Construction and Building Materials 114 (2016) 297306

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Construction and Building Materials

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

Internal heat liberation and strength development of self-cured

geopolymers in ambient curing conditions
Teewara Suwan, Mizi Fan , Nuhu Braimah
College of Engineering, Design and Physical Sciences, Brunel University, Uxbridge, UB8 3PH London, United Kingdom

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Inclusion of OPC increased early

strength and shortened setting time

of GeoPC system.
 Heat liberation in GeoPC system was
mainly influenced by (inclusion) OPC
hydration.
 Pre dry-mixing process released
intensive heat when reacted with
water.
 Pre dry-mixing process provided
ability for practical work and in-field
applications.
 GeoPC system and Pre dry-mixing
could achieve the Self-cured GP
production.

a r t i c l e

i n f o

Article history:
Received 1 November 2015
Received in revised form 24 March 2016
Accepted 29 March 2016

Keywords:
Ambient curing
Heat liberation
Manufacturing procedure
Microstructure
Self-cured geopolymers

a b s t r a c t
Curing geopolymers with a temperature around 4090 C can significantly improve the mechanical properties and mechanisms of reaction. There is a challenge to develop GP with its abilities of curing in ambient temperature (22 2 C) without external source of heat supply for on-site practices. This study is
extended from the previous research work on the influence of OPC inclusion and manufacturing process.
The main aim is to study and evaluate the effects of additional OPC (GeoPC system) and manufacturing
procedures on accumulated-internal heat liberation and strength development of low calcium fly ashbased geopolymer paste. The results showed that the GeoPC compounds and manufacturing procedures
were closely related to the curing process, internal heat, microstructure development and hence properties of the end products. Both optimum GeoPC mixtures and new-introduced mixing method (pre drymixing) have been generated, providing clear potential and basis of the development of self-cured
geopolymers to achieve the mechanical strength and for on-site construction under ambient conditions.
2016 Published by Elsevier Ltd.

1. Introduction
Ordinary Portland cement (OPC) is an energy consuming product with high carbon dioxide (CO2) emission along its production
process. To reduce the amount of greenhouse gas, alternatives have
been studying to partially or totally replace the consumption of
Corresponding author.
E-mail address: mizi.fan@brunel.ac.uk (M. Fan).
http://dx.doi.org/10.1016/j.conbuildmat.2016.03.197
0950-0618/ 2016 Published by Elsevier Ltd.

OPC [1]. Many research studies have revealed that fly ash, blast furnace slag and other aluminosilicate materials can be used as prime
materials to produce a cementitious binder by activating with
alkaline solutions, which is known as alkaline-activated cement
or geopolymer cement [25]. Due to the complexity of various factors affecting its reaction, the definite mechanism of the alkalineactivated cement is not yet fully understood. However, many
researchers agree that its mechanism consists of three-stage model
which are dissolution, gelation and polymerization/hardening

