Cement and Concrete Composites 97 (2019) 226–238

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Cement and Concrete Composites

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Effect of sodium carbonate/sodium silicate activator on the rheology, T

geopolymerization and strength of fly ash/slag geopolymer pastes
Ishwarya Ga,∗∗, B. Singhb,∗, S. Deshwalb, S.K. Bhattacharyyac
a
Academy of Scientific and Innovative Research (AcSIR), CSIR-Central Building Research Institute, Roorkee, 247667, India
b
CSIR-Central Building Research Institute, Roorkee, 247667, India
c
Department of Civil Engineering, IIT-K, 721302, India

ARTICLE INFO ABSTRACT

Keywords: Reactions between the fly ash/slag composite mix and the Na2CO3/Na2SiO3 activator were monitored through
Fly ash Isothermal conduction calorimetry. The resulting products were analyzed with the help of XRF, XRD and FT-IR
Geopolymer techniques. In calorimetric response, the composite pastes had more total heat release than the fly ash paste
Calorimetry requiring ∼50% less activation energy to yield reaction products. These products were largely amorphous as
Rheology
observed in the XRD patterns. Rheological studies indicated that composite pastes were very stiff above 25 wt%
Compressive strength
slag addition as its yield stress was almost doubled to fly ash paste. The compressive strength of hardened pastes
increased with increasing slag content and activator dosage and decreased with increasing water-binder ratio.
The deposition of reaction products onto the fly ash/slag particle surfaces and also the dense microstructures as
observed in FESEM supported higher strength of geopolymer pastes at higher activator and slag contents. The
developed paste with standard sand at 1:2 ratio produced mortar with a compressive strength of ∼72 MPa.

1. Introduction
In recent years, geopolymers are attracting increasing attention as
binder alternatives to ordinary Portland cement due to the limited reserves
of raw materials especially limestone and emission of huge amount of CO2
during Portland cement production [1–5]. They are usually produced by
the alkaline activation of solid aluminosilicates such as fly ash, metakaolin,
mine tailings etc. at high pH under an elevated temperature curing. As a
means of activating these aluminosilicates, the knowledge of amorphous
content and also their ability to release aluminum is essential to produce
geopolymeric binders with many advantages over the traditionally used
Portland cement in terms of their early strength gain, low water permea-
tion, high chemical & fire resistance and also on the issue of sustainability.
This binder has a great potential in the concrete industry as it cures and sets
to a material with an X-ray amorphous structure. However, the main issues
related to geopolymer development are its elevated temperature curing and
safe handling of highly alkaline activator to achieve acceptable mechanical
properties and durability [6–9]. Therefore, the necessity of developing a
viable ambient cured geopolymer with safe and cost-effective activating
systems is realized for its wide scale adoption in the field.
Several attempts [10–15] have been made on the development of
ambient cured fly ash-based geopolymers by adding calcium enriched
compounds especially ground granulated blast furnace slag with a view
to expand its applications in both in-situ and precast construction.
Calcium derived from the slag modifies sodium aluminosilicate (N-A-S-
H) gel, partially replacing sodium ion with calcium ion to form (Ca,Na)-
A-S-H gels which cause rapid hardening in the fly ash-based geopo-
lymer at room temperature [10]. The availability of free calcium ions in
the system prolongs the dissolution of fly ash and also enhance the
geopolymer strength due to the higher heat of hydration [11,12]. It is,
however, also reported [16,17] that higher heat flow under calorimetric
response for the fly ash/slag mix (∼30 wt% slag) activated with sodium
hydroxide/sodium silicate does not relate always to higher compressive
strengths. Puertas et al. [13] observed that the mix containing 50 wt%
fly ash and 50 wt% slag activated with 10 M sodium hydroxide solution
develops a compressive strength of ∼50 MPa at 25 °C after 28 days.
Acceleration in the early age strength is further observed when 3%
hydrated lime is added to the fly ash/slag mix activated with sodium
hydroxide/sodium silicate solution [18]. Chi and Huang [19] con-
sidered 6% Na2O by mass of fly ash/slag mix (50:50) along with sodium
silicate with modulus of 1 as the optimum mix design for making
mortar (105.80 MPa). A moist curing regime is preferred over a dry
open air curing system for fly ash/slag blends to obtain higher strength
and less porous systems as open air curing is allowing water to

∗
Correspondence.
∗∗
Correspondence.
E-mail addresses: ishwaryarose@gmail.com (I. G), singhb122000@yahoo.com (B. Singh).

https://doi.org/10.1016/j.cemconcomp.2018.12.007
Received 16 September 2018; Received in revised form 7 December 2018; Accepted 12 December 2018
Available online 13 December 2018
0958-9465/ © 2018 Elsevier Ltd. All rights reserved.
I. G et al. Cement and Concrete Composites 97 (2019) 226–238

