated the reaction simulating oven curing conditions. The reaction developed
faster compared to tests carried out at 20 °C. After about three hours, residual heat flows of 2 mW/g were recorded,
see Figure 6(c). Peaks shifted toward shorter times as GGBS content increased as was observed for samples tested
at 20 °C. Peaks however occurred earlier, i.e., about 30 minutes, and with much higher intensities than those
Cumulative heat generally increased with the increase in GGBS content, as the reaction of GGBS is exothermic
involving mainly a hydration process. Cumulative heat outputs recorded for mixes 0/100, 30/70, and 60/40 for up
to 50 hours were comparable to the values recorded at 20 °C, see Figure 6(d), suggesting that temperature
accelerates the speed of the reaction but does not increase the amount of the reaction products.
Fly ash-rich mixes (i.e. 80/20, 95/5, and 100/0 mixes) tested at 70 °C had heat outputs of 105, 75, and 60 J/g
respectively which are higher than those measured at 20 °C. These results confirmed that (a) fly ash reaction is
less exothermic than GGBS reaction as it does not involve hydration, and (b) fly ash-rich mixes require energy
(in the form of curing heat) for the reaction to develop. This was expected because of the low compressive strength
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Figure 6. Ex-situ IC test results. (a) Heat flow at 20°C. (b) Cumulative heat output at 20 °C. (c) Heat flow at
70°C. (d) Cumulative heat output at 70 °C.
In-situ isothermal calorimeter tests were carried out at 20 °C on four blends, i.e. 100/0, 80/20, 60/40, and 30/70
fly ash/GGBS mixes. The constituent materials were placed in the testing chamber of the calorimeter which was
then left to stabilise in terms of temperature before mixing the solid part with the liquid activator.
Two peaks were recorded in the first hour of testing. The first peak was recorded for all the samples (including
neat fly ash sample) within about five minutes from the start of the mixing. This can be attributed to the wetting
and dissolution of Si, Al and Ca species from fly ash and GGBS [33, 34], see Figure 7(a). The highest initial peaks
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were recorded for fly ash-rich samples, whilst the lowest was recorded for GGBS-rich sample, i.e. 30/70. A second
peak with a lower magnitude occurred after around 30 minutes of reaction, over a period of about 2 hours, in all
the samples except neat fly ash, see Figure 6(a). This peak increased with the increase in GGBS content in the
blend, and it can be attributed to the formation of C-A-S-H product from the reaction between Ca2+ dissolving
from GGBS particles and silica anions from the activators [32, 35]. This reaction was reported to play an important
A third peak was detected in samples with high content of GGBS i.e. 60/40 and 30/70 after about 10 to 15 hours,
see Figure 7(a). These peaks can be attributed to the subsequent precipitation and formation of C-A-S-H reaction
products, as these were not observed for fly ash-rich samples. These peaks were also found with the ex-situ
technique.
The cumulative heat of the reaction increased with increasing GGBS content, confirming the exothermal nature
of the GGBS hydration reaction, see Figure 7(b). Cumulative heat values after 100 hours were found to be similar
Figure 7. In situ IC curves for different fly ash/GGBS pastes: (a) heat flow in mW/g. log scale for time was
used for magnifying the occurrence of early peaks. (b) Cumulative heat output in J/g of paste.
Results from isothermal calorimeter analysis seemed to suggest the presence of two different reaction
a) With no or low GGBS content, the main exothermic reaction is due to the dissolution of Si and Al species
from the binder. This reaction takes place very early (only observed with in-situ technique), but the
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hardening of geopolymeric matrix is slow at ambient temperature and needs external energy input (in the
form of curing heating) to develop. This is confirmed by the comparison between the total heat output
generated at 20 °C and 70 °C and it is consistent with the results from compressive strengths on mortar
samples.
b) With higher GGBS contents, the main exothermic reaction is due to the formation of C-A-S-H gel with
the hydration of calcium silicate species. The heat output values increased with increasing GGBS content,
in terms of heat flow rate peak intensity and cumulative heat of reaction, indicating that higher amounts
of Ca species available for hydration resulted in higher volume of C-A-S-H produced, which may lead
to denser and stronger gel structure. Samples with higher GGBS content showed higher compressive
strength.
Increasing the curing temperature for high GGBS content mixes did not result in an increase of the total heat
output (hence of the C-A-S-H gel production) but only in a faster reaction. This seems to suggest that curing
GGBS-rich samples in oven would not result in an increase in the final compressive strength, but would only
An extensive investigation on microstructural properties of eight sample pastes was carried out in order to assess
in a qualitative and quantitative way the reaction products and to determine the effect of GGBS substitution on
the microstructural development of the paste. Neat fly ash mixes (100-FA-1.25, 100-FA-0.85 and 100-FA-0.85b
which had higher M+) were oven cured at 70 °C for 7 days then stored in air tight containers at 20 °C until testing
(after 28 days). Samples with blends of fly ash and GGBS (05-GGBS-1.25, 20-GGBS-1.25, 40-GGBS-1.25, 70-
GGBS-0.95 and 70-GGBS-∞) were cured at 20 °C. Unreacted fly ash and GGBS samples were also analysed for
defining a baseline for comparison. Details of the samples are shown in Table 6.
Fly ash samples 100-FA-1.25, 100-FA-0.85 and 100-FA-0.85b were used as the control, i.e., for determining the
microstructure and the reaction products with no GGBS. The effects of higher silicate dosage (100-FA-0.85) and
The changes in reaction products when the GGBS content was increased from 5% to 70% was investigated for
samples 05-GGBS-1.25, 20-GGBS-1.25, 40-GGBS-1.25, and 70-GGBS-0.95. The mix 70-GGBS-∞ used sodium
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Table 6. Details on pastes investigated with microstructural techniques.
100-FA-0.85b 100/0 70 °C 11.5 0.85 Neat fly ash – effect of increased amount of activator.
Fly ash/GGBS – effect of GGBS substitution on the
05-GGBS-1.25 95/5 20 °C 7.5 1.25
microstructure (5% GGBS).
Fly ash/GGBS – effect of GGBS substitution on the
20-GGBS-1.25 80/20 20 °C 7.5 1.25 microstructure (20% GGBS).
Fly ash/GGBS – effect of GGBS substitution on the
40-GGBS-1.25 60/40 20 °C 7.5 1.25 microstructure (40% GGBS).