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[6,7]. Apart from that, the term Geopolymers (by Davidovits J.,
1979) is also used and receives much more attention as an alternative binder for construction material [8,9]. The final reaction products of those systems can be C-S-H (Ca + Si), zeolite/polymers (Si
+ Al) or C,N-A-S-H (Ca,Na + Al + Si) which mainly depend on the
characteristics of raw starting materials and alkaline activators
[6,1017].
In construction sector, Geopolymers (GP) is developed and theoretically produced by utilising industrial by-products or wastes
such as fly ash, silica fume or even agro-waste ashes. Fly ash, a
by-product from coal-fired power station, seems to be the most
widely used prime material for the production of geopolymers
because of its richness in alumina-silica composition and the considerable un-utilised quantity [18]. The most commonly used alkaline materials are a combination of sodium hydroxide or potassium
hydroxide (NaOH, KOH) with sodium silicate or potassium silicate
(Na2SiO3, K2SiO3) [8,19]. Curing condition is one of the major factors affecting the mechanical properties and micro-structures of
geopolymers. At ambient temperature around 2025 C, fly ashbased geopolymers does not completely harden and could not be
tested on compressive strength in the first day after synthesis
[20,21]. Somehow, it has been found to achieve very high strength
in both early and later stages when cured in high temperature e.g.
4090 C [2,3,2224]. Furthermore, some of its properties have
also been reported to be similar as or even better than those of
OPC [4,18].
A numerous researchers have studied on the improvement of
setting and strength properties of fly ash-based geopolymers without high temperature curing. The considered challenge is to step
over the limitation of heat curing process: precast components,
and to be more convenient in practical works or in field applications. Some additives such as ground granulated blast furnace slag,
gypsum, Portland cement or even high calcium fly ash are studied
in order to enhance the reasonable strength development in ambient curing conditions [14,18,2528]. The use of OPC as an additive
in geopolymers is widespread due to its uniformity complied with
any standard and its global availability as a commercial construction material. This hybrid cementitious system is generally classified as an alkali-activated Portland blended cements or alkaliactivated Portland fly ash cement [29] or, sometimes, called
Geopolymer-Portland cement (GeoPC) [21]. Incorporating Portland
cement to the system leads to significant effects on the setting
behaviour and early strength development. The extra heat liberated by exothermic reaction of OPC and water could also provide
a positive effect enhancing its mechanical properties and
microstructures [10].
Another latent factor influencing the properties of geopolymers
is mixing order. It is confirmed that the optimum/proper mixing
order leads to better results, especially for any alkaline-activated
binder [19,30]. For general mixing, alkaline solutions (e.g. NaOH
and Na2SiO3) are firstly prepared and left over-night to confirm a
complete dissolution. Prime materials and those alkaline solutions
are incorporated and mixed together at the same time [3134].
Apart from that, the separate mixing is also studied. Hydroxide soluble (e.g. NaOH) is initially mixed with prime materials, and subsequently added by silicate soluble (e.g. Na2SiO3) [17,25,34,35].
Those two aforementioned procedures, general mixing and separate mixing, provided a satisfactory result as fully dissolved alkaline activators are used. However, the separate mixing process
seemed to get slightly higher strength than that of normal mixing.
As the initial mixing with NaOH solution led to a high rate of leaching, more silica, alumina and other ions from prime materials are
therefore obtained, leading to more degree of geopolymerization
[31,34,36,37]. In addition, pre-dry mixed process (working with
solid activators instead of alkaline solutions) was proposed to be
developed by just mix with water [29]. The attempts to simplify

geopolymers mixing process, by crushing fully-activated final product into powder, and adding water to re-activate the reaction
again as called one-part geopolymers or just adding water
geopolymers, were also studied [3840]. With the pre drymixed process, extra water in the system might be required in
order to sufficiently activate all solid materials, therefore, low
mechanical strength may be obtained by the increase of waterto-solid (w/s) ratio. However, the main aims of the development
of this dry-mixed process should be primarily focused on its
advantages in term of practical work in field applications, and
properties.
The previous work, from our intensive study on self-curing
geopolymers, concluded that the self-cured geopolymers could
be developed with the setting time and early strength being
affected by the OPC replacement and the manufacturing procedures [21]. The main aim of this paper is to study and evaluate
the effects of additional OPC (GeoPC system) and potential manufacturing procedures (pre dry-mixing process) on accumulatedinternal heat liberation and strength development of low calcium
fly ash geopolymer paste as Self-cured geopolymers.

2. Materials
Coal-fired fly ash was supplied by the Drax power station, North Yorkshire, UK.
Its properties comply with BS EN 450-1:2012, fineness category S and loss on ignition category B (similar to low calcium fly ash class F specified by ASTM: C618). OPC
was commercial CEM II/A-L under the brand name of Cemex. The chemical compositions of fly ash and OPC were examined by using the Energy dispersive X-ray Analysis (EDXA) technique and are summarised in Table 1. Alkaline materials used in
this study were sodium hydroxide (NaOH) and sodium silicate (Na2SiO3). The
sodium hydroxide pearl was purchased from the Fisher Scientific, UK and prepared
as a solution with the concentration of 15 M (M). Sodium silicate powder was also
purchased from the Fisher Scientific, UK with a SiO2 to Na2O ratio (Ms Modulus) of
2.0. The sodium silicate solution with 48.20% w/w was used in the experimental
work. To prepare sodium silicate solution, solid powder was weighted in the container and filled with the designated amount of purified water (e.g. 48.20 g of
sodium silicate powder and 51.80 g of purified water).

