Heliyon 5 (2019) e02255

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Heliyon
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Mechanical and microstructural properties of high calcium fly ash one-part

geopolymer cement made with granular activator
Bashar S. Mohammed a, *, Sani Haruna a, b, M.M.A. Wahab a, M.S. Liew a, Abdulrahman Haruna a
a
Department of Civil and Environmental Engineering, Universiti Teknologi Petronas, Seri Iskandar, Perak, Malaysia
b
Department of Civil Engineering, Bayero University, Kano, Nigeria

A R T I C L E I N F O A B S T R A C T

Keywords: In this present experimental study, geopolymer cement is developed using high calcium fly ash and used in the
Civil engineering production of one-part alkali-activated binders. At 8–16 percent of the total precursor materials, the HCFA was
Structural engineering activated with anhydrous sodium metasilicate powder and cured in ambient condition. Five mixtures of one-part
Materials application
geopolymer paste were intended at a steady w/b proportion. Density, flowability, setting time, compressive
Materials characterization
Materials physics
strength, splitting tensile strength and molar ratio impact were envisaged. It was observed that the setting time of
One-part geopolymer cement the designed one-part geopolymer paste decreases with higher activator content. The experimental findings
Setting time showed that the resistance of one-part geopolymer cement paste increases with comparatively greater activator
High calcium fly ash content. However, raising the granular activator beyond 12 percent by fly ash weight decreases the strength and
Granular activator compressive strength workability of the established one-part geopolymer cement. The optimum mix by weight of the fly ash was
discovered to be 12 percent (i.e. 6 percent Na2O). At 28 days of curing, one-part alkali-activated paste recorded
the greatest compressive strength of almost 50 MPa. The density of the one-part geopolymer paste is nearly the
same regardless of the mixes. Microstructural assessment by FESEM, FTIR and XRD has shown that the established
geopolymer paste includes quartz, pyrrhotite, aluminosilicate sodium and hydrate gels of calcium aluminosilicate.
Based on the experimental information acquired, it can be deduced that the strength growth of one-part geo-
polymer cement is similar to that of Portland cement.

1. Introduction tetrahedral structure, offering extended chains that can be cross-linked

based on the activator used [2, 5]. Geopolymer binders are
The evolution of low-carbon binders is realized as one of the possible environmentally-friendly material used as a substitute for ordinary
solutions to reduce the environmental impact associated with Portland Portland cement (OPC) binder. Geopolymer's polymerization mechanism
cement binders [1, 2, 3]. Aluminosilicates materials react very slowly is an intensely rapid chemical reaction on silica-alumina minerals in an
with water but react under hydrolysis and condensation reactions in an alkaline environment that yields a 3-dimensional polymeric sequence
alkaline medium to form inorganic polymers capable of resisting loads. and ring structure consisting of Si–O–Al–O bonds. Geopolymer concrete
The binding property resulting from the amorphous aluminosilicate gels production does not require the use of any OPC, but the binder is pro-
and the reactivity of the source materials is strongly affected by the duced by the reaction of an aluminosilicate ingredient with strong
structure of the aluminosilicates, and various research has been alkaline liquids. It is evident that, in addition to depleting existing re-
committed to this problem [4]. Depending on the calcium composition of sources in Portland Cement production, an enormous amount of carbon
the source materials, the synthesis of alumino-silicates with alkalis can be dioxide has been emitted into the surrounding atmosphere. A substitute
categorized into two forms: low and high calcium aluminosilicates. green material is required to mitigate these effects. It is therefore
Aluminosilicates materials containing low metal content result in the essential to use substitute ingredients for the development of environ-
formation of a metallic element aluminosilicate hydrate (N-A-S-H) mentally favorable concrete [6]. Collectively, cement gel geopolymer
product, whereas high metal content causes the formation of calcium binds aggregates and unreacted material to yield geopolymer concrete
aluminosilicate hydrate (C-A-S-H) almost like Portland cement C–S–H. [7, 8]. It is worth mentioning that the production of geopolymer cement
However, the former contains essential replacement in connecting releases 80 to 90 percent less CO2 (greenhouse effect gas) compared to

* Corresponding author.
E-mail address: [email protected] (B.S. Mohammed).