Fly ash/GGBS – effect of GGBS substitution on the
70-GGBS-0.95 30/70 20 °C 7.5 0.95 microstructure (70% GGBS).
NaOH Fly ash/GGBS – effect of GGBS substitution on the
70-GGBS-∞ 30/70 20 °C 7.5 microstructure (70% GGBS) without silicates addition.
only
XRD, FTIR, TGA and SEM-EDX were the techniques used in this investigation. XRD analysis was used to
identify the formation of some C-A-S-H in samples with GGBS, but it was not effective in assessing differences
between other phases due to the amorphous nature of the main reaction products. With FTIR technique, qualitative
differences among samples were observed, whilst TGA was used to estimate in a quantitative way the amount of
hydrated reaction products. SEM-EDX methods were used to determine the morphology of reaction products and
their chemical composition, and to assess the nature of the reacted gel.
The crystalline phases observed with XRD analysis on three neat fly ash samples (i.e. 100-FA-1.25, 100-FA-0.85
and 100-FA-0.85b) were the same phases identified in the unreacted (raw) fly ash, namely Mullite, Quartz and
traces of Hematite, see Figure 8(a). Corundum was used as an internal standard to quantify the amorphous
percentage of the fly ash. No crystalline reaction product was observed in the reacted samples. This is due to the
amorphous nature of the aluminosilicate hydrate binding gel rich in sodium (N-A-S-H). Peaks for the crystalline
17
Figure 8. XRD spectra. (a) Neat fly ash pastes. (b) Pastes with GGBS.
The XRD pattern of unreacted GGBS showed traces of Akermanite and Gehlenite as the only crystalline phases,
see Figure 8(b). The crystalline phases observed in the raw fly ash, i.e., Quartz and Mullite, were also observed
in fly ash/GGBS samples, although in a lower amount, due to the dilution resulting from blending. Sample 05-
GGBS-1.25, which contained only 5% GGBS, showed a pattern similar to that of neat fly ash samples, with no
presence of the C-A-S-H type gel hump. On the contrary, this latter was detected as the main reaction product in
samples with GGBS > 20% (20-GGBS-1.25 to 70-GGBS-∞). The peak attributed to C-A-S-H seemed to increase
with increasing GGBS content, which is in agreement with the increase in compressive strength of corresponding
mortars: cube compressive strengths of about 20, 30, 45 and 70 MPa were obtained for samples having GGBS
contents of 5%, 20%, 40% and 70% respectively. The presence of C-A-S-H gel has previously been reported for
alkali-activated slag [37] and slag and fly ash systems for slag contents > 25% [7, 38].
Hydrotalcite was identified in the sample activated with NaOH solution only (i.e., 70-GGBS-∞). Hydrotalcites
are a class of anionic clays that are formed in highly caustic conditions (pH greater than 9) as hydrated compounds
of Mg, Al and CO32-. The absence of silica in the activating solution might have prevented the formation of
geopolymeric gel (C-A-S-H), and consequently the Al was available for the crystallization of hydrotalcite. This
is in agreement with the lower strength (30 MPa) obtained with the mortar with 70% GGBS and AM ∞ (i.e. no
silicate in the activator solution). The compressive strength of mortar sample with 70% GGBS and AM 1.25 was
above 70 MPa. Hydrotalcite has been identified in slag systems activated with different activators [37, 39, 40].
18
The amount of precipitation of hydrotalcite was found to increase with the increase of MgO content in the slag
[41].
Due to the generally amorphous nature of precursors and reaction products, XRD analysis allowed qualitative
assessments only. The utilisation of advanced approaches for the quantification of phases with partial or no known
crystal structures (PONKCS) could give further quantitative insight into the nature of the reacted phases [62, 64].
FTIR spectroscopy analysis was used to determine the presence and the position of peaks in the transmittance
spectra obtained with raw materials and reacted pastes, see Figure 9.
In unreacted fly ash, the Si-O-(Si or Al) band was centred around 1057 cm-1, whereas a shift towards 1004, 995
and 995 cm-1 was observed for 100-FA-1.25, 100-FA-0.85 and 100-FA-0.85b respectively. This shift can be
attributed to the change of microstructure and the formation of the amorphous reaction products, with the partial
replacement of SiO4 units by tetrahedral AlO4 units [42]. This confirmed the reaction development in the three
samples, with 100-FA-1.25 showing a lesser extent of reaction compared with 100-FA-0.85 and 100-FA-0.85b.
The peak observed at the wavenumber of 1650 cm-1 is attributed to the –OH bending vibration of chemically
bound water, and it is present in all the three samples, confirming the presence of the reaction products. In the
range 3200-3600 cm-1 a hump that is due to the stretching vibration modes of H-OH groups has been identified
for the reacted materials. This increased or broadened with the increase in the activator dosage (i.e. passing from
100-FA-1.25 to 100-FA-0.85 and 100-FA-0.85b), presumably due to the increase in the volume of reaction
products. This may explain the improvement in compressive strengths of mortars produced with same activation
dosages, i.e. 100-FA-1.25, 100-FA-0.85 and 100-FA-0.85b which had compressive strengths of 30, 45 and 75
MPa respectively. Quartz was observed in both the unreacted fly ash and the reacted pastes with bands at 795 and
Figure 9(b), i.e. samples with GGBS, shows a main band centred at 985 cm-1 in the unreacted GGBS sample,
which is assigned to the asymmetric stretching vibration of T-O-T bond (T is tetrahedral Si or Al). In the reacted
blended fly ash/GGBS samples (05-GGBS-1.25 to 70-GGBS-∞), the T-O-T band shifted toward a lower
wavenumber as the content of slag increased. The bands were centred at 975, 965, 958, and 952 cm-1 for 05-
GGBS-1.25, 20-GGBS-1.25, 40-GGBS-1.25 and 70-GGBS-0.95 respectively, see Figure 9(b). Shifting of the
peaks toward a lower wavenumber in reacted pastes of GGBS rich blends can be due to the simultaneous activation
of fly ash leading to the formation of a binding gel with more cross-linked aluminosilicate geopolymer gel (N-A-
19
S-H) [7] and consequently increasing the compressive strength. However, the presence of GGBS in blended
samples would shift the position of this peak for blended samples to a lower wavenumber irrespectively of the
actual reaction, the main band of raw GGBS being at 985 cm-1. Further confirmation needs to be found from other
microstructural analysis.
