Journal of Cleaner Production 378 (2022) 134370

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Journal of Cleaner Production

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

Towards greener one-part geopolymers through solid sodium

activators modification
Ooi Wan-En a, b, Liew Yun-Ming a, b, *, Heah Cheng-Yong a, c, Ho Li Ngee b,
Mohd Mustafa Al Bakri Abdullah a, b, Mohd Suhaimi Bin Khalid d, Foo Kai Loong e,
Ong Shee-Ween a, b, Tan Pei Seng f, Hang Yong Jie a, b, Khairunnisa Zulkifly a, b
a
Geopolymer and Green Technology, Centre of Excellence (CEGeoGTech), Universiti Malaysia Perlis (UniMAP), 01000, Perlis, Malaysia
b
Faculty of Chemical Engineering and Technology, Universiti Malaysia Perlis (UniMAP), 01000, Perlis, Malaysia
c
Faculty of Mechanical Engineering and Technology, Universiti Malaysia Perlis (UniMAP), 01000, Perlis, Malaysia
d
Chemical Service and Environment (Technical Support) Section, Sultan Azlan Shah Power Station, TNB Janamanjung Sdn Bhd, 32040, Seri Manjung, Perak, Malaysia
e
Institute of Nano Electronic Engineering (INEE), Universiti Malaysia Perlis (UniMAP), 01000, Perlis, Malaysia
f
Department of Electrical and Electronic Engineering, Universiti Teknologi Petronas (UTP), 32610 Seri Iskandar, Perak, Malaysia

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

Handling Editor: Jian Zuo This paper investigates the influence of various solid activators and their mixing parameters on the physical,
mechanical and microstructural characteristics of greener one-part geopolymers (OPG) based on high calcium fly
Keywords: ash. The high calcium fly ash that has rarely been explored was utilised to develop OPG in this study. The
One-part geopolymer anhydrous sodium metasilicate (Na2SiO3) with negative environmental impact propelled the partial replacement
High calcium fly ash
of Na2SiO3 with sodium hydroxide (NaOH) and sodium carbonate (Na2CO3). Two sets of high calcium fly ash
Sodium carbonate
OPGs were developed: (1) the MH-OPG comprised Na2SiO3 and NaOH; (2) the MC-OPG comprised Na2SiO3 and
Anhydrous sodium metasilicate
Sodium hydroxide Na2CO3. The optimal MH-OPG (73 MPa) and MC-OPG (75 MPa) exhibited superior compressive strength, higher
Embodied carbon than the minimal requirement (>28 MPa) of ASTM C150/C150M-18 for construction binder material. Various
solid alkali activators triggered different reaction mechanisms, yielding distinctive reaction products that
contributed to strength growth. The sodium calcium aluminosilicate hydrate ((N,C)-A-S-H) gel was developed in
MH-OPG, whereas the sodium carbonate hydrate, sodium aluminosilicate hydrate (N-A-S-H) and calcium
aluminosilicate hydrate (C-A-S-H) binding phases were developed in the MC-OPG. Although Na2CO3 reduced the
water demand, improved the fluidity and setting time, the MC-OPG was more sensitive to the alteration of mixing
compositions, suggesting a tougher performance control during field application than the MH-OPG. The total
embodied carbon (EC) of MC-OPG was lowered by 15.4% compared to that of MH-OPG. The embodied carbon
index (ECI) of MH-OPG and MC-OPG were 81.3% and 84.7% less than that of OPC products. This work suggests
that substituting Na2SiO3 with NaOH or Na2CO3 effectively produced a greener construction material without
compromising mechanical strength.

1. Introduction associated with the fuel burning in the calcination of limestone in

cement kiln. Urbanization projections for the next century suggest an
During the past decades, the need for sustainable development has increase in cement consumption, necessitating measures to mitigate the
intensified as a result of global warming. The cement industry is the material’s environmental impact. The introduction of an alternative
second largest contributor to carbon dioxide (CO2) emission, accounting material, geopolymer, is a solution to the OPC’s massive carbon emis­
for 7% of global CO2 emissions (International Energy Agency, 2018). As sion. The production of this inorganic material entails waste recycling,
one of the most extensively used building materials, ordinary Portland low energy consumption, minimal CO2 emission and avoidance of nat­
cement (OPC), emits a significant amount of greenhouse gas (0.83 kg of ural resources exploitation. Most importantly, heating is not necessary,
CO2/kg of OPC) (Adesina, 2021). This carbon emission is highly which saves time and energy. Geopolymer is produced from silica and

* Corresponding author. Geopolymer and Green Technology, Centre of Excellence (CEGeoGTech), Universiti Malaysia Perlis (UniMAP), 01000, Perlis, Malaysia.
E-mail address: [email protected] (L. Yun-Ming).