evaporate which reduces the water availability causing drying

shrinkage [20]. Experiences have shown some drawbacks related to
workability of the fresh geopolymer mix during casting [21,22] and
also tendency towards efflorescence formation in the hardened state
due to excess alkali [23]. Developing understanding on setting/hard-
ening behavior of fly ash/slag based geopolymer at ambient condition
is important in order to determine its time of transport, finishability,
time to remove formwork as well as microstructural changes leading to
hardening [12].
Although, fly ash/slag mix activated with alkali hydroxides/silicates
has received much attention, a necessity is further felt to find out alternate
activating systems to sort out the known issue of efflorescence associated
with sodium hydroxide and its handling issue due to the high alkalinity
[23–27]. The present programme, therefore investigated a new activating
system comprising sodium carbonate (Na2CO3), sodium silicate (Na2SiO3)
and chemical admixtures for geopolymerization of fly ash/slag composite
mix. Such attempt on this system is scanty and no report is available on its
rheology, geopolymerization kinetics and optimization of constituents. Fig. 1. Particle size distribution of fly ash and slag.
Na2CO3 was chosen over the conventionally used sodium hydroxide
(NaOH) activator because of its low cost, commercial availability and also
Ground granulated blast furnace slag was procured from M/s Rashtriya
helps in reducing the pH of activating solution. In prior art [28], Na2CO3
Ispat Nigam Limited, India (Blaine's surface area, 514 m2/kg and average
activation of blast furnace slag has been reported for the production of
particle size, 14.57 μm). About 97.84% of the particles were smaller than
activated slag products. At early stage, the formation of calcium carbonate
45 μm. Fig. 1 shows the particle size distribution of fly ash and slag. The
and sodium-calcium carbonate phases occurs as a result of reactions be-
chemical composition of fly ash and slag determined by X-ray Fluorescence
tween the calcium ions released from slag and dissolved carbonate ions of
Fpectrometer (XRF, Bruker B8) is given in Table 1. Sodium carbonate
Na2CO3 present in the pore solution on one hand while silicate and alu-
(Thomas Baker, purity 98.47% and specific gravity, 2.53) and sodium sili-
minate ions released by the dissolution of the slag react separately with the
cate (Na2O/SiO2, 0.96) were used as activators. Boric acid (Thomas Baker,
sodium of activator to form zeolite NaA [29]. Once, the carbonate is ex-
purity 99.5%) was used as a retarder for geopolymerization reaction.
hausted, the activation proceeds in a similar way as in NaOH activated
Standard sand [2-1 mm: 33.33%, 1 mm-500 μm: 33.33%, 500-90 μm:
slag forming the typical binder phases of calcium aluminium silicate hy-
33.33%] was procured from M/s Tamin limited, India to produce mortars.
drate (C-A-S-H) and hydrotalcite along with Ca-heulandite as a further
(Ca,Al)-rich product [30]. These phases do not give the high degree of
cohesion necessary for the development of high mechanical strength. To 2.1. Sample preparation
overcome this shortcoming, attempts have been made to activate slag with
the combined use of various activators such as Na2CO3 & NaOH and 2.1.1. Synthesis of geopolymers
Na2SiO3 & lime [31–33]. Xu et. Al [31] reported that the main reaction Composite mix: Fly ash and slag were initially dried in an oven at
product formed during activation of the aged slag with Na2CO3/NaOH is a 100 ± 5 °C for 24 h to remove their surface moisture. Thereafter, these
highly crosslinked C-A-S-H type phase with a reduced content of calcium were proportioned at different ratios (fly ash: slag: 4:1, 3:1 and 2:1) and
in the outer product along with an inner product involving carbonate inter-ground in a planetary ball mill (Retsch PM-400) at 80 RPM for
anions. Collins and Sanjayan [32] found that the 5% NaOH and 4% 5 min keeping tungsten carbide ball-material ratio of 1:1. The resulting
Na2CO3 had the best combination of 1-7 days strength development with composite mix had the mean particle size of 19.43 μm.
reasonable workability equivalent to ordinary Portland cement at normal Activating solution: The Na2CO3 and sodium silicate solution were
curing temperature. They also reported that slag concrete had more drying blended in the ratio of 1.5:1 and thoroughly mixed with the help of a
shrinkage than the OPC concrete [33]. Jolicoeur et al. [34] observed that mechanical stirrer. Prior to use, the aqueous solution of Na2CO3 was
the improved workability of Na2CO3/NaOH activated slag can be obtained prepared by dissolving its fine ground particles into the warm water
with the addition of sodium polynephthanate and sodium gluconate. In (∼40 wt%). The activating solution was formulated by adding 1.0 wt%
addition to these two part mix systems, solid silicates, hydroxides and boric acid (of binder) into it. The pH of resulting activating solution was
carbonates have been used for activation of various systems such as fly found in the range of 12.5–13.5.
ash/slag mix [35], geothermal silica and sodium aluminate (with or Geopolymer pastes: The composite mix powder and activating so-
without fly ash) [36], and also with thermally treated feldspar [37] to lution were thoroughly mixed in a laboratory mixer for 5 min to obtain
produce one part geopolymer solid binders. These binders have great
potential to be used corresponding to OPC. Table 1
In the present paper, geopolymer cured at room temperature was Chemical composition of fly ash and ground granulated blast furnace slag.
synthesized from composite mixes of fly ash & slag and Na2CO3/
Constituent Fly ash (wt %) Slag (wt %)
Na2SiO3 activating solution. Rheology, geopolymerization kinetics,
strength development and microstructure of the resulting pastes were SiO2 56.95 31.90
discussed. A comparison was also made between the room temperature Al2O3 31.17 16.17
and heat cured geopolymer pastes to assess their suitability for the end CaO 1.416 40.73
Fe2O3 5.04 0.86
use applications. The performance of the developed binder was also MgO 0.464 6.519
assessed in producing geopolymer mortars. SO3 0.13 1.32
MnO 0.03 0.07
2. Materials and methods Na2O 0.078 0.202
K2O 1.414 0.64
TiO2 2.39 0.89
Low calcium fly ash was collected from M/s Suratgargh Super Thermal LOIa 0.92 0.69
Power Station, India (Blaine's surface area, ∼409 m2/kg and average par-
ticle size, 39 μm). About 82.81% of the particles were smaller than 45 μm. a
Loss on Ignition.

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Table 2 Mini slump flow test [39] was also carried out for various geopo-
Mix composition of fly ash/slag geopolymer pastes. lymer pastes (steel slump mould: 57 mm height, 19 mm top diameter
Parameter Activator (wt Activating solution Water (g) Water- and 38 mm bottom diameter). The flow spread diameter for the pastes
%) binder ratio on the glass plate was measured after 60 s.
Na2CO3 (g) Na2SiO3 (g)