Figure 9. FTIR spectra. (a) Neat fly ash pastes. (b) Pastes containing GGBS.
In sample 70-GGBS-∞ (70% GGBS activated with NaOH only) the T-O-T band was centred at a lower
wavenumber (944 cm-1) compared to the samples activated with both sodium hydroxide and sodium silicate
activators. Activation dosage used for the production of this sample (only NaOH was added in the mix at a
relatively low M+ of 7.5%) may have hindered the reactivity of fly ash, and therefore prevented the formation of
either N-A-S-H or Al rich C-A-S-H binding gels. As a result, low Al C-A-S-H binding gel was formed along with
hydrotalcite. SEM images of sample 70-GGBS-∞ which is discussed later in this paper showed a larger extent of
A band centred at 1400 cm-1 was detected in all fly ash/GGBS samples and was attributed to CO 32- probably due
As observed in neat fly ash reacted samples, the stretching-bending mode of H-OH groups was centred at around
3400 cm-1 and appeared to increase or broaden with the increase of GGBS content, probably due to the
development of the reaction products. Another band related to the reaction products was identified at around 1650
cm-1 due to the bending vibration of O-H of the hydrated reaction products.
20
3.4.3. Thermo-gravimetric analysis
TGA was performed on raw materials (as baseline for subsequent analysis) and on reacted pastes. Both unreacted
fly ash and GGBS powders were found to be stable in terms of thermal decomposition, see Figure 10. A mass loss
of about 4% was observed for fly ash in the range 600 to 1000 °C, which was presumably due to the loss of
ignition of carbon compounds (L.O.I. from XRF analysis was about 3.6%). Gas emission analysis obtained with
the mass spectrometer confirms this, since emissions recorded starting from 600 °C were attributed to CO2.
TGA analysis on neat fly ash pastes (samples 100-FA-1.25 to 100-FA-0.85b) showed moderate mass losses. In
these materials, the reaction product is mainly a N-A-S-H (sodium – aluminium – silicate – hydrate) binding gel
system. The mass loss at 300 °C (when water from the aluminosilicate type-gel is removed) was between 7 and
9%, see Figure 10. The amount of hydrated product in the paste is a proxy for the degree of reaction. Different
amounts of hydrated compounds, according to the intensity of differential curve peaks centred at around 150°C,
were observed for 100-FA-1.25 on the one hand and 100-FA-0.85 and 100-FA-0.85b on the other. Such increased
intensity has been attributed to a higher amount of aluminosilicate gel formation [45] and consequently leading to
a higher compressive strength. Results suggest that 100-FA-1.25 reacted to a lesser extent compared to 100-FA-
0.85 and 100-FA-0.85b, and this is in agreement with the lower strengths obtained from mortar with AM 1.25.
Mortars produced with same activator dosages as 100-FA-1.25, 100-FA-0.85 and 100-FA-0.85b gave compressive
strength of 30, 45 and 75 MPa respectively. 100-FA-1.25 showed a mass loss at high temperature (associated with
CO2 emission at 600 – 800°C) similar to that of the unreacted fly ash, see Figure 10. This behaviour can be related
to the relatively poor reactivity of sample 100-FA-1.25, which resulted in a proportion of unreacted fly ash
particles higher than in the other two samples, i.e., 100-FA-0.85 and 100-FA-0.85b, and consequently in a lower
The analysis of the TG curves and the derivative TG (DTG) curves of samples containing GGBS (samples 05-
GGBS-1.25 to 70-GGBS-∞) indicated that the main mass losses occurred in the region 40 – 160 °C, with peaks
centred in the range 90 – 130 °C. This region corresponds to the dehydration of physically bound water in the gel
structure (mainly in the pore network). The water gas emission curves are the mirror image of the DTG,
confirming that the main mass loss happens due to the dehydration process.
21
Figure 10. Thermo gravimetric curves of raw materials (fly ash and GGBS), neat fly ash pastes and pastes
containing GGBS.
GGBS-rich pastes (high calcium pastes) show higher mass losses due to the dehydration process. In these
materials, the hydration products are mainly related to the C-(N)-A-S-H (calcium – aluminium – silicate – hydrate)
systems, with sodium ions in the structure. The dehydroxylation occurs from around 300 °C to 600 °C [46], and
it is completed by 550-600 °C. The total mass loss up to 600°C can be taken as a relative measure of the degree
of reaction. Mass losses increasing from 10% (05-GGBS-1.25) to around 24% (70-GGBS-0.95) were observed
with increasing GGBS content, which corresponded to an increase in the volume of reaction products. This
explains the high compressive strength obtained in these formulations, see Figure 11. The analysis confirmed that
increasing GGBS content in the mix resulted in a higher volume of C-(N)-A-S-H gel.
22
Figure 11. Relationship between compressive strength and hydrated products (observed as mass loss up to 600
The comparison between samples 70-GGBS-0.95 and 70-GGBS-∞ gave insights into the effects of silicates in the
activating solutions on the reaction products. Sample 70-GGBS-∞ was activated with NaOH only, and shows a
reduced amount of hydration products when compared to 70-GGBS-0.95 (18.2% vs. 20.3% at 300 °C
respectively). This indicates a lack of reactivity and therefore a deficiency in binding gel formation (in agreement
with the difference in compressive strength mentioned above). Furthermore, an isolated peak at around 350 °C
can be observed in sample 70-GGBS-∞, see Figure 12. This peak is associated with the dehydration of
hydrotalcite, which decomposes in the range of 270 – 400 °C [7, 41]. The presence of hydrotalcite as a reaction
product when NaOH only was used as an activator was also confirmed from XRD analysis. On the other hand,
70-GGBS-0.95 differential thermogram shows a broader hump in the range 300 – 600 °C, which is due to the
dehydroxilation by condensation of the bound silanol (-Si-OH end group) groups, and is completed at around 600
23
Figure 12. Thermogravimetry and H2O emission curves for 70-GGBS-0.95 and 70-GGBS-∞ samples.