https://doi.org/10.1016/j.heliyon.2019.e02255
Received 7 February 2019; Received in revised form 1 April 2019; Accepted 5 August 2019
2405-8440/© 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
B.S. Mohammed et al. Heliyon 5 (2019) e02255

the production of Portland cement [9]. geopolymer binders. Therefore, this research may be of significant in-
Notwithstanding the reality that the geopolymer system has been terest in the production of one-part geopolymers based on fly ash. In
developed since the 1970s [7,10,11] and has numerous beneficial attri- addition, there are limited studies of the fresh, mechanical and micro-
butes, yet it is not widely used in concrete compared to ordinary Portland structural properties of high calcium fly ash one-part geopolymer binders
cement. Due to its restrictions in terms of slow setting, high porosity, synthesized using anhydrous sodium metasilicate powder. In this study,
elevated temperature curing and sluggish strength growth, comprehen- one-part geopolymer pastes are prepared and cured at ambient temper-
sive use of low calcium fly-ash geopolymers is hampered. Curing geo- ature. Flowability, setting time, strength and effect of one-part geo-
polymer concrete at ambient temperature led to slow growth of strength polymer paste molar ratios at different activator dosage were examined
at the initial stage while curing at relatively high temperatures resulted in to determine the fundamental properties of one-part geopolymer paste
a better development of strength [12]. Haruna et al. [13], reported that cured in the ambient. The optimum mixture of one-part geopolymer
outdoor cured geopolymer concrete has developed reasonable strength, cement achieved could be a substitute for Portland cement and further
but high molarity degrades the strength properties under the same con- use by adding water similar to OPC to produce geopolymer concrete and
dition. Improving the stated properties is vital for maximizing the use of mortar. The idea of using C-class fly ash in geopolymer manufacturing
geopolymers in construction as a substitute for the energy-demanding would be helpful for this by-product's long-term applications.
OPC binder. Efforts have been made to produce one-part mix geo-
polymer [5, 14, 15], their findings focused on producing commercially 2. Materials and methods
and environmentally suitable one-part binders.
One-part geopolymer binders are known as alkaline cement, they are 2.1. Materials
a new geopolymer production approach that has been recently developed
with the aim of reducing complications in dealing with silicate solution High calcium fly ash was used as the primary binder in this investi-
activated geopolymers, produced by mixing aluminosilicate source ma- gation. The chemical components of the high calcium fly ash used were
terials with solid activators [14, 16]. Unlike normal geopolymer binders detected by X-Ray fluorescence (XRF) and presented in Table 1. The fly
where solutions are used to trigger the activation process, the activator ash was acquired from the Manjung Power Plant in Perak, Malaysia as a
remains in dry powdered form in the one-part binder and the reaction source of aluminosilicate materials for the production of one-part geo-
starts as water is poured into the binder resembling ordinary Portland polymer binder. Field emission scanning electron microscope (FESEM)
cement [14, 17, 18]. This method helps to avoid using corrosive and examined the morphology of fly ash and shown by the micrograph in
viscous solutions for large-scale geopolymer concrete production and Fig. 1. Based on the FESEM micrograph, all fly ash particles appeared to
encourages the commercial suitability of geopolymer binder, this concept be spherical in different sizes, allowing it to mix freely in mixtures. It is
is called just adding water. There are many attempts to synthesize well recognized that the percentage of CaO used for HCFA was greater
aluminosilicate materials together with alkaline solutions at higher than 10 percent. Additionally, the total sum of SiO2, Al2O3 and Fe2O3 is
temperatures to produce one-part binders [14, 15, 19, 20, 21, 22]. As less than 70 percent, hence the fly ash in this study meets the requirement
reported by Provis [18] the activating agent in a one-part geopolymer of C-class fly ash as per ASTM 618–10 [30].
binder can be any material that supplies alkali cations, amplifies the pH Granular sodium metasilicate anhydrous (50 percent Na2O, 46
level of the combination, and accelerates the dispersal of silica and percent SiO2 and 4 percent H2O) and modulus ratio of 0.92 was used as a
alumina into the system. Different types of activators were used in the solid activator to activate fly ash. The use of granular alkaline activators
formation of one-part geopolymers consisting of sodium aluminate, so- in geopolymer systems is easier and less time consuming than the
dium silicate, sodium sulfate, sodium carbonate, sodium silicate penta- frequently used alkaline solutions as there is no need to prepare NaOH
hydrate and many more. Kolousek et al. [19] developed one-part solution before mixing. The granular activator was used by weight of the
geopolymer systems by burning kaolinite with powdered hydroxides. primary ingredients as 8 percent-16 percent. Portray Sdn Bhd located in
After 7 days of curing, which was inferior to conventional geopolymer Selangor, Malaysia, provided the granular sodium metasilicate anhy-
systems, the strength gain was only 1 MPa. Other interesting findings drous used in this work.
[16] also used red mud and silica fume to produce one-part geopolymer
and realized a compressive strength of about 32 MPa at 28 days of 2.2. Mixing procedure and test methods
ambient curing which proves to be a vital improvement to the findings
reported by [19]. In addition, one part of the geopolymer binder for One-part geopolymer paste was made in accordance with the stan-
ambient healing was produced by [23, 24] using fly ash and slag as the dard practice of ASTM C305-14 [31]. Five different levels of geopolymer
primary ingredients and acting with sodium silicate and sodium hy- pastes were produced by mixing fly ash with anhydrous sodium meta-
droxide powder. The binder produced with 100 percent slag gained a silicate at five different levels as shown in Table 2. HCFA and granular
compressive strength of about 50 MPa, while that of 100 percent fly ash anhydrous sodium metasilicate were thoroughly mixed in a small Hobart
yields 9.45 MPa strength after 28 days of healing at room temperature.
One-part geopolymers are reported to have low green gas emissions
Table 1
compared to conventional geopolymers as the polymerization process
Fly ash chemical composition.
constitutes a small portion of the matrix [25, 26, 27]. They also revealed
that the one-part geopolymers binding phases are similar to the two-part Chemical oxide Percentages (%)