Fly ash/slag ratio (activator 18%) 2.2.3. Isothermal conduction calorimetry

2:1 18 16.2 10.8 25.83 0.21 Isothermal Conduction Calorimeter (TAM Air, TA Instruments Inc.,)
3:1 18 16.2 10.8 25.83 0.21
was used to monitor the geopolymerization reaction of fly ash, slag and
4:1 18 16.2 10.8 25.83 0.21
Activator dosage (fly ash/slag ratio 2:1)
their composite mixes activated with 22 wt% activating solution as per
16 – 14.4 9.6 26.46 0.21 ASTM C 1679–14. The samples were prepared externally and about 6 g
18 – 16.2 10.8 25.83 0.21 of it was transferred into disposable glass ampoule. Subsequently, the
20 – 18 12 25.20 0.21 ampoule was loaded into an eight-channel calorimeter. The test was
22 – 19.8 13.2 24.57 0.21
conducted at 25 °C for 7 days for each composition. The test was also
25 – 22.5 15 23.63 0.21
30 – 27 18 22.05 0.21 run at 35 °C and 45 °C for 72 h to know its calorimetric response against
Water-binder ratio (fly ash/slag ratio 2:1) the rise of temperature. The cumulative heat during the geopolymer-
0.2 18 16.2 10.8 24.6 – ization reaction was recorded by integrating its heat flow with time.
0.21 18 16.2 10.8 25.83 –
0.24 18 16.2 10.8 29.52 –
0.29 18 16.2 10.8 35.67 – 2.2.4. X-ray diffraction (XRD)
The paste samples were ground and sieved into fine powder
(∼75 μm). XRD patterns of these powdered samples were recorded on a
a homogeneous paste. The composition of various geopolymer pastes is X-ray Diffractometer (Bruker D8 Advance) using Cu-Kα radiation by
given in Table 2. The said paste was cast in a 25 × 25 × 25 mm cube scanning from 5° to 80° 2 Ɵ with 0.1° step size.
mould and then covered with a plastic sheet to prevent its loss of
moisture. The activator dosages in the mix varied between 16 wt% and
30 wt% of the total mix. Water-binder ratio was kept at 0.20, 0.21, 0.24 2.2.5. Fourier transform infra red spectroscopy (FTIR)
and 0.29. It is mentioned that water of activating solution was included FTIR Spectrophotometer (Perkin Elmer-GX) was employed to collect
in calculating water-binder ratio of the geopolymer pastes. The samples the spectra of paste samples in the range of 4000–370 cm−1 at a re-
were cured at room temperature (27 ± 2 °C) for 24 h, demoulded and solution of 4 cm−1. The ground powdered sample (∼3 wt%) was ra-
then stored for 28 days prior to test. The specimens were also cured tioed against KBr and prepared a pellet for recording of spectrum.
under an elevated temperature (80 ± 2 °C) for comparison purpose.
2.2.6. Field emission scanning electron microscopy (FE-SEM)
2.1.2. Geopolymer mortars FE-SEM (QUANTA) was used to examine the microstructure of
Geopolymer mortar was produced using an optimized fly ash/slag com- geopolymer pastes. Prior to an examination, a thin film of Au/Pd
posite mix (2:1), standard sand and activator in a Hobart mixer. The com- coating was applied onto the surface of samples to render them con-
posite mix-sand ratio was kept as 1:1, 1:2 and 1:3. The activator dosage was ductive. The elemental mapping in microstructure of the samples was
used in the range of 10–50 wt% of composite mix. A minimum of 105 ± 5% also carried out at different locations with the help of an energy dis-
flow was maintained in all mixes as per ASTM C 1437 to ensure that mortar persive spectroscopy (EDS) to know its compositional variation.
could be poured easily into mould without exudation. The mortar was cast
into 50 × 50 × 50 mm cube mould. The demoulded samples after 24 h were
2.2.7. Surface area and porosity analyzer
stored at room temperature for 7 days and 28 days prior to test.
Surface area/Porosity Analyzer (Micrometrics, ASAP 2010) was used for
the determination of porosity in the samples via adsorption and desorption
2.2. Test methods isotherms. Prior to analysis, the hardened pastes were immersed into
acetone to stop the geopolymerization reaction. Subsequently, the granular
2.2.1. Surface area and particle size distribution specimens were degassed under vacuum at 350 °C for 6 h to evacuate their
Automatic Blaine's apparatus (Testing instrument) was used for the moisture which will negatively impact the surface interaction with the ni-
determination of fineness of the fly ash and slag particles according to trogen gas. The temperature is set at 350 °C knowing that no damage
IS 1727–1967 [38]. The particle size of fly ash and slag was determined happens to any physical and chemical changes in the samples that could
by a Laser Particle Size Analyzer (Horiba, LA-950V2). About 5 g of affect their surface characteristics. At the end of 6 h, the samples were
sample dispersed in an acetone was placed in the flow cell and a laser completely dehydrated. Nitrogen adsorption measurement was performed
beam was allowed to pass through the sample in the sample bath. After at 10 cm3/g STP pressure onto the specimen surface. Pore size distribution,
a sonic vibration, a plot between cumulative percentage passing and pore volume and pore diameter in the samples were measured.
particle size was recorded.

2.2.8. Setting time

2.2.2. Rheological test
Rheological test of geopolymer pastes was carried out as per ASTM
C 1749–12 with the help of a Rotational Viscometer using a co-axial
cylinder measuring tool (Grace, 3500). The sample containing different
fly ash/slag ratios (2:1, 3:1 and 4:1) were prepared at 22 wt% activator
dosage in a laboratory mixer. It was then transferred into sample cup
(300 g) of a Viscometer and was sheared in steps from 0 to 50 s−1 for
5 min. The space between the bottom of rotor and bottom of the sample
holder was 12.70 mm. The shear stress versus shear rate for the paste
samples was recorded. The rheo test was further conducted for the
optimized composite paste (fly ash: slag: 2:1) with different water-
binder ratios (0.35–0.50) to know its yield stress value.
The geopolymer pastes containing different fly ash/slag ratio (2:1,
3:1, 4:1) were prepared at 0.21 water-binder ratio and 22 wt% activator
dosage. The setting time of these pastes was determined by the Vicat's
apparatus (AIMIL) as per IS: 4031(Part 5)-1988 [40].
2.2.9. Compressive strength
The compressive strength of specimens (paste: 25 × 25 × 25 mm
and mortar: 50 × 50 × 50 mm) was performed on a Universal testing
machine (Testometric, 50 kN capacity) at a cross-head speed of 5 mm/
min according to IS: 4031(Part 6)-1988 [41]. The average value of five
specimens was reported.