3. Experimental details
3.1. Mixture designation of OPC, geopolymers and GeoPC pastes
OPC paste was made of cement powder and the purified water
with the water-to- cement ratio (w/c) at its standard consistency of
0.25. Geopolymer paste was manufactured with general mixing
process (process B, see Section 3.2) and composed of fly ash,
sodium hydroxide and sodium silicate. The sodium hydroxide
and sodium silicate solutions were prepared and left overnight
before uses to ensure a thorough solution achieved. The sodium silicate solution-to-sodium hydroxide solution (SS/SH) ratio by mass
was 1.50 and the constant alkaline liquid-to-fly ash (A/FA) ratio by
mass was 0.40. A series of Geopolymer-Portland cement paste
(GeoPC) was made from the designation mass of GP and OPC paste
in general mixing process (process B, see Section 3.2). The mass of
each material used, including alkaline solution and water, was calculated individually from the designed GP and OPC pastes (e.g.
GeoPC30 is composed of 70% GP-paste and 30% OPC-paste). The
mass of each material used in GeoPC system, including alkaline
solution and water, was calculated individually from the designed
GP and OPC pastes). A standard mortar mixer with speed of
140 5 rpm was used to synthesize each mixture in ambient temperature of 1822 C. It is noted that the GeoPC mixtures which
have OPC replacement from GeoPC30 to GeoPC90 were synthesized with 4% added-water in order to obtain the workability in
practical work.

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T. Suwan et al. / Construction and Building Materials 114 (2016) 297306

Table 1
Chemical composition of fly ash and commercial OPC.
Materials

SiO2

Al2O3

FeO

CaO

Na2O

TiO2

MgO

K2O

SO3

Fly ash
OPC

50.97
12.22

27.83
3.85

9.21
2.85

2.62
73.82

1.13

1.15

1.43
0.78

3.73
1.17

1.93
5.30

machine (UTM) in accordance with the British Standard EN 1961 [42]. All samples for compression test were kept in plastic bags
and cured in the temperature controlled chamber at 20 2 C until
reach the testing age of 7, 14 and 28 days for GP and 3, 7, 14 and
28 days for GeoPC mixtures. The X-Ray diffraction (XRD) patterns
were recorded on a Bruker D8 Advance diffractometer fitted with
a Lynxeye XE high-resolution energy dispersive 1-D detector. The
samples were determined by using DIFFRAC.SUITE software. The
scanning range between 5 and 100 2h was covered in a 35-min
period. Scanning Electron microscope (SEM) was used to observe
the microstructures, and the Energy dispersive X-ray Analysis
(SEM-EDXA) technique was used to identify the chemical compositions of the resulted products.
Measurement of internal heat accumulated inside the samples
was carried out by recording temperature using thermocouples
embedded in three different positions in specimens. Type K thermocouples were placed inside the cylindrical samples (100 mm
dia. and 200 mm height; Volume = 1570 cm3) along with the centre of its vertical axis. The probes were aligned vertically with 5 cm.
spacing from base plate to the top. The heat liberation at the position of bottom (ai0), middle (ai1) and top (ai2) was recorded,
together with the temperature inside (ai3) and outside (ai4) the
insulated container. An average temperature of ai0 to ai2 was used
to represent the heat liberated from each specimen. The thermocouples were connected to a National Instrument 16-Channel thermocouple input module (NI 9213), which was run concurrently
with Labview Signal Express programme. A high performance insulator, 10 mm aerogel, was attached to the bottom, side and top
cover of the container in order to protect the heat loss during the
experiment. The physical properties of that aerogel are 0.15 g/
cm3 of density, 0.014 W/m K of thermal conductivity and 1 kJ/
kg K of specific heat capacity. The designation of delay time (the
period of time from the mixing to recording the data) was
15 min to allow placing paste into the mould and setting up the
measurement equipment. The data was recorded every 60 s for a
period of 24 h to observe the heat generated inside specimens
(Fig. 1). It is, however, noted that the measurement is intended
to report in degree Celsius (C) rather than the rate of energy evolution (J/g) because it can be practically compared with that of typical geopolymers curing at the temperature of 4090 C in the
oven. In addition, the temperature in SI unit (Kelvin; K) is also presented along with that degree Celsius for all measurement of the
samples in this test.