3.4.4. Scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX)
SEM and EDX techniques were used to study the morphology and the chemical composition of the geopolymeric
matrix such as: (a) unreacted or partially reacted particles (cenospheres for fly ash and flakes for GGBS); (b)
matrix gels; (c) crystals from raw materials or from precipitation during the reaction. Due to the unavailability of
Neat fly ash pastes (samples 100-FA-1.25 to 100-FA-0.85b) activated with different dosages resulted in three
different observed morphologies. The magnification 3000X (30 µm) allowed to observe much larger amount of
unreacted (or partially reacted) cenospheres in sample 100-FA-1.25 than those observed in samples 100-FA-0.85
and 100-FA-0.85b. Denser microstructures were found in samples 100-FA-0.85 and 100-FA-0.85b. This indicated
better reactivity of fly ash and therefore better mechanical properties as confirmed by higher compressive strength.
When low quantities of free Si ions were available, i.e., for low activation dosages, Al was present in the
cenospheres only and did not fully participate in the formation of the gel structure, limiting also the presence of
Na in the binding gel. With higher Si availability, i.e. higher activator dosages, the distribution of Al, Na and Si
was found to be more even in the matrix, and the dissolution of solid aluminosilicates was nearly complete [48].
Higher Si availability resulted in higher compressive strength and this has been associated with a more thorough
dissolution of Al [24].
The SEM and EDX analysis confirmed therefore that 100-FA-1.25 did not fully react, whereas 100-FA-0.85 and
24
Samples with lower GGBS content i.e. 05-GGBS-1.25 and 20-GGBS-1.25 showed larger amounts of unreacted
particles, and a less dense matrix was found in sample 05-GGBS-1.25. When GGBS content was increased to
20% (i.e., sample 20-GGBS-1.25), the matrix became denser with smaller amount of unreacted particles and fewer
visible pores. The structure of the matrix increased in density and homogeneity with increasing GGBS, i.e.,
samples 40-GGBS-1.25 and 70-GGBS-0.95, with a better-developed microstructure showing more glassy texture,
which in turns implied more binding gels. Thus the higher compressive strengths obtained with increasing GGBS.
The effects of different activating dosages on a sample containing 70% GGBS on the morphology were assessed
by comparing 70-GGBS-0.95 (30/70 blend activated using sodium silicate and sodium hydroxide) with 70-GGBS-
∞ (30/70 blend activated with sodium hydroxide only). Sample 70-GGBS-∞ showed a larger amount of unreacted
(or partially reacted) particles, both from fly ash and from GGBS precursors, with a coarse bonding with the gel.
Sample 70-GGBS-0.95, on the other hand, showed a very dense and uniform matrix. The difference in
compressive strength was significant (above 70 MPa for sample 70-GGBS-0.95 and around 30 MPa for sample
70-GGBS-∞), confirming a lack of reaction due to the lack of silicates in the solution, which led to a reduced
The chemical composition of the reaction products, assessed via EDX analysis, varied depending on the GGBS
amount in the blend, see Table 7. In the sample with low GGBS content such as 05-GGBS-1.25, Si/Al atomic
ratios ranged from 2.5 to 2.9 with an average ratio of 2.8. Ca/Si ratios were in the range of 0.1 to 0.3 with an
average ratio of 0.2. The Si/Al ratio of sample 05-GGBS-1.25 was similar to that of neat fly ash samples (100-
FA-1.25 to 100-FA-0.85b) suggesting the dominance of fly ash-driven reactions in these samples due to the low
GGBS content. The reaction products in sample 05-GGBS-1.25 consisted mainly of Si, Al and Na whereas the
content of Ca was relatively low in the matrix. As the content of GGBS increased in the sample, the amount of
Ca increased and the amount of Si and Al appeared to decrease in the matrix. Furthermore, the amount of the main
elements and their atomic ratios varied depending on the blend. Ca/Si and Si/Al ratios (in samples 05-GGBS-1.25
to 70-GGBS-0.95) increased with increasing GGBS. The highest Ca/Si ratio was obtained in sample 40-GGBS-
1.25 (Ca/Si = 0.7) which was similar to that of 70-GGBS-0.95 (0.6) and the highest Si/Al ratio was found in
sample 70-GGBS-0.95 (Si/Al = 3.1). This is because of the higher Si content in the activating solution and explains
the high compressive strength obtained for mortar samples with the same composition (above 70 MPa). The higher
strengths are due to the better geopolymerization or highly cross-linked structures of the binding gels [10], which
lead to more compact and denser matrix and therefore better mechanical properties.
25
Table 7. Average values (%) and the standard deviation in the brackets of the main elements and their atomic
05-GGBS-1.25 2.5 (0.7) 13.3 (0.4) 4.8 (0.2) 0.2 (0.0) 2.8 (0.2)
20-GGBS-1.25 4.3 (1.7) 12.0 (1.0) 5.3 (1.4) 0.4 (0.2) 2.3 (0.4)
40-GGBS-1.25 6.7 (1.4) 9.9 (1.6) 3.9 (0.4) 0.7 (0.2) 2.5 (0.6)
70-GGBS-0.95 6.5 (1.9) 10.3 (1.8) 3.3 (0.6) 0.6 (0.1) 3.1 (0.6)
70-GGBS-∞ 12.5 (4.2) 8.6 (2.5) 3.7 (0.9) 1.5 (0.6) 2.3 (0.3)
The chemical composition of the reaction products of sample 70-GGBS-∞ (i.e., activated with NaOH solution
only) was different from that of the other blends, especially in the amount of Ca. The amount of Ca in the matrix
was higher than that of the other samples including 70-GGBS-0.95, which had the same GGBS content. The Ca/Si
ratio was 1.5, i.e., the highest amongst all investigated blends. This ratio is higher than the typical ratios which
are reported in the literature in the range of 1.0 to 1.2 for neat alkali-activated slag systems [7, 39, 49]. This high
Ca/Si ratio is more similar to that found in C-S-H gel in Portland cement systems, which varies from 1.2 to 2.3
[50]. The reaction in this sample seems to be the hydration of GGBS, leading to the formation of C-A-S-H gel
that is high in Ca. There is very little contribution from the fly ash as unreacted fly ash particles were easily
identified in SEM images. The compressive strengths were about 30 MPa regardless of the dosage (M+),
suggesting that the reaction involves mainly the hydration of GGBS, since there is absence of silicate into the
activating solution,
The variation of the chemical composition of the binding gel due to the increasing GGBS content suggests the
development of different reaction products. In sample 05-GGBS-1.25, the reaction product was mainly alkaline
aluminosilicate hydrate geopolymer gel (N-A-S-H) with Si/Al ratios of 2.5-2.9 and a low Ca/Si ratio of 0.1-0.3.