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Fig. 2. Rheological Hysteresis loop of fly ash paste and composite pastes with varying fly ash/slag ratio of 2:1, 3:1 and 4:1 at 22 wt% activator dosage.
3. Results and discussion
3.1. Rheological behavior
Fig. 2 shows rheological curves of the fly ash paste and fly ash/slag
composite pastes at 22 wt% activator dosage using 0.45 water-binder
ratio. At low shear rate, the pastes become flocculated and gained viscosity
with shear time whereas at higher shear rate, the floccs were broken down
attributable to the shear-induced dispersion of particle aggregate in the
pastes. In a hysteresis loop, the shear stress of upward curve was higher
than the downward curve for all the pastes, supporting partial breaking of
bonds in the pastes during shearing. As the slag content in the mix was
increased, the degree of thixotropy increased. The thixotropic index of
downward shear rate curve was also estimated by measuring the viscosity
at speeds that differ by a factor of 10 (viscosity ratio = log (Mx/M10x),
where Mx is the Viscometer reading at speed x and M10x is the Viscometer
reading at speed 10x). It was found that the viscosity ratio of all the pastes
was less than 1 (0.70–0.82) which supported their higher thixotropic be-
havior. The downward curve of fly ash geopolymer paste was straight
showing Bingham rheology (Eq. (1)) whereas composite pastes followed
Herschel-Bulkley model (Eq. (2)) exhibiting a curved down ramp whose
structure was still being broken down by the shear.
τ = τ0+ μ γ
τ = τ0+ a γ b
where, τ is the shear stress in Pa, τ0 is the yield stress in Pa, μ is the
plastic viscosity in Pa.s, γ is the shear rate in 1/s, a is the consistency
index and b is the power law index. It was observed that the area of
hysteresis loop increased as the slag content was increased in the
composite pastes. An increase of 73–334% in the hysteresis area was
observed for composite pastes over the fly ash paste. This result can be
used as a basis to quantify the degree of structure in the paste as a
function of mixing shear rate [42,43]. In terms of yield stress, the values
for composite pastes containing fly ash and slag at 3:1 and 4:1 ratio
Cement and Concrete Composites 97 (2019) 226–238
were slightly lower (7.0–8.7 Pa) than the fly ash paste (9.8 Pa) because
slag was almost dissolved resulting in low solid content [44]. This
suggested that slag upto a level of 25% (fly ash: slag: 3:1) has no effect
on the rheology of paste. Above this level (2:1), its yield stress (18.6 Pa)
was almost doubled the fly ash paste and other composite pastes which
is an indicative of its stiffness. This can also be evidenced during mini
slump test wherein a reduction of ∼14% in the slump spread diameter
was observed over the fly ash paste. It is believed that composite paste
was not completely sheared due to the progress of geopolymerization
reaction. Agglomerated structure in the paste still existed and the par-
ticles were also not dispersed. Such flocc formation is explained with
the help of early formation of C-S-H/(Ca, Na)-A-S-H gel as a result of
bonding of the calcium ions present in the slag to the silicate ions of the
activating solution [45,46].
For making high strength binders, the rheological behavior of compo-
site paste (fly ash/slag mix in 2:1 ratio) was studied as a function of water-
binder ratio at 22 wt% activator dosage. As it can be seen in Fig. 3, the flow
behavior of pastes increased with the increase of water-binder ratio which
indicated a shear thinning behavior. The paste having a low water-binder
ratio of 0.35 was very stiff. Its yield stress value was ∼30 Pa. A decrease in
the value was noticed when the water-binder ratio of the geopolymer
pastes increased from 0.35 to 0.50. The shear thinning response of paste
disappeared at a water-binder ratio of 0.5 and the paste behaved like a
(1)
pseudo-plastic fluid. The mini slump spread also supported lowering in
(2) yield stress of the pastes. An increase of ∼47% slump spread was observed
when water-binder ratio increased from 0.35 to 0.50. The reduction in
particle aggregation in the pastes was attributed to the dominance of hy-
drodynamic forces over the attractive inter-particle forces [47].
3.2. Geopolymerization kinetics
Geopolymerization reaction of the fly ash, slag and their composite
mixes was studied at 22 wt% activator dosage at 25 °C, 35 °C and 45 °C.
It can be seen in Fig. 4 that the initial dissolution peak appeared within
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Fig. 3. Shear stress Vs shear rate of fly ash/slag composite paste (2:1) at dif-
ferent water/binder ratios.
4 min for all mixes at 25 °C followed by an induction period where early
reaction slowed down as a result of depositing a layer of precipitates
onto the particles which isolated the part of unreacted particle surface
from the main solution. The emergence of an acceleration peak
(second) in the curve was attributed to the formation of reaction pro-
ducts probably the C-A-S-H/C-S-H and (Ca, Na)-A-S-H during con-
densation process [11]. This peak also corresponds approximately to
the completion of setting process. The existence of a shoulder on the
heat evolution curve of slag paste and composite paste (2:1 ratio) im-
plied probably the reaction between the residual unreacted slag parti-
cles and activator. The gradual decreasing rate of heat evolution cor-
responds to the slow reactions at the later stage because unreacted
particles do not pass through a true solution. It was noted that in ca-
lorimetric response, the heat evolution rate for the fly ash paste during
acceleratory period was 0.049 mW/g only. There was no acceleration
peak in the curve because the network structure does not form at room
temperature due to its high activation energy barrier [17]. When slag
was added to the fly ash paste, the heat production rate during accel-
eration period increased in the range of 0.27–2.47 mW/g. The peak
position also shifted towards a lower time scale. Compared with the
slag paste (33 min), the composite pastes took more time to reach
Fig. 4. Normalized heat flow curve of fly ash paste, slag paste and their com-
posite pastes in the ratio of 2:1, 3:1 and 4:1 at 25 °C.
230
Cement and Concrete Composites 97 (2019) 226–238
Fig. 5. Cumulative heat release for fly ash paste, slag paste and their composite
pastes in the ratio of 2:1, 3:1 and 4:1 at 25 °C.
acceleration peak (3.26 h for 2:1 ratio, 8.37 h for 3:1 ratio and 12.17 h
for 4:1 ratio). Due to presence of fly ash in the mix, the induction time
lengthened which was associated with the workability of geopolymer
pastes. Contrary to this, the slag paste had less distinct and short in-
duction period as reported earlier [48] which was an indication of
faster setting. Higher the intensity of an acceleration peak, higher the
reaction product formation which is related to the hardening and
strength development in the pastes.
Fig. 5 shows the cumulative heat release of fly ash paste, slag paste
and their composite pastes after 7 days at 25 °C. It was observed that the
total heat released for fly ash paste was 18 J/g only at 7 days. Contrary
to this, the total heat released for the fly ash/slag composite pastes was
78 J/g for 2:1 ratio, 62 J/g for 3:1 ratio and 60 J/g for 4:1 mix ratio.
The enhancement in the total heat release was 230–300% over the fly
ash paste attributable to the existence of more reaction products in the
system. It was also noted that the total heat released for composite
pastes was lower than the slag paste (90 J/g). It is believed that the total
heat released during geopolymerization reaction of composite pastes
would help in developing an understanding on the reaction product
formation which in turn defines its strength development.
The effect of temperature on the calorimetric response of fly ash
paste, slag paste and their composite pastes is shown in Table 3. As
would be expected, increasing temperature enhanced the height of ac-
celeration peak and shifted their occurrence to a lower time scale. In the
case of composite pastes, an increase of 136–1300% in the peak intensity
was observed when the test temperature increased from 25 °C to 45 °C.
The time to reach an acceleration peak was also reduced by manifolds. At
45 °C, the peak in the curve appeared only after 35–46 min supportive of
acceleration in condensation reaction between the dissolved species (Si,
Al and Ca) under the influence of temperature. It was noted that the
acceleration peak in fly ash paste was non-existent at all temperatures
(25 °C, 35 °C and 45 °C) although the heat evolution rate at 45 °C was
0.73 mW/g. Contrary to this, slag paste had an acceleration peak at 25 °C
with a heat evolution rate of 3.90 mW/g. At 45 °C, the peak was sharper
and its height increased by 237% when compared with the peak at 25 °C.
The time to reach an acceleration peak also got reduced by 57%. This
indicated the significant role of slag in geopolymerization of the com-
posite mixes as reported earlier [11,17]. Fig. 6 shows cumulative heat
release for various pastes at different temperatures for 72 h. It was ob-
served that fly ash paste had a plateau in the curve whereas, the heat
curves of slag paste and composite pastes continued to increase with
I. G et al. Cement and Concrete Composites 97 (2019) 226–238