3.2. Manufacturing process of geopolymer paste

3.2.1. Separate mixing process (A): fly ash + NaOH solution, then
Na2SiO3 solution
Fly ash was firstly mixed with sodium hydroxide solution for
90 s to form slurry. The mixer was then stopped for 30 s to remove
all the paste adhered to the wall and the bottom to the middle part
of the bowl. During this period, sodium silicate solution was added
into the mixer and mixed together for another 90 s. After wellmixing, the homogenous slurry was placed in the prepared moulds.
3.2.2. General mixing process (B): prime material(s) + mixed NaOH
and Na2SiO3 solutions
Sodium hydroxide and sodium silicate solutions were firstly
prepared and mixed together until becoming homogenous before
uses. To mix GeoPC, the designated amount of OPC powder and
fly ash were initially dry-mixed together for 90 s in the mixer.
Then, the combined solution (plus OPC-water for GeoPC mixture)
was then mixed with prime material(s) for 90 s. The mixer was
then stopped for 30 s to remove all the paste adhered to the wall
and the bottom to the middle part of the bowl. Then, the mixer
was restarted again and run for further 90 s. After well-mixing,
the homogenous slurry was placed in the prepared moulds.
3.2.3. Pre dry-mixing process (C): fly ash + alkaline solids, then add
with water
Fly ash, sodium hydroxide pearl and sodium silicate powder
were firstly dry-mixed together. The specific amount of water
based on the same ratio of water-to-solid as those used in the process A and B was then added in the mixture and mixed together for
90 s. The mixer was then stopped for 30 s to remove all the paste
adhered to the wall and the bottom to the middle part of the bowl.
Then, the mixer was restarted again and run for further 90 s. After
well-mixing, the homogenous slurry was placed in the prepared
moulds. Details of mixture designation and its overall water-tosolid (w/s) ratio are as given in Table 2.
3.3. Analytical techniques
The results of setting time were extendedly studied from previous research by using Vicat apparatus (EN 196-3) [41]. Compressive strength of prismatic samples (40 * 40 * 160 mm3) of all
pastes was determined by using the Instron universal testing
Table 2
Details of mixture designation and the overall water-to-solid ratios.
Mixture

Fly ash (g)

OPC (g)

Na2SiO3 soln (g)

NaOH soln (g)

Na2SiO3 solid (g)

NaOH solid (g)

Purified water (g)

Overall w/s ratios

GeoPC system
OPC
GeoPC90 (B)a
GeoPC70 (B)a
GeoPC50 (B)a
GeoPC30 (B)a
GeoPC10 (B)
GP (B)

45.2
138.5
236.3
338.3
444.6
500.0

500.0
455.0
361.0
264.0
162.0
55.2

10.9
33.2
56.7
81.2
106.7
120.0

7.2
22.2
37.8
54.1
71.1
80.0

126.5
141.5
118.3
94.4
69.2
14.0

0.253
0.298
0.285
0.272
0.259
0.197
0.191

120.0
120.0

80.0
80.0

57.8

30.0

112.2

0.191
0.191
0.191

Manufacturing process of geopolymers

GP (A)
500.0

GP (B)
500.0

GP (C)
500.0

4% added water.

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(a) Thermocouple set up diagram

(b) Insulator and container

(c) Connection module

Fig. 1. Set up of the curing measurement in insulated container.

4. Results and discussion

4.1. Setting time of GeoPC system and GP in different manufacturing
processes
The results of setting time, which was extendedly studied form
previous work [21], are presented in Fig. 2. Rapid solidifying process was observed in all GeoPC pastes when compared to fly ashbased GP. An increase in solidification rate and rapid setting were
influenced by the main contribution of extra precipitation of (C,N)A-S-H from calcium mineral (in OPC) with alkaline activators [10].
Moreover, the significant increase in compressive strength was
also obtained when the amount of OPC replacement increase.
The formation of mixed amorphous geopolymeric gel and (C,N)A-S-H phases were also proved by the XRD analysis (Fig. 7). It is,
alternatively, can be summarised that the amount of OPC inclusion
could control the setting behaviour of GeoPC system. In addition,
for GP in different manufacturing processes, it was found that
the setting time of the mixtures with all those manufacturing processes were not able to be measured in the first 24 h. However, the
process C clearly liberated much more heat and solidified faster
than the processes A and B.
4.2. Measurement of internal heat accumulated inside the samples
4.2.1. Internal heat of GeoPC systems
The internal heat accumulated inside the samples from three
embedded thermocouples of each combination was recorded for
a period of 24 h. It should be noted that the temperature measured