The chemical composition for sample 20-GGBS-1.25 was different from that of 05-GGBS-1.25, as higher Ca/Si
ratios 0.2 to 0.6 were obtained, indicating more Ca in the gel. This suggests the formation of C-A-S-H type binding
gel along with the geopolymer gel (N-A-S-H). The existence of C-A-S-H gel in samples with as low as 20%
GGBS content was confirmed by TGA and XRD analyses discussed earlier. The dominance of the geopolymer
gel (N-A-S-H) among reaction products with GGBS content less than 25% has also been reported by others [10,
51]. In samples with high GGBS content such as 40-GGBS-1.25 and 70-GGBS-0.95, the ratios of Ca/Si increased
significantly compared to samples 05-GGBS-1.25 and 20-GGBS-1.25. The two samples had similar Ca/Si ratios
26
in the range of 0.5 – 1.0 with average values of 0.7 and 0.6 for 40-GGBS-1.25 and 70-GGBS-0.95 respectively.
These ratios are consistent with the chemical composition of C-A-S-H gel in slag systems and therefore the
dominant reaction product in the gel was C-A-S-H, possibly coexisting with geopolymer type binding gel N-A-
S-H. These findings are in agreement with previous studies [3, 30, 51, 52]. The evolution of the reaction resulted
in higher compressive strength and reduced setting time with increasing GGBS content, which can also be
attributed to the co-existence of the above mentioned binding gels [3]. However, using morphological images and
EDX chemical analysis of the gels, it was not possible to clearly distinguish the two reaction products as they
appear to be intermixed at a too small scale to be spotted by EDX analysis [7, 51, 53]. This may suggest the
formation of a hybrid binding gel (C-N-A-S-H) that improved the mechanical properties of the matrix [7, 51, 54].
Pseudo-ternary diagrams of the ratios of Al, Ca and Na normalised by the quantity of Si for neat fly ash samples
and fly ash /GGBS blends are shown in Figures 13 and 14 respectively. The unreacted/partially reacted fly ash
particles appeared to have similar composition to that of the precursor material but with lower quantity of calcium.
This suggests that the calcium was dissolved by the activators. The difference between theoretical and EDX
measured gel composition was found to be higher for sample 100-FA-1.25 than for the other neat fly ash samples
(100-FA-0.85 and 100-FA-0.85b). The quantity of Al in the binding gel of sample 100-FA-1.25 also appeared to
be lower. This can be due to the poor dissolution of Al from the precursor, especially in samples with higher AM
(i.e., low soluble silicate), which reduced the availability of Al in the gel nucleation [24]. As the activator dosage
increased (samples 100-FA-0.85 and 100-FA-0.85b), the gel compositions obtained by EDX were closer to the
calculated values (see Figure 13). This indicates better reactivity and homogeneity of the binding gel. The quantity
of Al in the gel increased in samples 100-FA-0.85 and 100-FA-0.85b with lower alkali modulus (AM 0.85)
compared to sample 100-FA-1.25 (AM 1.25). An increase in alkali dosage (M+) from 7.5% (100-FA-1.25) to
11.5% (100-FA-0.85b) increased the sodium content of the binding gel as can be seen from Figure 13. Low
calcium N-A-S-H binding gel was identified as the main reaction product in these formulations.
27
Figure 13. Pseudo-ternary diagram showing Al/Si, Na/Si and Ca/Si molar ratios for neat fly ash samples.
In the case of fly ash/GGBS blends (see Figure 14), the unreacted GGBS particles analysed with EDX showed
similar chemical composition to those of the raw GGBS. However, the chemistry of partially reacted GGBS
particles was similar to the composition of the binding gel, indicating that those particles had reacted to some
degree that enabled the formation of the gel (C-A-S-H). Sample 05-GGBS-1.25 had a gel chemical composition
similar to that of neat fly ash samples. The increase of GGBS content in the system led to the formation of binding
Two main categories of the gel can be detected: (a) a low calcium gel with similar chemical composition as that
of neat fly ash systems, and (b) a binding gel with higher calcium content. It was also observed that both low
calcium and high calcium gels were present in the same samples (20-GGBS-1.25 and 70-GGBS-0.95), which may
confirm the coexistence of both N-A-S-H and C-A-S-H from the activation of fly ash and GGBS respectively.
Sodium silicate crystals were also detected mainly in sample 05-GGBS-1.25. This can be due to the poor reactivity
of this sample at room temperature due to its high fly ash content (95%), which led to some amount of activator
chemicals to crystalize.
28
Figure 14. Pseudo-ternary diagram showing Al/Si, Na/Si and Ca/Si molar ratios for fly ash/GGBS samples.
The compressive strength was generally found to increase with the increase in Ca/Si ratio, which is in agreement
with the increase in GGBS content in the sample. The highest compressive strength was obtained at Ca/Si of 0.6
in the sample with 70% GGBS. This increase in compressive strength with the increase in Ca/Si ratio is
presumably due to evolution of C-A-S-H binding gel with increasing GGBS content in the blend, leading to a
matrix with improved mechanical properties. Similarly, Si/Al ratios generally increase with increasing GGBS
content. This can be due to the more complete dissolution of Si and Al from the precursors, leading to a higher
degree of crosslinking in the structure of the reaction products comprising of N-A-S-H and C-A-S-H binding gels
[55]. However, sample 05-GGBS-1.25 showed lower compressive strength despite Si/Al ratio higher than that of
20-GGBS-1.25 and 40-GGBS-1.25. The lower compressive strength obtained for 05-GGBS-1.25 can be attributed
to the slow reactivity of fly ash rich samples at room temperature as previously discussed. The slower reaction
rate at room temperature may have hindered the dissolution of Al from fly ash leading to higher Si/Al ratio. This
together with the absence of C-A-S-H binding gel led to less compact matrix and therefore lower strength.