https://doi.org/10.1016/j.jclepro.2022.134370
Received 5 June 2022; Received in revised form 19 September 2022; Accepted 23 September 2022
Available online 28 September 2022
0959-6526/© 2022 Elsevier Ltd. All rights reserved.
O. Wan-En et al. Journal of Cleaner Production 378 (2022) 134370

alumina-containing pozzolanic material. In the presence of suitable furnace slag OPG. The environmental impact of the fly ash/ground
alkaline conditions, the dissolution of the pozzolanic materials and the granulated blast furnace slag OPG was not included. In addition, the
subsequent polymerization process generate a three-dimensional alkali activation by Na2CO3 delayed the setting time of geopolymer
aluminosilicate network (Davidovits, 1994) that gradually gains me­ paste (Li and Sun, 2000). When Na2CO3 solution was used exclusively
chanical strength through ambient ageing. Geopolymer demonstrates for concrete production, the setting period was exceptionally long (455
high mechanical strengths, low drying shrinkage, good heat and min of initial setting time) (Kovtun et al., 2015). The incorporation of
chemical resistance (Luukkonen et al., 2018), making them a promising extra ingredients in the mixtures, such as calcined dolomite (Yang et al.,
green alternative material to OPC. 2019) and magnesia (from calcination of magnesite) (Abdalqader et al.,
One-part geopolymer (OPG) is an advanced counterpart of the 2015) accelerated the setting. However, additional thermal treatment
traditional (two-part) geopolymer, that uses a more convenient mixing was required, which consumed a high amount of energy and has a
procedure. The OPG utilised aluminosilicate pozzolanic materials, solid negative contribution on sustainable development. Thus, this study also
alkali activators and water. Forgoing the use of extremely alkaline so­ serves the purpose of improving the setting properties of OPG by pro­
lutions has aided the storage, transport and handling processes. Previous posing high calcium fly ash as the aluminosilicates.
research has utilised several types of aluminosilicate materials in the Past literatures showed that low calcium fly ash and slag were widely
production of OPG and the performances strongly correlates with their used as the aluminosilicates for the synthesis of OPG. High calcium fly
calcium content. Niu et al. (2022) found out that replacement of slag ash has rarely been employed, leading to the unknown performance of
with sulfidic mine tailings beyond 20% hindered the hydration process the OPG. It is known that the chemical composition of aluminosilicates
of OPG due to the lower content of highly reactive calcium oxide (CaO). varies from one to another. Thus, manipulating the aluminocilicates as
Sood and Hossain (2021) reported that the using calcium-rich precursor well as the type and dosage of alkali activators exerts tremendous in­
drove a quicker setting of the one-part alkali-activated material due to fluence on the reaction kinetics, reaction products and the geopolymer’s
the early formation of Ca-containing hydrate gels. Most research studied performances (Dong et al., 2020; Mohammed et al., 2019). Regardless of
the activation of ground granulated blast furnace slag (GGBFS). How­ the types of alkali activators, there is usually a threshold for the activator
ever, the carbon emission by GGBFS (0.052–0.143 kg CO2/kg) is higher dosage. The use of NaOH and Na2CO3 in combination with Na2SiO3 as
than fly ash (0.004–0.027 kg CO2/kg) due to the need for grinding the solid alkali activator for OPG formation was comparatively less
process (Black, 2016). Thus, the high calcium fly ash (Class C fly ash) investigated, particularly the effects of mixing parameters on the fresh,
becomes a better option in delivering greener OPG. physical and mechanical properties, microstructural characteristics and
The solid alkali activator can be sodium metasilicate (Na2SiO3), so­ phases in the final product. This is especially significant and critical in
dium aluminate (NaAlO2), sodium hydroxide (NaOH) or sodium car­ reducing the reliance on the less environmentally friendly anhydrous
bonate (Na2CO3). Na2SiO3 is the most common solid activator, with Na2SiO3 in OPG production, as well as achieving a good balance of fresh,
anhydrous Na2SiO3 as the most effective solid alkali activator (Nem­ physical and mechanical properties for construction applications.
atollahi et al., 2015). However, anhydrous Na2SiO3 releases a high Therefore, this work aims to evaluate and compare the performances
amount of CO2 (Wang et al., 2021). The production of Na2SiO3 requires of greener OPGs using high calcium fly ash by combining Na2SiO3,
heat treatment to approximate 1000 ◦ C. Reducing the amount of NaOH and Na2CO3. This research contributes to the in-depth under­
Na2SiO3 could reduce environmental impact, but the performance of standing of the influence of mixing parameters, including the alkali
OPG would be less ideal due to alkali deficiency. This necessitates the activator-to-fly ash (AA/FA) ratio, alkali activator content and water-to-
use of alternative or supplementary activators with lower environmental binder (W/B) ratio on the fluidity, setting time, physical properties,
impact. compressive strength, microstructures, functional groups and phases of
The combination of Na2SiO3 and NaOH has been used as a solid the OPGs. The significance of mixing factors towards the compressive
activator in OPG formation. NaOH is produced from the electrolysis of strength was also explored quantitatively for post hoc validation as a
brine solution (Adesina, 2021), which is comparatively cleaner and novel aspect of the study. A preliminary environmental impact assess­
more favourable for the production of a greener OPG. Hajimohammadi ment was conducted to justify the environmental benefits. The findings
and van Deventer (2017) produced OPG using on low calcium fly ash of this research facilitate the development and production of greener
activated with NaOH and Na2SiO3 and achieved a 21-d compressive and load-bearing cementitious materials, repair materials or 3D
strength of 65 MPa. Their study focused on the mechanical strength and printable-materials for sustainable construction applications.
microstructural characteristics under the effect of water content and
Si/Al ratio. Yin et al. (2022) investigated the effect of rice straw ash 2. Methodology
incorporation on the physical, mechanical and microstructural proper­
ties of one-part alkali-activated slag activated with Na2SiO3 and NaOH 2.1. Materials
attained a compressive strength of merely 20 MPa after 28 d. Nem­
atollahi et al. (2015) reported that the compressive strength of the low The fly ash was supplied by a coal-fired power plant in Manjung,
calcium fly ash OPG containing Na2SiO3 and NaOH was 31% lower than Perak Malaysia. Table 1 tabulates the chemical composition of the fly
the two-part geopolymer. Their study focused on the effects of different ash analysed by X-ray Fluorescence (XRF PAN Analytic PW4030). The
curing regimes, slag and hydrated lime replacement on the fresh and fly ash mainly consisted of SiO2, CaO, Al2O3 and Fe2O3. The calcium
hardened properties of the OPG. The past research on OPG activated content was higher than 18%, meeting the criteria of high calcium (Class
with Na2SiO3 and NaOH is relatively limited. C) fly ash in ASTM C618-19. The morphological feature and particle size
Na2CO3 has also been used with Na2SiO3 as the solid alkali activator distribution of the fly ash are presented in Fig. 1a and Fig. 1b respec­
for OPG formation. The manufacturing of Na2CO3 is much simpler, less tively. The fly ash particles are spherical in shape with particle sizes
expensive, less corrosive and less polluting (Bernal et al., 2015). It can be ranging from 0.53 to 171.61 μm. The particle size was determined by the
expected that a greener cementitious material could be attained by Malvern Mastersizer 2000 particle size analyser. The percentile values of
incorporating Na2CO3 in the development of OPG. Ma et al. (2019) used the particle sizes are listed in Fig. 1b.
Na2SiO3 and Na2CO3 as the solid alkali activators to prepare OPG based
on fly ash sinking beads and GGBFS. However, their study focused only Table 1
on the effect of replacement dosage of Na2SiO3 with Na2CO3 on the fresh Chemical composition of fly ash.
properties, hardened properties, reaction kinetics, microstructures and Oxides SiO2 CaO Al2O3 Fe2O3 SO3 K2 O TiO2 Others
environmental impact of the OPG. An almost similar study has been
Mass (wt%) 36.7 19.1 18.7 17.2 3.04 1.78 1.68 1.80
carried out by Wang et al. (2021) on fly ash/ground granulated blast