Table 3
Effect of temperature on the calorimetric response of fly ash paste, slag paste and their composite pastes (fly ash/slag ratio of 2:1, 3:1 and 4:1).
Mix Temperature (°C) Acceleration peak (mW/g) Time to peak (min) Cumulative heat at 72 h (J/g) Activation energy, Ea (KJ/mol)

Fly ash 25 0.049 898 19.995 287 ± 6.0

35 0.118 181 21.966
45 0.733 46 41.267
Composite paste (4:1) 25 0.266 737 58.215 160 ± 5.0
35 2.034 87 87.498
45 3.733 46 86.913
Composite paste (3:1) 25 0.433 519 60.954 139 ± 4.0
35 2.532 71 87.521
45 4.8033 37 103.59
Composite paste (2:1) 25 2.473 206 66.704 128 ± 0.7
35 2.819 81 92.692
45 5.827 35 111.485
Slag 25 3.904 33 86.65 84.9 ± 0.9
35 8.0319 40 144.309
45 13.139 21 157.66

Fig. 6. Cumulative heat release for fly ash paste, slag paste and their composite pastes at 25 °C, 35 °C and 45 °C.

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lower slope supporting reaction product formation with the progress of
time. The composite pastes had 110–320% more total heat release than
the fly ash paste and 23–45% less than the slag paste. It was noted that
the total heat release decreased when fly ash content in the composite
mixes was increased at all temperatures.
In order to study the kinetics of geopolymerization reaction, heat
production data obtained from the isothermal calorimetric run was
used in the Arrhenius model as mentioned in earlier work [49]. Because
geopolymerization process is composed of several reactions, the term
apparent activation energy is used here. The apparent activation energy
was calculated using the following formula.
Ea (T,Q) = -RT1T2/(T2-T1) ln K2/K1 (3)
Ea is the apparent activation energy, R is the ideal gas constant, T1
and T2 are the temperatures, K1 and K2 are the rate of hydration at two
isothermal curing temperatures T1 and T2 respectively. In the plot be-
tween heat flow and reciprocal of temperature, Ea was calculated from
the slope. It was found that Ea of fly ash paste and slag paste was 287 kJ/
mol and 84.9 kJ/mol respectively. The high value of Ea for fly ash paste
was attributed to its low total heat released during reaction, thereby
requiring higher temperature for the strength development. For fly ash/
slag composite pastes, the value of Ea varied between 128 kJ/mol and
160 kJ/mol. However, these values were higher than the reported values
for the Portland cement (38 kJ/mol) and slag paste (80 kJ/mol) [50].
3.3. Reaction products characterization
Reaction products formed during geopolymerization of the fly ash,
slag and fly ash/slag composite mixes were analyzed with the help of
XRF, XRD and FT-IR techniques. The chemical composition as observed
under XRF technique indicated that silica and alumina contents after
the activation of fly ash remained 54.28% and 23.45% respectively
which were 4.50% and 22.60% lower than the raw fly ash. In the case
of slag, CaO, SiO2 and Al2O3 contents after its activation were reduced
by 10.53%, 8.24% and 28% respectively. When the slag was mixed with
fly ash in different ratios (4:1, 3:1 and 2:1), silica and alumina contents
in the pastes remained 47–50% and 19–21% respectively. As the slag
content was increased in the mix, the silica and alumina contents re-
duced and CaO content increased in the resulting pastes showing their
involvement in the formation of phases. The reaction products in the
pastes had SiO2/Al2O3 ratio in the range of 2.38–2.41, Na2O/Al2O3
ratio, 0.62–0.66 and CaO/SiO2 ratio, 0.16–0.26 which were probably
adequate for the strength development in the binders.
Fig. 7 shows the XRD patterns of fly ash paste, slag paste and fly/
slag composite pastes. In all diffractograms, the halo region (hump)
attributed to the amorphous phase has been identified with small
crystalline peak of various phases. It is believed that crystal growth
from the zeolitic nuclei formed in the pastes was extremely slow under
low liquid/solid ratios and high pH conditions and therefore, resulting
in an amorphous cementitious matrix [29]. The mineralogical compo-
sition of composite pastes showed a diffuse broad hump with a shift to
the right in the range of 16°–39° 2Ɵ when compared with the fly ash
paste (15°–30° 2Ɵ) and slag paste (23°–40° 2Ɵ) indicating formation of
the sodium aluminosilicate hydrate (Na2Al2Si14O32.3H2O)/calcium si-
licate hydrate gel of an amorphous character. The area of these humps
increased with increasing slag content in the pastes. The higher the
amount of gel in pastes, the higher the mechanical strength of geopo-
lymers. In addition, several sharp characteristic peaks also appeared in
the XRD patterns. Based on the XRD reference database (COD-Inorg
REV184208), these peaks were identified as zeolite products having
various polytypes such as chabazites (Ca1.74Al3.48Si8.52O42.15H70, Si/
Al = 1.96, JCDPS 00-019-1178), sodalite (Na5.28K1.40Ca1.23Al6Si6
ClCO28S, Si/Al = 1, JCDPS 00-011-0401), analcime (Na1.862Al2Si4
O13.667H4, Si/Al = 2.32, JCDPS 00-019-1180) and calcium containing
compounds such as tobermorite (Ca2.25Si3O11H7, Ca/Si = 0.75, JCPDS
232
Cement and Concrete Composites 97 (2019) 226–238
Fig. 7. XRD patterns of fly ash paste, slag paste and their composite pastes in
the ratio of 2:1, 3:1 and 4:1. (M: Mullite, Q: Quartz: C: Calcite: Ch: Chabazite, S:
Sodalites, A: Analcime, G: Gismondine, C-S-H: C-S-H gel, N: Natrite).
00-033-0306), gismondine (CaAl2Si2O12.303H8.606 Ca/Si = 0.5, Si/
Al = 1, JCPDS 00-039-1373), hydrotalcite (Mg6Al2CO3(OH)16.4H2O,
JCPDS 00-014-0191) and calcite (CaCO3, JCDPS 00-047-1743). The
presence of natrite (sodium carbonate hydrate, JCPDS 00-037-0451)
was excessive in the pastes (∼7% by wt). The crystalline phases such as
quartz (SiO2, JCPDS 00-046-1045), mullite (Al6Si2O13, JCPDS 00-015-
0076) and magnetite (Fe2O3) present in the raw fly ash remained un-
altered after the activation of fly ash/slag composite mixes as also re-
ported earlier in geopolymeric studies [51,52]. The existence of these
reaction products is controlling the compressive strength gain observed
in the geopolymer pastes.
-The formation of reaction products in the pastes was further evi-
denced with the help of FTIR spectra as supplement to X-ray structural
analysis (Fig. 8). The characteristic broad asymmetric absorption bands
in 1300–850 cm−1 and 500-420 cm−1 spectral regions of Si-Al frame-
work were assigned to the Si-O-Si and Si-O-Al stretching vibration and
bending vibration respectively [53]. When compared with the fly ash
paste, the composite pastes had overlapped peaks in 1300–850 cm−1
region and also exhibited a peak shift towards lower frequency possibly
due to the increasing number of tetrahedral aluminum atoms in the
framework [54]. The peak at around 992 cm−1 corresponds to Si-O
stretching vibration of SiO4 tetrahedron of slag implying the formation
of C-S-H type gel in the pastes [55]. Absorbance peak height at around
1050 cm−1 was increased by 37% for 20% slag containing composite
paste. Above this level, a decrease in the peak height (42–54%) was
unexpectedly noticed with respect to fly ash paste probably due to the
overlapping of several absorption bands. However, the peak area cen-
tered at around 1050 cm−1 was increased by 7–570% when compared
with the fly ash paste possibly indicating more reaction products for-
mation. The presence of broader bands with respect to raw materials is