The investigation described in this paper allowed to link the mechanical behaviour of alkali activated mortars with
the microstructure of the binding matrix, and contributed towards the understanding of a number of key aspects
related to activation of fly ash and fly ash/GGBS based binders. The mechanisms governing the reaction of low-
29
Ca and high-Ca binders respectively are different, as it has been reported in the literature, but the behaviour of
blended systems is still under investigation [56, 57]. The research provided insights into the following:
Silicate content in the activating solution: compressive strength results suggested that the silicate content in
the activating solution has a direct influence on the strength development of neat fly ash samples. Ca-rich
blend showed a lower dependence on the silicate contents, allowing a reduction in the activator dosage for
developing satisfactory strengths. However, it was observed that the presence of silicates influenced the type
of reaction. Hydration of Ca species only (leading to very similar values of compressive strength irrespective
of the alkali dosage) was observed when no silicates were added, whilst production of C-A-S-H gel was
found with the use of silicates in the activating solution. This finding was confirmed by results from XRD,
FTIR and TGA analyses as well as by SEM images. The absence of silicates in Ca-rich blends proved to be
responsible for the formation of hydrotalcite, as shown by XRD, TGA, and FTIR analyses and discussed by
others [58]. A recent publication pointed out the possible role of hydrotalcite in the immobilisation of
chlorides [59], although SEM images obtained in this investigation suggested that neat NaOH activation for
Ca-rich system resulted in poorly compacted matrix, with clear repercussions in terms of resistance to
degradation attacks.
Effect of calcium content in the blend: blended systems appeared to be mainly influenced by the presence of
Ca-rich precursor, which allowed the hardening of samples at room temperature (i.e. 20 °C). Microstructural
analysis indicated that the presence of GGBS resulted in the production of C-A-S-H gel in the matrix, even
with as low as 20% GGBS content, and this was confirmed by both XRD and EDX analysis. The use of slag
in the blend was found to be linearly related to the increase of compressive strength, whereas recent studies
found that a slag content higher than 50% led to non-significant strength contribution [60]. The chemical
composition of pastes obtained through EDX and their representation in pseudo-ternary plots allowed to
identify the nature of the binding gel, confirming and expanding available literature on the topics of phase
diagrams and co-existence of C-A-S-H and N-A-S-H gels [10, 17, 61]. The mass loss up to 600 °C, used as
proxy for the hydration products, proved to be related to the compressive strength of mortars in Ca-rich
samples.
Effect of curing temperature on the reaction: the effect of the curing temperature on the reaction was
investigated through isothermal calorimetry. The analysis confirmed and expanded results from recent
publications [62, 63]. The study demonstrated that the temperature has a clear effect on the rate of dissolution
of Si and Al in neat fly ash samples. The cumulative heat release increased by a factor of 4 by increasing the
30
curing temperature from 20 °C to 70 °C, in line with what was observed by Sun and Vollpracht [62] on neat
precursors heated up to 40 °C. The catalyst effect of temperature was also observed with Ca-rich blends, i.e.
the final cumulative heat release did not vary under different temperatures (20 °C and 70 °C), but the reaction
was concluded in about 1/3 of the time when increasing the curing temperature from 20 °C to 70 °C.
Isothermal calorimetry results confirmed the findings of Singh and Subramaniam [63] on compressive
4. Conclusions
This study focused on the effects, such as mechanical and microstructural properties, of fly ash replacement with
GGBS in alkali activated mortars and pastes. The conclusions from the work reported in this paper are:
The partial substitution of fly ash with GGBS reduced the activator dosages required for obtaining high
compressive strength. This has cost and environmental benefits. Whilst neat fly ash mortar mixes (cured
at 70 °C) needed alkali modulus (AM) of 0.85 and alkali dosage (M+) of 11.5% for obtaining a 7-day
compressive strength in excess of 70 MPa, high GGBS content mixes gave similar strength with AM of
1.25 and M+ of 7.5%. The addition of GGBS in the mix also eliminated the need for oven curing.
Two reaction mechanisms were identified from IC analysis. With no or low GGBS content, the
exothermic reaction was mainly due to the dissolution of aluminosilicate precursor from fly ash. This
reaction took place very early but required external energy (i.e., heating) for its full development. A more
exothermic reaction was observed with higher GGBS contents. This was due to the hydration of calcium
silicate species and formation of C-A-S-H gel. An increase in the curing temperature for high GGBS
content mixes resulted in a faster reaction, whilst the volume of C-A-S-H gel produced did not change
significantly.
The increase of GGBS content in the blend allowed the formation of C-A-S-H gel which improved the
matrix and thus the mechanical properties of the mortars. XRD, FTIR and TGA results confirmed the
presence of C-A-S-H-like gel as a reaction product. A correlation between the amount of such gel in the
The main reaction product in neat fly ash samples was an amorphous aluminosilicate hydrate gel with
sodium in the structure (N-A-S-H). More compact and dense matrix was observed as the content of
GGBS increased in the blend. C-A-S-H was the main binding gel found in formulations with 40% GGBS
content or higher. XRD and EDX chemical analysis suggested the formation of C-A-S-H gel in the
31
sample with as low as 20% GGBS content. Compressive strength was found to increase with the increase
in Ca/Si and Si/Al ratios suggesting an increase in the degree of cross-linking of the reaction products
Alkali activation of GGBS-rich mix with neat sodium hydroxide solution (i.e., no silicate in the
activation) resulted in morphology, gel chemistry and reaction products different from the mix activated
with a mixture of sodium hydroxide and sodium silicate solution at a fixed alkali dosage M+ of 7.5%.
Micrographs showed a heterogeneous matrix with larger extent of unreacted fly ash and GGBS particles
indicating poor reactivity. Hydrotalcite was also identified in this sample through TGA and XRD
techniques.
Acknowledgements
This research was carried out in the framework of the SUS-CON ‘‘Sustainable, Innovative and Energy-Efficient
Concrete, based on the Integration of All-Waste Materials’’ project, which has received funding from the
European Union Seventh Framework Programme (FP7/2007-2013) under Grant Agreement No. 285463 (Call
The Authors would also like to acknowledge the Government of the Sultanate of Oman represented in the Ministry
of Manpower, for funding this project by sponsoring the principal author’s PhD study at Queen’s University
Belfast.
References
[1] J.L. Provis, Green concrete or red herring? – future of alkali-activated materials, Advances in Applied
[2] J.L. Provis, A. Palomo, C. Shi, Advances in understanding alkali-activated materials, Cement and Concrete
[3] S. Kumar, R. Kumar, S.P. Mehrotra, Influence of granulated blast furnace slag on the reaction, structure and
properties of fly ash based geopolymer, Journal of Materials Science, 45(3) (2009) 607–615.
[4] M.A. Smith, G. J. Osborne, Slag/fly ash cements, World Cement Technology 8, no. 6 (1977).