geopolymers. Alkali activation process includes concentrated fluid ar- Al2O3 14.9
rangements that are harmful, sticky, making it difficult to deal with and SiO2 37.3
Fe2O3 16.5
not easy to use. Therefore, the improvement of alleged one-part geo-
CaO 17.1
polymers or "simply include water" geopolymers may have more prom- MgO 3.72
inent potential than traditional two-part geopolymers, particularly in P2O5 2.59
cast-in-situ applications [26, 27]. It is interesting to note that one-part SO3 2.56
geopolymers have proved cost-effective than the two-part counterpart Na2O 1.74
K2O 1.66
geopolymers [28], but it is still costly compared to the one-part geo- TiO2 1.07
polymers [28]. Others 0.69
Recent studies have used anhydrous sodium metasilicate powder to LOI 0.17
synthesize one-part geopolymers from fly ash blended slag [14, 20, 29]. Blaine fineness (m2/Kg) 385
Specific gravity 2.35
High calcium fly ash has rarely been used in the production of one-part

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evaluated using ASTM C109/109M [36] for 3, 7 and 28 days. At each

testing age, three sets of the specimens were used to conduct the
compressive strength test. Similarly, the tensile strength of the geo-
polymer paste was split in accordance with BSEN12390-6 [37].

3. Results and discussion

3.1. Flow characteristics

The flowability of the mixtures decreases with an increase in sodium

oxide content in the paste. This is attributed to the Na2O's higher mo-
lecular mass, which immediately binds the fly ash particles as water was
added to the mix. Basically, the flow resistance of the mix worsened at a
higher percentage of Na2O and therefore reduces the flowability as
shown in Fig. 2(a) and subsequently result in highly viscous mixtures
Fig. 1. FESEM micrograph of high calcium fly ash. [24, 38]. The behavior of the one-part geopolymer paste is found to be
thixotropic in nature as shown in Fig. 2(b) When stirred, the gels become
mixer for about 2 min. Potable tap water was gently poured into the dry more workable and less viscous. It is predicted that the powder-activated
mix and mixed for 3 more minutes until it becomes homogeneous and geopolymer has a moderate rate of alkali release into the binder resulting
consistent. The details of the proportions of the mixture were presented in a steady initial reaction, making the paste flowable for a relatively
in Table 2. Mixing was performed at approximately 25
C in a laboratory. longer time [17]. It is worth noting that for one-part geopolymer pastes,
Immediately after mixing, the fresh geopolymer paste was poured into increasing the quantity of the solid activator leads to a decrease in
50/50/50 mm cubic moulds. After 24 h, the specimens were dislodged flowability as shown in Fig. 3, this finding is in line with the work of [14].
from the molds and cured at ambient temperature (25–27
C). The Nevertheless, improving water content enhanced workability but leads to
samples and moulds were left in the laboratory until the 3, 7, and 28 day a decline in compressive strength. The results shown in Fig. 3 show that
test period. The percentage of granular sodium metasilicate anhydrous sodium metasilicate content in the mixes relatively influenced the
used is the parameter considered in this investigation. flowability of one-part geopolymer paste. The flowability of the devel-
The flowability of the fresh one-part geopolymer paste was measured oped pastes was measured in terms of relative slump values, a relative
using a flow table. The flow table test was used to evaluate the fresh slump value of 6.13 was recorded for N1 samples. The relative slump
properties of the one-part geopolymer paste as it is easy to perform and values were obtained in a decreasing pattern for N1 by 2.5 percent, 4.9
uses simple handling equipment. The flow table consists of a complete percent, 6.7 percent, and 7.3 percent for N2, N3, N4, and N5 respectively.
cast immovable iron frame and a circular static table top. Other flow table It is interesting to note that the flowability of N4 and N5 remains almost