from these three thermocouples were slightly different: the top

position (ai2) had the highest temperature followed by the middle
(ai1) and the bottom (ai0) position, e.g. a set of ai2 = 30.2 C,
ai1 = 29.8 C and ai0 = 29.5 C. The reason is that the nature of heat
moves upward, resulting in higher temperature in the upper section of specimens than that in the lower section.
It can be seen that the OPC had the highest heat accumulation of
73 C, while the maximum temperature of GeoPC90, GeoPC70,
GeoPC50 and GeoPC30 were 42 C, 39 C, 35 C and 29 C respectively. GeoPC10 had low internal heat measured with the maximum temperature of 26 C, similar as the controlled GP that
liberated heat at the peak of 27 C (Fig. 3). The internal heat accumulated inside the samples of GeoPC mixtures may be induced by
the hydration reaction of OPC, which consisted of high potential
energy compound, C3A (Tricalcium aluminate, 866 J/g) and C3S
(Tricalcium silicate, 460 J/g) [43]. The main heat evolution of the
GeoPC mixtures may thus be obtained from the contained OPC,
together with minor heat being promoted by the reaction of OPC
and alkaline solution.
It is interesting that increasing OPC not only increased the temperature of the mixtures but also relatively shifted the peak of temperature toward the 10th h (peak of controlled OPC). The peak of
temperature measurement of GeoPC10, GeoPC30, GeoPC50 and
GeoPC70 were at the 3rd, 5th, 5th and 9th hour respectively, while
GP was in the first 20 min of mixing (Fig. 4). The time of peak temperature was mainly shortened (less than 10th h of the controlled
OPC) by the appropriate proportion with forceful reaction between
calcium mineral (Ca) in OPC and alkaline soluble in GP which led to
a rapid formation of the mixed C-S-H and N-A-S-H [1117]. For the

Fig. 2. Setting time of OPC, GP and GeoPC paste.

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301

Fig. 3. Heat evolution during a 24 h-period of GeoPC.

mixtures with low OPC content (or higher alkaline soluble from
GP), e.g. GeoPC10, most of Ca may react with abundant alkaline
in the mixtures and very little amount of Ca may be left for OPChydration reaction. Less internal heat and low peak time, therefore,
were recorded. It can be concluded that higher GP content (i.e.
higher alkaline soluble) in GeoPC system requires shorter time
for the mixtures to reach their peak temperature.
On the other hand, although GeoPC90 achieved higher temperature than other GeoPC combinations (GeoPC70, 50, 30 and 10), the
peak of temperature were at the 14th h or 4 h longer than OPC. It
seems that the reaction was retarded with this low-alkalinity combination. This behaviour conforms to the results of setting time
(Fig. 2) that GeoPC90, including GeoPC85 and GeoPC5, exhibited
longer setting time than OPC. It is apparent that the peak temperature of GeoPC systems which have OPC content less than approximately 85% (GeoPC85) would occur earlier than that of OPC (10 h),
while the rest of mixtures studied took longer time to reach the
peak. Therefore, the maximum temperature and time to reach
the peak were noticeably influenced by the rate of reaction
between prime constituents, and alkaline activators in the systems.

However, the internal heat accumulated inside the controlled OPC

in this test had similar characteristic as that of the general rate of
heat evolution of pure OPC paste when measured with isothermal
calorimeter (mW/g s or J/g) [44].
4.2.2. Internal heat of geopolymers in different manufacturing
processes
The heat liberation of alkaline activators, sodium hydroxide and
sodium silicate, during aqueous alkaline preparation (of 500 g.
solution) was previously measured in order to calculate its effect
in the process C. It can be seen that the temperature abruptly
increased after adding water to alkaline solids and then steadily
decreased to room temperature in approximately 4 h. It is apparent
that the sodium hydroxide (NaOH) dissolution produced more heat
than sodium silicate and, in addition, a higher concentration of
NaOH generated higher temperature (Fig. 5). The reasons is that
the chemical species of alkaline materials were brought to a lower
energy state when dissolved with water (H2O) to be Na+ and OHfor sodium hydroxide and 2Na2+ + SiO2((OH)2)2 for sodium silicate [45]. In general, the cross-linked SiO4 and AlO4 tetrahedral

Fig. 4. The maximum temperature against the time of each combination.