an indication of the amorphous nature of geopolymer pastes. This
supported the existence of mixed phases (N-A-S-H, (Ca, Na)-A-S-H and
C-A-S-H/C-S-H) in the reaction products as observed in the XRD pat-
terns which was in agreement with the rise in the mechanical strength
of pastes. The existence of hydrogen bonded -OH stretching band at
around 3455 cm−1 and usual bending vibration of water at around
1645 cm−1 suggested the presence of water either trapped in the large
cavities released during geopolymerization reaction or surface ad-
sorbed. These -OH/H2O peak intensities increased with decreasing slag
content in the composite pastes probably due to their zeolitic pore
opening as evidenced by the appearance of absorption bands in the
region of 420–370 cm−1. The doublet peak in the range of
I. G et al.
Fig. 8. FT-IR spectra of fly ash paste, slag paste and their composite pastes in
the ratio of 2:1, 3:1 and 4:1.
1418–1488 cm−1 and absorption band at around 870 cm−1 were at-
tributed to O-C-O (CO3 2-) asymmetric stretching and out plane bending
vibrations in all samples except fly ash paste [53]. This could be ex-
plained by the presence of excess sodium ion deposited on the pore
surfaces and also due to the presence of unreacted sodium carbonate in
the pastes. This suggests that sodium carbonate used in the activation
process was in excess.
3.4. Setting time
The initial setting time for the fly ash/slag composite pastes ranged
between 21 min and 44 min. As the slag content was increased in the
mix, the initial setting time of the resulting pastes decreased. To make a
workable mix for specified time needed for their transport and finish-
ability at working place, the initial setting time of composite pastes was
extended by adding ∼1 wt% boric acid (of binder) as a set retarder into
the mix. The resulting initial setting times for various fly ash/slag
composite pastes made in the ratio of 2:1, 3:1 and 4:1 were 72 min,
83 min and 105 min respectively. Boric acid reacted with calcium ion
(released from the slag) to produce calcium borate [56] which might
have slowed down the formation of C-S-H/C-A-S-H gel, thereby en-
hancing the setting time. When compared with the Portland cement,
geopolymer pastes satisfied the criteria of initial setting time but
showed relatively fast final setting. Since initial setting time for Port-
land cement is specified for min. 30 min, therefore, the same initial
setting time was targeted for fly ash/slag geopolymer pastes also.
3.5. Optimization of constituent parameters
3.5.1. Fly ash/slag ratio
Fig. 9 shows the compressive strength of fly ash/slag composite
pastes at 18 wt% activator dosage and 0.21 water-binder ratio. As the
slag content was increased in the mix, the compressive strength of the
resulting pastes also increased. This is in good agreement with an in-
crease of heat release under calorimetry with increasing slag content in
the pastes. It was noted that strength gain in the samples at 28 days was
30-40% higher than those cured for 7 days. Puertas et al. [13] reported
that slag in the mix is almost completely dissolved. The fly ash is par-
tially dissolved and precipitated in the reaction process even in the
paste activated at ambient temperature. As a result, the strength
forming amorphous hydrated C-S-H like gel with aluminium and
233
Cement and Concrete Composites 97 (2019) 226–238
Fig. 9. Compressive strength of geopolymer pastes as a function of different fly
ash/slag ratios at 7 and 28 days.
sodium ions in its structure is produced. As the geopolymerization re-
action proceeded, the voids and pores were filled with these reaction
products thus, increasing the compactness and consequently, the me-
chanical strength of hardened pastes.
The strength development in the pastes can be further explained on
the basis of their microstructures observed under FESEM (Fig. 10). At
higher fly ash/slag ratio (4:1 and 3:1), the existence of unreacted fly ash
particles was viewed as the dominant feature. The layered micro-
structures at certain places were also seen (Fig. 10 a & b). In the case of
higher slag containing composite paste (2:1), the particle morphology
has markedly changed showing that calcium released from slag was
acting as a precipitation agent [11]. The deposition of reaction products
onto the surface of particles was clearly evident. The remnants of fly ash
along with cavities were also seen (Fig. 10c). The microstructure ap-
peared to be denser than those pastes made with fly ash/slag ratio of
4:1 and 3:1 supportive of its higher compressive strength.
As it was observed in the EDAX, the sodium and calcium ions were
distributed throughout the microstructure (Fig. 10). The partially reacted fly
ash core particles had Si/Al = 1.94, Na/Al = 0.37 and Na/Si = 0.19 and
that of reaction products had an elemental ratio of Si/Al = 2.06–2.1., Na/
Al = 0.42–1.19, Ca/Si = 0.17–0.32 and Na/Si = 0.36–0.42. This was pos-
sibly indicating an intermixed microstructure of N-A-S-H, (Ca, Na)-A-S-H
and C-S-H phases as reported previously [11–13]. The reaction products
also contained magnesium (0.72–0.95), iron (0.5–1.40) and titanium
(0.33–0.67) which were derived from the raw materials. The Ca/Si ratio in
the pastes increased with increasing slag content in the mix indicating dif-
ferences in dissolution of fly ash/slag particles and subsequent reaction
product formation as evidenced in other techniques (Calorimetry, XRD &
FTIR). The pastes made with fly ash/slag in the ratio of 3:1 and 4:1 had
lower Na/Al ratio (0.42–0.8) than the reported ratio of 1.0 for aluminosi-
licate gel [57] which indicated that only sodium as the cation was in-
sufficient for charge balancing in the geopolymer skeleton favoring the
explanation for their low strength development. At certain locations, Na/Al
ratio was more (1.15–1.19) than the specified ratio supporting higher ten-
dency of alkali binding of C-A-S-H gel in the pastes.
3.5.2. Activator dosage
The effect of activator dosage on the compressive strength of fly
ash/slag composite pastes (2:1) is shown in Fig. 11. At 7 days, the
maximum strength in the pastes was obtained at 22 wt% activator do-
sage. Contrary to this, the pastes cured for 28 days showed an initial
strength gain upto 22 wt% activator, followed by its leveling off and
then it increased with increasing activator dosage. Above 30 wt% ac-
tivator dosage, considerable amount of efflorescence was visually no-
ticed on the surface of specimens. As room temperature curing does not
I. G et al.
Fig. 10. FESEM-EDAX images of geopolymer pastes at 18 wt% activator dosage
containing fly ash/slag ratio (a) 4:1, (b) 3:1, (c) 2:1.
Fig. 11. Compressive strength of fly ash/slag geopolymer pastes (2:1) as a
function of different activator dosages.
234
Cement and Concrete Composites 97 (2019) 226–238
Fig. 12. Pore size distribution of fly ash/slag geopolymer pastes (2:1) at 18 wt%
and 30 wt% activator dosages.
promote setting of N-A-S-H phase arose from the fly ash, the excess
alkaline solution was crystallized on the surface at high activator do-
sages causing efflorescence [20]. A maximum strength of ∼56 MPa was
achieved with 30 wt% activator dosage. It was noticed that the pastes
cured for 28 days had 60–90% higher strength than the pastes cured for