information is mounting and lubrication as mentioned in ASTM C230/ constant at high activator content. It should be noted that the relative
C230M-14 [32]. Mini slump test was used to determine paste flowability. slump values depend on the mini-slump test without any compaction or
Each mixture was twice tried. The mini slump test procedure was per- external pressure. Subsequently, there was no problem with the casting
formed in accordance with [14, 33, 34]. The conical mold was used to and compaction of the samples and these results are in good agreement
cast the one-part geopolymer paste while the caliper was used to measure with those published by [14, 36, 39].
the mortar diameter. The fresh one-part geopolymer pastes were
designed to weigh the binder at 8 percent, 10 percent, 12 percent, 14 3.2. Setting time of one-part geopolymer paste
percent and 16 percent of granular anhydrous sodium metasilicate.
Setting time for one-part geopolymer pastes was performed as per ASTM With the help of the Vicat apparatus, the setting time behavior of one-
C807 [35] to determine the influence of sodium metasilicate activator part geopolymer paste was performed. For each test, as suggested by
content on one-part geopolymer pastes. Vicat apparatus was used to [40], two sets of readings were recorded for initial and final setting time,
conduct the one-part geopolymer cement setting time behaviour. and the average was reported. The initial setting time was recorded as the
One-part geopolymer pastes were placed in an exceedingly conic Vicat moment from which water is added to the dry mixture at which time the
equipment mould. Vicat needle infiltration of approximately 1 mm in needle resists penetration from the bottom plate to a depth of 3 mm–5
diameter on the geopolymer paste was recorded at orderly time intervals mm, while the final setting time is recorded as the time from which water
for initial setting. The initial stiffening time of the one-part geopolymer is is added to the dry mixture at which time the needle does not affect the
recorded as the period during which the needle does not penetrate 3 surface of the one-part geopolymer paste. The results shown in Fig. 4
mm–5 mm from the bottom of the conical mould. The final setting time of show that sodium metasilicate content in the mix considerably influ-
the paste was also observed once the needle failed to make any impres- enced the setting time of one-part geopolymer paste. One-part geo-
sion on the surface of the paste. The test was performed at 25–27
C polymer pastes quickly hardened, which is associated with the heat
laboratory temperature. produced from the dissolution of anhydrous sodium metasilicate result-
The cubes specimens are weighed at the test date to obtain their ing in rapid geopolymerization on the surfaces of fly ash and sodium
respective densities. The compressive strength of the specimens was silicate grains. It is noteworthy that the mixing time significantly affects
the setting time of the one-part geopolymer paste, the higher the mixing
time and the faster the setting time. The initial setting time examines the
Table 2
mixing time of 3 and 5 min is found to be almost the same while the final
Mix proportion of one-part geopolymer paste.
setting time changes slightly. In the process of releasing alkali and silica
Mix. No. Fly ash Na2SiO3 water w/s ratio ions from the granular sodium metasilicate activator, one-part geo-
Anhydrous (%) [g] polymers made with higher activator content (N3, N4 & N5) tend to set
N1 1 0.08 225 0.25 rapidly than N1 and N2, which is attributed to an increase in tempera-
N2 1 0.10 225 0.25 ture. The optimum mixing time for one-part geopolymer paste is found to
N3 1 0.12 225 0.25 be 5 min at normal mixing speed based on the data obtained from this
N4 1 0.14 225 0.25 study. The initial setting time varied from 45 to 25 min as shown in Fig. 4,
N5 1 0.16 225 0.25
and the final setting time was recorded from 125 to 55 min. It was also