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of GP are formed when the negative charge on Al3+ is balanced with

positive charge of alkaline ion (Na+), forming N-A-S-H [11]. The
presence of Ca2+ (from OPC) in alkaline solution could lead to the
formation of natural hydration-CSH or C-A-SH or N-A-S-H. The
final reaction products of those systems can be C-S-H (Ca + Si), zeolite/polymers (Si + Al) or C,N-A-S-H (Ca,Na + Al + Si) which mainly
depend on the characteristics of raw starting materials and alkaline
activators. In addition, the presence of C-S-H and C,N-A-S-H can be
observed in XRD analysis (Fig. 7) [1217].
As seen in Fig. 6, the measurement of internal heat accumulated
inside the samples were examined as the rise of temperature of GP
mixtures with three different processes A, B and C. It is apparent
that the processes A and B release very limited heat above room
temperature at the peak of approximately 28 C and 27 C in the
first 20 min of mixing. After that, the temperature reduced steadily
to room temperature at 21 C and 19 C within 24th h. On the other
hand, the process C had much higher temperature than A and B
after mixing with water. Its highest temperature reached around
54 C in the first 20 min and maintained above 40 C for over 8
hours. Then, it cooled down slowly to around 24 C at the 24th h.
The limited heat liberated in the processes A and B was generated
by the chemical reactions among various alkaline ions and fly ash
inside the paste (hydration and geopolymerization). The dissolution of fly ash, in initial stage, underwent with a slight exothermic
reaction which led to less heat emission. On the contrary, the heat
emitted from the process C was almost two times higher than
those of the processes A and B. This means that the dry-mixed
method (process C) could be able to produce heat during the
hydration of alkaline solid, which could realise the development
of a heat based- self cured geopolymer cement. For general case,
the temperature could be kept inside the mixture for longer than
8 hours if this process (C) is used to produce geopolymer mortar
(paste and sand) or concrete (paste and aggregates) due to the heat
accumulated by those aggregates. As far as geopolymers was produced with the huge volume (massive amount) together with good
protection in heat and moisture loss, it could also maintain internal
heat and provide positive curing conditions itself.

4.3. Compressive strength of GeoPC system and GP in different

manufacturing processes
The compressive strength of GeoPC system was examined with
samples at 3, 7, 14 and 28 days (Table 3). It can be seen that the

strength development of GeoPC systems follow that of OPC, i.e.

gradually strengthening with the increase of time from the first
three day to 28 day-aged. The strength increased when the amount
of OPC increased, corresponding to the internal heat liberation,
although the strength of the GeoPC cannot reach to the level of that
OPC. For example, at the 28 day-aged, GeoPC30, GeoPC70 and
GeoPC90 achieved the strength of 35.69, 39.11 and 51.32 MPa
respectively, while the controlled OPC achieved that of 70.06 MPa.
In GeoPC systems, soluble hydroxide strongly dissolves the
minerals from source of materials, indicated by the forming character of the mixtures, while soluble silicate, which is normally used
as another source of silica, improves the binding activity or
geopolymerization of geopolymers [31,36,37]. The strength of
GeoPC in ambient temperature resulted from participation and formation of calcium silicate hydrate, C-S-H (main hydration product
of Portland cement) and C-S-H co-existed with N-A-S-H gel, which
is responsible for the fast setting and early strength development
[1117,28,32]. Moreover, the internal heat which was generated
inside the specimens would further enhance the formation of
geopolymeric gel, improving its mechanical strength [46]. Nevertheless, overall lower strength of GeoPC mixtures was obtained
in an ambient-curing temperature because those mixtures may
still have less crystallinity as well as poor reactivity than that of
normal OPC C-S-H phases as indicated by XRD analysis (Fig. 7)
[4749].
All of GP pastes could not set in the first 3 days, therefore, the
first compression test was carried out at 7 day-age, followed by
14 and 28 day-aged (Table 3). The structural formation of GP was
very slow in the ambient curing condition, therefore, a prolonged
period of time was required for the paste solidification (over 3
5 days). Uncompleted reaction of geopolymeric gelation also
affected the early strength of geopolymer paste.
Process A resulted in the highest mechanical strength due to
more dissolution rate (from initial mix of hydroxide solution)
and more binding activity (from later added of silicate solution)
[25,35]. Process B, the most widely used method, provided a better
uniformity but the structural formation appeared to be inert and
led to slightly lower compressive strength than process A
[12,19,30]. Process C solidified much more intensively than those
occurred in the process A or B by the strong hydration among starting materials, alkaline solids and water in the system. Without
moisture protection, the heat generated from process C can lead
to a rapid loss of moisture. Micro cavities, which were left in the
structure, could give rise to an adverse effect in mechanical
strength. Although the obtained heat provided good curing conditions as similar as happened in mild-to-medium temperature curing [50,51], incomplete dissolution could lead to low reaction rate.
The compressive strength of process C was, thus, lower than that of
process A and B. In contrast, it can be summarised that the process
C could achieve the quickest setting characters with intensive heat
liberation, while the processes A and B took longer time to set. Process A gained the highest compressive strength followed by process B and C in all testing ages. Overall, the extra heat obtained
from OPC hydration (GeoPC system) and strong exothermic reaction from alkaline dissolution (Dry-mixing process) could provide
a positive effect for curing purpose of that geopolymers which give
rise in its mechanical strength.
4.4. Morphology analysis and microstructures of GeoPC systems