7 days at various activator dosages. This can be attributed to the sus-
tained reaction between the fly ash/slag particles and activator over a
period of time.
The evidences for strength in the fly ash/slag composite pastes can
be explained with the help of their microstructural evolution such as
reaction products, unreacted particles, voids and cracks. Fig. 12 shows
incremental pore size distribution of composite pastes made with 18 wt
% and 30 wt% activator dosages. It was observed that the pastes ex-
hibited bimodal peak with larger scattering of pores at lower activator
dosage. The pore size ranged from 19.8 to 2342.1 Å. The maximum
pore diameter was ∼133.58 Å. The pore volume varied from
1.8 × 10−4 to 5.8 × 10−3 cm3/g. Contrary to this, at 30 wt% activator
dosage, the pore size in the paste varied between 19.8 Å and 1155 Å.
The maximum pore diameter was ∼94.24 Å. The pore volume varied
from 2.13 × 10−4 to 2.35 × 10−3 cm3/g. This implied that a pore re-
finement that occurred at higher activator dosage could be responsible
for compact microstructure of the pastes and consequently, the superior
strength development. Supportive of this, image processing of back-
scattered electron images was carried out with a view to know reaction
product content and void content in the pastes. It was found that the
paste containing 30 wt% activator dosage had 60% reaction products
and 38% voids whereas the paste with 18 wt% activator dosage had
46% reaction products and 41% voids. The gel/space ratio in the pastes
was 0.61 at 30 wt% activator compared to 0.53 at 18 wt% activator. The
surface area of gels was in the range of 8–15 m2/g. As the surface area
of gels was increased, the compressive strength of pastes increased from
34 MPa to 56 MPa. Collins and Sanjayan [58] reported that higher
mesopores in the activated mix led to higher capillary stress and greater
shrinkage during drying resulting in low compressive strength.
Fig. 13 shows FESEM images of the fly ash/slag composite pastes
with different activator dosages. The paste with 18 wt% activator do-
sage had a porous microstructure as also observed in the porosity
measurement along with partially reacted fly ash/slag particles (Fig. 13
a). The inter-connectivity between the particles was inadequate. EDAX
mapping indicated that Si/Al ratio in the paste was 2.06 similar to fly
ash. Because of low Na/Si ratio (0.42), the dissolution of particles in the
solution and their conversion into gels were slow at this activator level.
The Ca/Si ratio was 0.32. At 22 wt% activator dosage, the micro-
structure appeared to be denser and partially reacted particles were
well connected through the gel networks (Fig. 13 b). The existence of
voids and cracks was also seen. EDAX spectra indicated that Si/Al, Na/
I. G et al.
Fig. 13. FESEM-EDAX images of fly ash/slag geopolymer pastes (2:1) at dif-
ferent activator dosages (a) 18 wt%, (b) 22 wt%, (c) 30 wt%.
Al and Ca/Si ratios in the pastes were 2.30, 1.02 and 0.34 respectively.
At certain locations, the concentration of aluminium was high which
might have disturbed the charge balance in the Si-Al skeleton, conse-
quently, cracking occurred in the internal structure. At 30 wt% acti-
vator dosage, the microstructure was smooth, inter-mixed and denser as
compared with the other pastes because of its higher Na/Si ratio (0.82)
(Fig. 13 c). The voids appeared to be superficial and distributed
throughout the microstructure. The concentration of calcium in the gels
was in the range of 4–7 wt% indicating the existence of inter-mixed
phases of C-S-H, N-A-S-H and (Ca,Na)-A-S-H. It was noted that in-
creasing activator dosage resulted in pastes with less unreacted parti-
cles. As the calcium dissolved, it preferentially combined with silicon in
the solution to precipitate as C-S-H gels which could be enriched with
alkali [12]. The precipitation of C-S-H and (Ca,Na)-A-S-H gels forms the
basic structure of solids which defines the times for the onset of hard-
ening/strength development.
3.5.3. Water-binder ratio
Fig. 14 shows the effect of water-binder ratio on the compressive
strength of fly ash/slag composite pastes (2:1). As the water-binder
ratio was increased from 0.20 to 0.29 in the mix, the compressive
strength of resulting pastes got decreased. It was noted that below 0.20
235
Cement and Concrete Composites 97 (2019) 226–238
Fig. 14. Compressive strength of fly ash/slag geopolymer pastes (2:1) as a
function of water-binder ratio.
water-binder ratio, the mix was not workable due to the insufficient
wetting of particles. At higher water-binder ratio, the molarity of ac-
tivator decreased substantially which in turn, affected surface hydro-
xylation of fly ash particles resulting in low Si and Al species in the
aqueous phase [59]. Consequently, it resulted in pastes with poor
strength. The increase in molarity of activator by reducing water con-
tent caused a substantial acceleration of dissolution rate. This enhanced
the polycondensation of the Si − Al oligomers and the hardening of
network skeleton into a final geopolymeric structure, thus improving
the strength with a reduction in water-binder ratio.
3.5.4. Room temperature Vs heat curing
A comparative evaluation of fly ash/slag composite pastes cured at
ambient as well as elevated temperatures was made to know the difference
in strength development (Fig. 15). The composite pastes with fly ash/slag
in a ratio of 2:1 were prepared with different activator dosages and cured
at 27 °C and 80 °C for 7 days and 28 days. It was observed that the samples
cured at 80 °C for 7 days gained 41–163% more compressive strength than
the samples cured at 27 °C for all mixes studied. The increasing effect was
more pronounced at higher activator dosage due to the combined action of
temperature and alkali activation. The increased dissolution of fly ash/slag
particles and subsequent acceleration in the polycondensation reaction
supported the formation of more reaction products and consequently, the
higher strength development in the paste. Contrary to this, the pastes
cured at room temperature for 28 days had 6–18% more compressive
strength than the samples cured at 80 °C for 28 days. This is mainly due to
the formation of strength forming calcium containing phases (C-S-H/C-A-
S-H) which developed over a period of time at room temperature similar to
Portland cement. The prolong storage of samples (28 days) at 80 °C re-
sulted in dehydration and excessive shrinkage due to the contraction of
gels which caused breakdown of the paste skeleton [60]. The differences
in microstructure of the samples cured under the ambient and elevated
temperature conditions can be seen in FESEM images (Fig. 16). The heat-
cured samples had rough and hard microstructure (Fig. 16 a). The voids
were distributed throughout the surface which could be linked with water
evaporation from the gels during heat curing. Cracks were also seen. In
contrast, the ambient cured samples exhibited smooth, compact and soft
microstructure with low void content which could be responsible for their
superior strength at 28 days age (Fig. 16 b).
3.6. Efficacy of paste in mortars
The performance of developed fly ash/slag composite paste was
assessed for producing mortars and tested for their flow and
I. G et al. Cement and Concrete Composites 97 (2019) 226–238