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B.S. Mohammed et al. Heliyon 5 (2019) e02255

Fig. 2. (a). Flowability property of the one-part geopolymer paste before stirred, (b) one-part geopolymer paste after stirred.

reaction process, which later evaporated from the paste surface, the
decrease may also be associated with the water loss. Accordingly, it can
be deduced from these findings that at the initial stages the reaction
process is faster. These findings are quite the opposite of [44]. Fig. 5
shows the densities of the different mixes and it was observed that the
density of the one-part geopolymer pastes is almost the same. This shows
that the amount of solid activator present in the mixtures has a negligible
or small influence in the mixtures.

3.4. Compressive strength of one-part geopolymer pastes

The compressive strength growth of various combinations of geo-

polymer paste was evaluated at 3–28 days of ambient healing. Fig. 6
Fig. 3. Relative slump the one-part geopolymer pastes. represents the compressive strength profile of user-friendly geopolymer
pastes at different activator content. The results shown in Fig. 6 are the
mean result of three specimens tested during the testing period. The
observed that the setting time of the designed one-part geopolymer paste
compressive strength of nearly 50 MPa was obtained for N3 geopolymer
decreases for both final and initial setting time at higher concentration of
paste which was the highest strength and occurred at 12 percent of the
sodium metasilicate activator. This is associated with the number of
solid activator (6.1 percent Na2O). It is pointed out that the strength
reactive elements in the content of the source materials that ultimately
gained at lower activator content is minimal leading to lower strength
led to the development of N-A-S-H and C-A-S-H gels. It is noteworthy that
development, this is due to insufficient alkali that will trigger the system's
in the NaOH solution medium, silica, alumina and other minerals are
geopolymerization process. However, increasing the activator content
leached from fly ash [41], while in the system with high calcium content
from 8 to 10 percent increases the strength by 24.6 percent. The high
in the precursor material, silica and alumina with high CaO content lead
early strength in the geopolymeric system may be associated with the Si/
to C-A-S-H formation which coexisted with N-A-S-H at the initial stage
Al ratio. The presence of comparatively lower Si constituents in N1 to N5
which later contributed to the rapid reaction process [42, 43].
geopolymer pastes with a Si/Al ratio of 2.75–3.0 as shown in Table 3
makes it viable that additional Al species were present at the initial stages
3.3. Hardened density for contraction in the ingredients. It is noteworthy that the higher Si/Al
ratio reduced the quantity of silicon in the geopolymer paste and the rate
The hardened density of one-part geopolymer paste was evaluated by of geopolymerization reaction in an excessively fly ash-based one-part
weighing the mass and dimensions of the cube specimens per mix, geopolymer. This could be due to the development of fewer reactive
initially two cubes per mix were measured, and if the difference in silicon dioxide oligomers instead of small reactive species at high SiO2/
densities between the two is more than 5 percent, then a third cube was Al2O3 ratios [5]. Subsequently, the aluminum element is likely to
used. The investigation revealed that hardened densities of the devel- dissolve faster compared to the silicon element and thus allows a faster
oped one-part geopolymer pastes decrease slightly with age attributable condensation rate between silicate and aluminum elements than the
to a relatively low geopolymerization reaction at a later age. During the condensation between silicate elements. It is worth mentioning that N3's

Fig. 4. Setting time of one-part geopolymer pastes. Fig. 5. Densities of one-part geopolymer pastes.

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B.S. Mohammed et al. Heliyon 5 (2019) e02255