Fig. 5. Heat evolution of alkaline solution preparation.

The XRD patterns GeoPC mixtures are as presented in Fig. 7. At

the testing age of 28 days, GP consists mainly of semi-crystalline
and amorphous phases which are indicated by the sharp peak
(quartz and mullite) and a broad hump in the region of 2035
2h respectively. The peaks which corresponding to C-S-H, calcite
and nepheline increased when additional OPC increase from 10%

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303

Fig. 6. Heat evolution during a 24 h-period of pure GP.

Fig. 7. X-ray diffraction patterns of GeoPC system at 28 days age.

Table 3
Compressive strength of GeoPC system and GP in different manufacturing processes.
Mixture

CaO/SiO2a

GeoPC system
OPC

GeoPC90
4.40
GeoPC80
3.14
GeoPC70
2.31
GeoPC50
1.26
GeoPC30
0.63
GeoPC20
0.40
GeoPC10
0.21
GP (B)
0.05

SiO2/Al2O3a

4.63
4.27
4.06
3.82
3.69
3.64
3.61
3.58

Manufacturing process of geopolymer

GP (A)
0.05
3.58
GP (B)
0.05
3.58
GP (C)
0.05
3.58
a

Oxide molar ratio.

Compressive strength (MPa)

3 days

7 days

14 days

28 days

48.8
30.2
18.2
21.9
14.1
13.8
11.1
5.7

59.5
36.2
24.6
23.4
19.0
15.4
14.8
5.8
2.9

63.1
44.6
33.8
34.1
33.9
32.4
29.4
18.2
6.9

70.1
51.3
39.2
39.1
36.5
35.7
35.7
23.5
13.2

4.8
2.9
2.4

7.2
6.9
6.0

13.6
13.2
11.3

(GeoPC10) to 90% (GeoPC90) while the intensity of quartz and mullite continuously decreased. More crystalline phases of portlandite,
ettringite and calcite are clearly appeared and increased with high
percentage of OPC from the GeoPC70 to the fully hydrated OPC.
The XRD analysis of 3 days age was also studied in order to
compare its changes in later stage. It, however, exhibited very similar characteristic as 28 days which could lead to good early
strength of the final products. The appearance of N-A-S-H compound was found according to the high alkalinity of Nacontaining solutions. The main composition of fly ash (silica and
alumina) could form C-A-S-H phase with the available calcium
mineral. The findings can be drawn that the GeoPC system has a
different reaction pathways depending on Na+ and OH- concentration and the composition of prime materials, forming the coexistence of amorphous C-S-H/semi-crystalline phases (XRD peak
and hump) or (C,N)-A-S-H (main reaction product of fly ash activation; 0.8CaO
0.2Na2O
Al2O3
3.0SiO2
6H2O) interfered in hydration
product of GeoPC matrices [11]. The coexistence formations of

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T. Suwan et al. / Construction and Building Materials 114 (2016) 297306

Table 4
Some of selected SEM images of GeoPC system at 28 days age.
Mixture

SEM images

SEM-EDX spectrums

(a) OPC

(b) GeoPC90

Microstructures of GeoPC50 and GeoPC10 were less homogeneous

than that of GeoPC90. Nevertheless, their structures looked denser
and more compact than that of the GP. Gel pores of spherical particles, loose matrices and some of remaining unreacted fly ash particles could be one of major factors of poor mechanical
performances for low-OPC content mixtures (GeoPC10 or even
GP) curing in ambient conditions. It can be seen in EDX spectrums
that high percentage of OPC inclusion (e.g. GeoPC90) had a considerable intensity in Ca with a majority of C-(A)-S-H gel, while low
percentage of OPC inclusion (e.g. GeoPC10) had a substantial
amount of Si and Al of (C,N)-A-S-H or geopolymeric gel.