[5] W.C. Wang, H.Y. Wang, M.H. Lo, The fresh and engineering properties of alkali activated slag as a function
of fly ash replacement and alkali concentration, Construction and Building Materials, 84 (2015) 224-229.
32
[6] X. Gao, Q.L. Yu, H.J.H. Brouwers, Reaction kinetics, gel character and strength of ambient temperature
cured alkali activated slag – fly ash blends, Construction and Building Materials, 80 (2015) 105–115.
[7] I. Ismail, Durability as a function of microstructure of alkali-activated slag/fly ash binders, Doctoral
[8] P.S. Deb, P. Nath, P.K. Sarker, The effects of ground granulated blast-furnace slag blending with fly ash and
activator content on the workability and strength properties of geopolymer concrete cured at ambient
[9] P. Nath, P.K. Sarker, Effect of ggbfs on setting, workability and early strength properties of fly ash
geopolymer concrete cured in ambient condition, Construction and Building Materials, 66 (2014) 163–171.
[10] I. Ismail, S.A. Bernal, J.L. Provis, R. San Nicolas, S. Hamdan, J.S. Van Deventer, Modification of phase
evolution in alkali-activated blast furnace slag by the incorporation of fly ash, Cement and Concrete
[11] ASTM C618, Standard specification for coal fly ash and raw or calcined natural pozzolan for use in
[12] British Standards Institution, Fly ash for concrete. Definition, specifications and conformity criteria, BS EN
450-1 (2012)
[13] R. Vinai, A. Rafeet, M.N. Soutsos, W. Sha, The role of water content and paste proportion on physico-
mechanical properties of alkali activated fly ash–ggbs concrete, Journal of Sustainable Metallurgy, 2(1) (2016)
51-61.
[14] M.N. Soutsos, A.P. Boyle, R. Vinai, A. Hadjierakleous, S.J. Barnett, Factors influencing the compressive
strength of fly ash based geopolymers, Construction and Building Materials, 110 (2016) 355-368.
[15] J.G. Jang, N.K. Lee, H.K. Lee, Fresh and hardened properties of alkali-activated fly ash/slag pastes with
[16] E.I. Diaz, E.N. Allouche, S. Eklund, Factors affecting the suitability of fly ash as source material for
[17] C.K. Yip, G.C. Lukey, J.S.J. Van Deventer, The coexistence of geopolymeric gel and calcium silicate
hydrate at the early stage of alkaline activation, Cement and Concrete Research, 35, (2005) 1688–1697.
[18] A. Palomo, M.W. Grutzeck, M.T. Blanco, Alkali-activated fly ashes: a cement for the future, Cement and
33
[19] P. Duxson, J.L. Provis, G.C. Lukey, S.W. Mallicoat, W.M. Kriven, J.S. Van Deventer, Understanding the
relationship between geopolymer composition, microstructure and mechanical properties, Colloids and Surfaces
[20] C. Lampris, R. Lupo, C. R. Cheeseman, Geopolymerisation of silt generated from construction and
properties prepared by alkali activation of black coal ashes with high content of loss on ignition, Acta
[22] Z. Xie, Y. Xi, Hardening mechanisms of an alkaline-activated class F fly ash, Cement and Concrete
[23] A.A. Adam, Strength and durability properties of alkali activated slag and fly ash-based geopolymer
[24] A. Hajimohammadi, J.L. Provis, J.S.J van Deventer, The effect of silica availability on the mechanism of
[25] J. Chang, A study on the setting characteristics of sodium silicate-activated slag pastes, Cement and
[26] H.S. Pietersen, A.L. Fraay, J.M. Bijen, Reactivity of fly ash at high pH, In MRS Proceedings Vol. 178,
[27] S.D. Wang, K.L. Scrivener, P.L. Pratt, Factors affecting the strength of alkali-activated slag. Cement and
[28] M. Chi, R. Huang, Binding mechanism and properties of alkali-activated fly ash/slag mortars, Construction
[29] H.F.W. Taylor H, Cement Chemistry 2nd ed., Thomas Telford Publishing (1997).
pulverised fuel ash and blast furnace slag activated by sodium silicate: effect of Na 2O concentration and
[31] S. Chithiraputhiran, N. Neithalath, Isothermal reaction kinetics and temperature dependence of alkali
activation of slag, fly ash and their blends, Construction and Building Materials, 45 (2013) 233–242.
[32] C. Shi, R.L. Day, Some factors affecting early hydration of alkali-slag cements, Cement and Concrete
34
[33] C. Shi, P.V. Krivenko, D. Roy, Alkali-Activated Cements and Concretes, 1st ed. Taylor and Francis, New
[34] S.A. Bernal, J.L. Provis, V. Rose, R.M. De Gutierrez, Evolution of binder structure in sodium silicate-
activated slag-metakaolin blends, Cement and Concrete Composites, 33(1) (2011) 46–54.
[35] C. Shi, R. Day, A calorimetric study of early hydration of alkali-slag cements, Cement and Concrete
[36] A. Fernández-Jiménez, F. Puertas, Effect of activator mix on the hydration and strength behaviour of alkali-
[37] S.D. Wang, K.L. Scrivener, Hydration products of alkali activated slag cement, Cement and Concrete
[38] S.A. Bernal, J.L. Provis, B. Walkley, R. San Nicolas, J.D. Gehman, D.G. Brice, D. G., J.S. van Deventer,
Gel nanostructure in alkali-activated binders based on slag and fly ash, and effects of accelerated carbonation,
products and reactivity of blast furnace slag activated by various alkalis, Journal of the American Ceramic
[41] M.B. Haha, B. Lothenbach, G. Le Saout, F. Winnefeld, Influence of slag chemistry on the hydration of
alkali-activated blast-furnace slag — Part I: Effect of MgO, Cement and Concrete Research, 41(9) (2011) 955–
963.
[42] M. Asadi, A. Nemati, R. Naghizadeh, K. Arzani, J. Fahim, Effect of temperature and activator molar of
Na2O to SiO2 in the process of synthesis and microstructure of cement geopolymer, Advanced Materials and
[43] A. Fernández-Jiménez, A. Palomo, Composition and microstructure of alkali activated fly ash binder:
Effect of the activator, Cement and Concrete Research, 35(10) (2005) 1984–1992.
[44] M. Criado, A. Fernández-Jiménez, A. Palomo, Alkali activation of fly ash: Effect of the SiO2/Na2O ratio.