compressive strength increased significantly by nearly three times that of

N1, which is attributed to sufficient Na2O in the one-part geopolymer
paste. Further increase in activator content (Na2SiO3) to 14 and 16
percent, which is 7 percent and 8 percent Na2O content tends to decrease
compressive strength by 12 percent and 14.5 percent respectively. This
can be attributed to heat energy released at the higher activator during
the geopolymerization process, resulting in the formation of minor cracks
on the surface of the specimens. These cracks are associated with heat
evolving during the process of reaction. In addition, the presence of
excess sodium oxide in the mix is suspected to slow down the develop-
ment of strength slightly.
In addition, the compressive strength of one-part geopolymer paste
gradually decreases with higher activator content. It is therefore deduced
that the improvement of the water content of the one-part geopolymer Fig. 7. Splitting tensile strength of one-part geopolymer pastes.
with the remaining uninterrupted variables leads to a significant increase
in flowability and subsequent decreases in the compressive strength of geopolymer's rheology and strength development was governed by the
the one-part geopolymer mix [14, 29]. alkali content. The reaction occurs immediately as soon as water reacts
with the solid precursors, the solid activator begins to dissolve in the mix,
3.5. Split tensile strength of the pastes thereby generating an exothermic reaction process which results in
elevating the temperature of the one-part geopolymer paste. The disso-
Fig. 7 shows the split tensile result of the one-part geopolymer paste lution of the granular activator dissociates the alkali and silica ions
for all design mixes considered. The test is conducted in accordance with thereby generating a heat of geopolymerization that accelerates the
BS EN 12390–6 [37]. To follow the same trend with compressive geopolymerization process on the source materials and the granular
strength, the split tensile strength of one-part geopolymer paste cured at anhydrous sodium metasilicate activator. The molar ratios of all mixes of
ambient temperature was obtained. At 4 percent Na2O that is N1, the one-part geopolymer pastes were calculated and presented in Table 3.
tensile strength of nearly 1.5 MPa is realized, but adding more Na2O The Silica-alumina ratio of the developed geopolymer paste ranges from
content in fly ash by 5 percent (N2) and 6 percent (N3) tends to increase 2.75-3.0 with a ratio of 2.87 appeared to be the best in this work.
strength by 26 percent and 66 percent respectively. It is noteworthy to Alumina emanates from the source materials of fly ash, while silica
explain that the split tensile strength of the developed one-part geo- evolves from fly ash and anhydrous sodium metasilicate. The higher Si/
polymer pastes increases with an increase in anhydrous sodium meta- Al values result from a high percentage of anhydrous sodium metasilicate
silicate and subsequently decreases at 14 percent and 16 percent in the blended paste. The formation of multiple polymeric silicate fam-
equivalent to (7 percent and 8 percent Na2O) respectively. As shown in ilies at higher sodium metasilicate is suspected to have slowed down the
Fig. 7, it is noteworthy that the split tensile strength of the one-part reaction process and consequently affected the strength of the geo-
geopolymer paste at 14 percent and 16 percent activator decreases polymer pastes. Accordingly, the Silica-alumina ratio can not be
slightly by 2 percent and significantly decreases by 22 percent compared increased infinitely as thoroughly deliberated for conventional geo-
to the N3 mix. This is attributed to the geopolymer's fast setting behavior polymer mixtures [5, 45, 46] as such patterns were adopted in this study.
whereby the Na2O content did not participate fully in the reaction pro- It is observed that the strength of the one-part geopolymer paste in-
cess. As such, some of the unreacted sodium oxides react with sur- creases rapidly with a decrease in H2O/Na2O ratios with the highest ratio
rounding CO2 to form sodium bicarbonate on the surface of the having the lowest strength. The compressive strength of the one-part
specimens and subsequently contribute to lower strength growth. The geopolymer significantly improved as the percentage of H2O/Na2O in
heat produced when water was added to the geopolymer cement is due to the mixes decreases by 14.8 percent, 25.6 percent, 34.1 percent, and 40.8
the dissolution of the solid sodium metasilicate which resulted in sig- percent for N2, N3, N4, and N5 respectively. The Na/Al ratio is found to
nificant water loss resulting in some minor crack formation on the surface be increasingly high at relatively higher activator content, resulting in
of the specimens. The cracks are associated with the stability of the excess concentration of Naþ in paste systems. The excess sodium oxide in
geopolymer paste. the mix combines with water to produce more hydroxyl ions in the
geopolymer paste which later reacts with calcium to form calcium hy-
droxide and thus decreases its strength [47]. Similarly, the surplus
3.6. Effect molar ratios on strength
amount of Na þ ions in the mix reacts with CO2 in the surrounding area
to form a white precipitate on the surface of the specimens, which
One of the notable parameters in making one-part alkali activated
significantly contributed to the lower strength evolution at higher
paste is the alkali activator content of the geopolymer paste as the
H2O/Na2O proportions, particularly at ambient temperature. This is due
to the fact that one-part geopolymer paste contains higher soluble con-
centrations of alkaline ions than Portland cement as such when it comes
into contact with water or due to higher humidity efflorescence, and this
study is in agreement with that of [48].