4.5. Effect of oxide molar ratio on setting time and compressive

strength of GeoPC system
CaO-to-SiO2 (C/S) and SiO2-to-Al2O3 (Si/Al) ratio were plotted
against setting time and 28-day compressive strength (Fig. 8).
The higher C/S ratio generally provides more C-S-H and C,N-A-SH formation, while higher Si/Al ratio offers more available silica
and alumina which resulted in an increase in the strength of
GeoPC.
The similar results of good strength from C-S-H forming were
also reported with the metakaolin-based geopolymers and GBFSas a source of calcium additive-geopolymers [12,52,53]. The setting
time had similar characteristic as open-up parabolic curve in both
C/S and Si/Al plotting. As aforementioned, the Ca from OPC
together with available Si and Al mainly provided an extra participation in the systems [10], thus, a proper setting time could be
achieved with an appropriate combination of those GeoPC mixtures. The self-cured optimum combinations in ambient temperature may be able to achieve the compressive strength with the C/S
ratio of 0.210.40 and Si/Al ratio of 3.613.64 (GeoPC10-GeoPC20),
providing the strength approximately 2335 MPa at 28 days age.
The benefits are not only in term of mechanical properties but also
in both economic and environmental aspects from replacing OPC
with industrial waste, fly ash.

(c) GeoPC50

(d) GeoPC10

(e) GP

both crystalline and amorphous were found in the GeoPC mixtures,

illustrating the mix of geopolymeric gel and hydrated OPC product
in the single binder.
Table 4 reveals some SEM images and EDX spectrums of GeoPC
mixtures varied from GeoPC90 to GeoPC10 at the age of 28 days. It
is apparent that a micrograph of GeoPC90 is very similar to those of
controlled OPC. High OPC content resulted in compact and firm
structure, leading to an increase in mechanical strength.

5. Conclusions
The internal heat liberation and the strength development of
the developed self-curing geopolymers have been studied with
the addition of OPC and their processing procedures in ambient
curing temperature. Some specific conclusions are summarised as
follows;

Fig. 8. CaO/SiO2 ratio (Left) and SiO2/Al2O3 ratio (Right) vs. 28d-strength and setting time.

T. Suwan et al. / Construction and Building Materials 114 (2016) 297306

(1) The internal heat accumulated inside the GeoPC samples

was mainly induced by the OPC hydration which could promote more appropriate curing condition. The optimum combination, which could achieve in term of mechanical
properties, economic and environmental aspects, is in the
range of GeoPC10 to GeoPC20. Whilst, pre dry-mixing process (C), it clearly generated much more heat and solidification characteristic which could provide a positive curing
condition to the fly ash-based geopolymers.
(2) The addition of OPC in the GP systems (GeoPC) hence
directly enhanced the setting time and early strength development. An extra participation of C-S-H and C,N-A-S-H from
available Ca (from OPC) in the systems resulted in the
microstructure improvement, indicating by dense and compact matrix.
(3) The formation of geopolymers in all manufacturing processes underwent with very slow rate in ambient curing
temperature in their early age. Separate mixing process (A)
achieved higher mechanical strength than process B due to
more dissolution rate and more binding activity of subsequent mixing order of alkaline solutions. As dry-mixing process (C) required extra water in the system, lack of
reasonable dissolution of solid materials could lead to poor
microstructure, resulting in the lowest strength.
(4) Overall, the enhancement in mechanical properties of suitable GeoPC mixtures, together with alternative heat supplies
from GeoPC combinations and dry-mixed process (C) could
provide sufficient internal heat for the curing regime of GP.
The experiment of this self-cured geopolymers has been
established forwarding the potential development for onsite
engineering applications.

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