Fig. 15. Compressive strength of fly ash/slag geopolymer pastes (2:1) cured at
ambient and elevated temperatures at different activator dosages.

compressive strength (Table 4). The mix was proportioned using com-
posite mix (fly ash:slag:2:1), standard sand and activator wherein the Fig. 16. FESEM images of fly ash/slag geopolymer pastes (2:1) (a) heat cured
ratio of binder and aggregate was kept as 1:1, 1:2 and 1:3. It was found (b) ambient cured.
that the initial flow of mixes varied between 102% and 137% de-
pending on the activator dosage (10–50%). As usual, increasing ag- Table 4
gregate content in the mix reduced the activator requirement of the Properties of geopolymer mortars made from fly ash/slag composite mix acti-
resulting mortars by 14–25% due to lesser amount of composite mix vated with sodium carbonate and sodium silicate.
powder. The mortars cured for 28 days had 37–64% more strength gain
Mix Aggregate- Activator Flow (%) Density (kg/m3) Compressive
than the mortars cured for 7 days. It was noted that geopolymer mortar Binder ratio (wt%) strength, 28
with binder-aggregate ratio of 1:2 gave the highest compressive days (MPa)
strength of ∼72 MPa which was comparable with the slag based mor-
1 1–1 10 100 ± 5 1872 ± 187 0.89 ± 0.09
tars activated with NaOH and sodium silicate [61]. While comparing
20 103 ± 5 1932 ± 193 34.29 ± 1.5
with OPC mortar, fly ash/slag geopolymer mortar made with Na2CO3/ 30 110 ± 5 2057 ± 206 67.63 ± 3.4
Na2SiO3 activator exhibited 67% higher compressive strength than the 40 124 ± 5 2018 ± 202 67.72 ± 3.4
minimum value specified in the code for Portland cement (binder-ag- 50 137 ± 5 2006 ± 201 69.32 ± 3.5
gregate ratio of 1:3). 2 2–1 10 104 ± 5 2013 ± 201 0.59 ± 0.03
20 113 ± 5 2103 ± 210 34.54 ± 1.7
In making fly ash/slag composite pastes, the selection of Na2CO3 as 30 105 ± 5 2146 ± 215 68.07 ± 3.4
part activator was motivated by the economic reasons since Na2CO3 is 40 131 ± 5 2115 ± 212 71.32 ± 3.6
cheap when compared with the conventionally used NaOH. Using blast 50 136 ± 5 2133 ± 213 68.94 ± 3.4
furnace slag in the mix, a cost- reduction from activator was further 3 3–1 10 104 ± 5 2026 ± 203 0.58 ± 0.03
20 105 ± 5 2146 ± 215 14.14 ± 0.7
achieved. Thus, Na2CO3 along with blast. furnace slag used in geopolymer
30 110 ± 5 2167 ± 217 63.20 ± 3.2
paste makes its cost-effective. Optimizing the dosage and sources of the 40 107 ± 5 2183 ± 218 68.84 ± 3.4
chemical activator is highly relevant in order to control the cost of the final 50 118 ± 5 2172 ± 217 61.51 ± 3.1
concrete products. The Na2CO3 also has the advantage of avoiding high pH
development which is very important with regards to safety issues.
an alternative to conventionally used sodium hydroxide for surface
hydroxylation of fly ash/slag particles to produce cost-effective geo-
4. Conclusions polymeric binders. Adequate workability in these binders can be
achieved through effective shearing as the area of hysteresis loop be-
Research results indicated that Na2CO3 in conjunction with high tween the shear stress and shear rate clearly indicated only the partial
modulus sodium silicate (Na2O/SiO2 = 0.9–1.1) can be safely used as structural break down of floccs at higher slag content (> 25 wt%). The

236
I. G et al.
formation of broaden XRD halo region, large IR peak area in the 1300-
850 cm−1 region and distribution of sodium and calcium ions
throughout the matrix with increasing slag content suggested the ex-
istence of amorphous inter-mixed phases of N-A-S-H, (Ca,Na)-A-S-H and
C-S-H/C-A-S-H. The developed composite paste had a compressive
strength of ∼56 MPa at 28 days room temperature curing with the fly
ash/slag ratio of 2:1, 30 wt% activator dosage and 0.21 water-binder
ratio and its mortar strength was found to be ∼72 MPa. The results
were comparable with the mortars produced with sodium hydroxide/
sodium silicate as described earlier [61]. On comparing, the samples
cured at 27 °C for 28 days gained higher compressive strength than the
samples cured at 80 °C. This may be attributed to the prolonged curing
at elevated temperature resulting in the formation of pores/cavities
after partial water evaporation from the paste and also due to the
thermolysis of Si-O-Al- bonds. These developments may lead towards
adoption of geopolymeric binders in producing concrete for site work
which has the potential for facilitating a wide range of technical ap-
plications as Portland cement. The work is being continued for produ-
cing concrete, self compacting concrete and building materials such as
bricks, blocks and light weight concrete using this geopolymeric binder.
Acknowledgements
The paper forms a part of Supra Institutional Project (SIP-29) of
CSIR R&D programme (Govt of India) and is published with the per-
mission of the Director, CSIR-Central Building Research Institute,
Roorkee (India).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cemconcomp.2018.12.007.
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