Table 3
Molar ratios of the one-part geopolymer pastes.
Mix ID SiO2 Al2O3 Na2O H2O Si/Al Na/Al H2O/Na2O

N1 368.82 134.1 52.38 227.16 2.75 0.39 4.34

N2 377.1 134.1 61.56 227.7 2.81 0.46 3.70
N3 385.38 134.1 70.74 228.24 2.87 0.53 3.23
N4 393.66 134.1 79.92 228.78 2.94 0.60 2.86
N5 401.94 134.1 89.1 229.32 3.00 0.66 2.57
Fig. 6. Compressive strength of one-part geopolymer paste.

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B.S. Mohammed et al. Heliyon 5 (2019) e02255

Fig. 8. X-ray diffraction (XRD) pattern of the fly ash.

3.7. Microstructural properties hydrate. The sharp characteristic quartz peak is associated with the
development of alkali-silicate glasses with the partial amorphization of
3.7.1. X-ray diffractometer (XRD) investigation the phases [49]. The crystalline phases (quartz and hematite) observed in
The XRD patterns of high calcium fly ash (HCFA) and one-part geo- the fly ash remained almost unchanged after synthesis. X-ray diffraction
polymer paste were obtained by Bruker's X-ray diffraction instrument characteristic for one-part geopolymer mixtures revealed the formation
and presented in Figs. 8 and 9. HCFA's primary mineral ingredients were of different reaction products that differed depending on the percentage
quartz, magnetite, and lime. HCFA's XRD pattern in Fig. 8 shows a broad of activator material used. It is interesting to note that the presence of
peak indicating that most of the HCFA structure is amorphous. The in- calcite (CaC03) was also observed in the N3 geopolymer sample as
tensity of disturbances can be taken by the approach that diffracts X-rays depicted in Fig. 9 in all geopolymer pastes, low-intensity pyrrhotite
to make a pattern. The intensity patterns were recorded using a constant (Fe11S12 is observed between 30
and 43
2 angles). There is the
divegence slit of 0.38 mm with Cu as the anode material using two appearance of a new phase of dorite compound for N4 and N5 geo-
distinct reflections coefficient Kα1 of 1.5406 and Kα2 of 1.5444. All polymers at higher activator content.
samples are scanned from 10
2Ө to 90
2Ө at 0.0262 step size and scan
range angle. Small portions of the geopolymer pastes were used for XRD 3.7.2. FESEM analysis
analysis after 28 days of ambient healing and the existence of distinctive Field emission scanning electron microscope (FESEM) was used to
phases within the developed one-part geopolymer pastes was observed. investigate the microstructural pattern of one-part geopolymer based on
The phases identified were Na aluminosilicate and Ca aluminosilicate fly ash. Before viewing the specimen in the FESEM, the specimens were

Fig. 9. X-ray diffraction (XRD) of one-part geopolymer mixtures cured at ambient temperature. Key to phases: Q- SiO2 ICDD#01-075-8320; P– Fe11S12 ICDD#06-89-
7439; C– CaCO3 ICDD#01-05-0586; H– Fe2O3 ICDD#01-33-0664; X–CaAl2Si2O8 .4H2O ICDD#00-039-1373; N– NaAlSiO3. 5H2O ICDD#09-00-1344; D- CaMg(CO3)2
ICDD#01-36-0426.

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B.S. Mohammed et al. Heliyon 5 (2019) e02255