Part I: FTIR study, Microporous and Mesoporous Materials, 106 (2007) 180–191.
35
[45] E.D. Rodríguez, S.A. Bernal, J.L. Provis, J. Paya, J.M. Monzo, M.V. Borrachero, Effect of nanosilica-
based activators on the performance of an alkali-activated fly ash binder, Cement and Concrete
[46] J.P. Brady, An examination of the applicability of hydrotalcite for removing oxalate anions from Bayer
process solutions, Masters by research thesis, Queensland University of Technology, Australia, (2011).
[47] L.T. Zhuravlev, The surface chemistry of amorphous silica. Zhuravlev model, Colloids and Surfaces A:
[48] M.N. Soutsos, R. Vinai, A. Rafeet, Effect of alkali dosage and modulus on strength development and
microstructure of alkali-activated binders, In 14th International Congress on the Chemistry of Cement, Beijing,
China (2015).
[49] I.G. Richardson, A.R. Brough, G.W. Groves, C.M. Dobson, The characterization of hardened alkali-
activated blast-furnace slag pastes and the nature of the calcium silicate hydrate (C-S-H) phase, Cement and
[50] I.G. Richardson, The nature of C-S-H in hardened cements, Cement and Concrete Research, 29(8) (1999)
1131–1147.
microstructural properties of alkali-activated fly ash–blast furnace slag blends, Ceramics International, 41(1),
(2015) 1421–1435.
[52] J.L. Provis, R.J. Myers, C.E. White, V. Rose, J.S. van Deventer, X-ray microtomography shows pore
structure and tortuosity in alkali-activated binders, Cement and Concrete Research, 42(6) (2012) 855–864.
[53] R.R. Lloyd, J.L. Provis, J.S.J. Van Deventer, Microscopy and microanalysis of inorganic polymer cements.
1: Remnant fly ash particles, Journal of Materials Science, 44(2) (2009) 608–619.
[54] I. Garcia-Lodeiro, A. Palomo, A. Fernández-Jiménez, D.E. MacPhee, Compatibility studies between N-A-
S-H and C-A-S-H gels. Study in the ternary diagram Na2O–CaO–Al2O3–SiO2–H2O, Cement and Concrete
[56] X. Zhao, C. Liu, L. Zuo, L. Wang, Q. Zhu, M. Wang, Investigation into the effect of calcium on the
existence form of geopolymerized gel product of fly ash based geopolymers, Cement and Concrete Composites,
36
[57] G. Fang, W.K. Ho, W. Tu, M. Zhang, Workability and mechanical properties of alkali-activated fly ash-
slag concrete cured at ambient temperature. Construction and Building Materials, 172 (2018) 476-87.
[58] K. Gong, C.E. White, Impact of chemical variability of ground granulated blast-furnace slag on the phase
formation in alkali-activated slag pastes, Cement and Concrete Research, 89 (2016) 310-319.
[59] X. Ke, S.A. Bernal, J.L. Provis, Uptake of chloride and carbonate by Mg-Al and Ca-Al layered double
hydroxides in simulated pore solutions of alkali-activated slag cement, Cement and Concrete Research, 100
(2017) 1-13.
[60] M.A. Yazdi, M. Liebscher, S. Hempel, J. Yang, V. Mechtcherine, Correlation of microstructural and
mechanical properties of geopolymers produced from fly ash and slag at room temperature, Construction and
[61] R.J. Myers, S.A. Bernal, J.L. Provis, Phase diagrams for alkali-activated slag binders, Cement and Concrete
[62] Z. Sun, A. Vollpracht, Isothermal calorimetry and in-situ XRD study of the NaOH activated fly ash,
metakaolin and slag, Cement and Concrete Research, 103 (2018) 110-122.
[63] G.B. Singh, K.V. Subramaniam, Influence of processing temperature on the reaction product and strength
gain in alkali-activated fly ash, Cement and Concrete Composites 95 (2019) 10-18.
[64] N.V. Scarlett, I.C. Madsen, Quantification of phases with partial or no known crystal structures, Powder
[65] G.B.Singh, K.V. Subramaniam, Evaluation of sodium content and sodium hydroxide molarity on
compressive strength of alkali activated low-calcium fly ash, Cement and Concrete Composites, 81(2017) 122-
132.
[66] J.L. Provis, J.S. Van Deventer (editors), Alkali activated materials: state-of-the-art report, RILEM TC 224-
37
Appendix A
Table A1. Mix proportions for mortar production batch. Asterisk denotes samples prepared with NaOH solution
at 40% conc.
38
FA-10.5-0.85 500 0 92 242 13 1375
FA-10.5-0.75 500 0 75 275 9 1375
FA-10.5-0.50 500 0 0 412 0 1375
FA-11.5-1.05 500 0 129 215 4 1375
FA-11.5-0.95 500 0 117 237 1 1375
FA-11.5-0.85 500 0 101 265 0 1375
FA-11.5-0.75 500 0 82 301 0 1375
FA-12.5-1.05* 500 0 105 233 23 1375
FA-12.5-0.95* 500 0 95 258 16 1375
FA-12.5-0.85* 500 0 83 288 8 1375
FA-12.5-0.75* 500 0 67 327 0 1375
FA-13.5-0.95* 500 0 103 279 3 1375
FA-13.5-0.85* 500 0 89 311 0 1375
FA-13.5-0.75* 500 0 72 353 0 1375
39
Table A2. Mix proportions for 1 litre of mortar. Asterisk denotes samples prepared with NaOH solution at 40%
conc.
40
FA-10.5-0.50 494 0 0 407 0 1359
FA-11.5-1.05 514 0 133 221 4 1415
FA-11.5-0.95 513 0 120 243 1 1409
FA-11.5-0.85 508 0 103 270 0 1398
FA-11.5-0.75 503 0 82 302 0 1383
FA-12.5-1.05* 507 0 107 237 23 1394
FA-12.5-0.95* 505 0 96 261 16 1389
FA-12.5-0.85* 503 0 83 290 8 1384
FA-12.5-0.75* 499 0 67 326 0 1373
FA-13.5-0.95* 502 0 103 280 3 1380
FA-13.5-0.85* 496 0 89 309 0 1365
FA-13.5-0.75* 488 0 70 345 0 1343
41
Table A3. Mix proportions for mortar production batch.
42
Table A4. Mix proportions for 1 litre of mortar.
43