coated with 200 A
Gold–Palladium and the micrograph image was ob- 3.7.3. Fourier transform infrared spectroscopy (FT-IR) analysis
tained for each surface area examined under the microscope. After 28 FT-IR spectra are frequently used in characterizing products and are
days of ambient curing, a small portion of the hardened geopolymer useful in characterizing the established HCFA one-part geopolymer paste
pastes was taken for observations and comparison of the microstructure in this job. FT-IR spectra were registered using the Perkin Elmer FT-IR
as shown in Fig. 10. As shown in Fig. 10(a-d), the microstructures of the spectrometer between 4000 cm1 and 500 cm1. Measurements were
paste show reacted amorphous microsphere, and some partially reacted done using 2 cm1 and 40 scans resolution. The peaks of the one-part
spheres of fly ash appear in the entire matrix. It is interesting to see that geopolymer paste happen for all mixtures at distinct wavelengths (i.e.
the formation of the geopolymer paste structure was based on the re- N1, N2, N3, N4 and N5), as shown in Fig. 11. The absorption band at
actions at the outer edge of the particles, forming reaction products 3430 cm1, -3438 cm1 and 1646 cm1 corresponds to OH stretching
adjoining cement particles [50, 51]. Different micrograph image is and bending vibration of adsorbed water molecules on the surface of
observed by increasing activator dosage from 8 percent to 12 percent binder components, the band at 1416 cm1 is connected with the
with some reaction products covering fly ash particles. N3 micrographs asymmetric increase of Si–O and Al–O bonds [53]. The band at 991 cm1
were observed to be very compact and dense with fewer cracks for N3 as through 956 cm-1 corresponds to the loss of undistorted CO2- 3 gel in the
shown in Fig. 10b. It is interesting to note that some isolated voids or scheme, absorption peaks at 742 cm1, 695 cm1, 618 cm1 correspond
pores and microcracks were observed in microstructures with higher to unequal stretching of Si–O–Si and Si–O–Al. These peaks show the
activator dosage (14 percent -16 percent) i.e. N4 and N5 as shown in magnitude of the source ingredients ' reactivity and are common in sili-
Fig. 10(c-d). The decrease in strength of one-part geopolymer pastes is cate coumpounds [53, 54]. A combination of aluminum–oxygen, sili-
attributable to the appearance of these pores and cracks. Partially reacted con–oxygen, silicon–oxygen–silicon, or slicon –oxygen–aluminum bonds
particles develop some pores in the structure spread in pores of small presented by unequal crest places is helpful in interpreting the geo-
shapes consequently small openings are noticed from the spots after the polymerization mechanism. It is worth mentioning that higher activator
fly ash particles have been dissolved [52]. High CaO content in fly ash content did not result in major structural modifications of the geo-
yields some Ca–Al–Si-hydrate gels in the microstructure. polymer pastes, but a slight movement in the peak position was noticed

Fig. 10. FESEM micrographs of one-part geopolymers: (a) N1 with 4% Na2O (b) N3 with 6% Na2O (c) N4 with 7% Na2O (d) N5 with 8% Na2O.

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B.S. Mohammed et al. Heliyon 5 (2019) e02255

Fig. 11. Combined FT-IR spectra of fly ash based one-part geopolymer paste at different activator content.

for all the mixtures. Although N4's transmittance is lower than the Declarations
remaining mixtures, it follows the same patterns as NI, N2, N3, and N5
respectively. Author contribution statement

4. Conclusion Sani Haruna: Performed the experiments; Analyzed and interpreted

the data; Wrote the paper.
This study shows a crucial step towards using high-calcium fly ash as a Bashar Mohammed: Conceived and designed the experiments.
substitute building material for in-situ and large-scale concrete Mohamed Mubarak & Abdulrahman Haruna: Analyzed and inter-
manufacturing. Granular anhydrous sodium metasilicate has been effec- preted the data.
tively used to create one-part activated alkali pastes. Understanding the Mohd Shahir Liew: Contributed reagents, materials, analysis tools or
perfect alkali activation circumstances is essential for producing environ- data.
mentally friendly products that will be used almost as worthy re-
placements for ancient cement material. Five mixtures of one-part
geopolymer pastes were intended for distinct activator structure. Work- Funding statement
ability, setting time, density and strength behaviour, impact of molar
proportions and microstructural characteristics were envisaged. The This work was supported by an internal fund (Universiti Teknologi
following findings are drawn from the present experimental consequence: PETRONAS).

i. Results showed that raising the granular activator by weight of the Competing interest statement
fly ash beyond 12 percent slightly decreases the strength and
workability of the one-part geopolymer cement pastes. The opti- The authors declare no conflict of interest.
mum mix by weight of the fly ash was discovered to be 12 percent
(i.e. 6 percent Na2O) at 28 days curing.
ii The developed one-part geopolymer paste exhibited a compres- Additional information
sive strength of nearly 50 MPa. The flowability of one-part geo-
polymer paste was comparatively affected by the content of No additional information is available for this paper.
sodium metasilicate in the mixtures. Flowability reduces with
regard to N1 by 2.5 percent, 4.9 percent, 6.7 percent, and 7.3 References
percent for N2, N3, N4, and N5 mixtures respectively.
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