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O. Wan-En et al. Journal of Cleaner Production 378 (2022) 134370

Fig. 1. (a) Morphological feature and (b) particle size distribution of fly ash.

The solid alkali activators used were anhydrous Na2SiO3, NaOH and
Table 3
Na2CO3. The Na2SiO3 granule (18-mesh) was supplied by Fisher Scien­
Factors and respective variation levels.
tific (M) Pvt. Ltd.; NaOH pellet with a purity of 97.0% by Progressive
Scientific Pvt. Ltd.; the Na2CO3 powder with purity a of 99.5%, was MH-OPG MC-OPG

purchased from Chemiz (M) Pvt. Ltd. Table 2 lists the particle sizes of the AA/FA SM/SH W/B AA/FA SM/SC W/B
solid alkali activators. ratio ratio ratio ratio ratio ratio

0.15 2.00 0.25 0.15 0.50 0.15

0.20 3.00 0.30 0.20 1.00 0.20
2.2. Mix design and sample preparation
0.25 4.00 0.35 0.25 1.50 0.25

To investigate the influence of mixing parameters on the perfor­

mance of OPGs, the mixtures were designed based on three mixing perpendicular to each other were obtained for each mix and the average
factors, each with varying levels. The details of mixtures for two sets of values were calculated.
OPGs are listed in Table 3. The two sets of OPGs were MH-OPG and MC- The setting times of the OPGs were determined using the Vicat
OPG, where the MH-OPG consisted of fly ash, Na2SiO3 and NaOH, while apparatus following ASTM C191-08. The mixtures were poured into a
the MC-OPG consisted of fly ash, Na2SiO3 and Na2CO3. The three mixing ring mould and allowed to sit for 15 min before the first release of the
factors considered in the study were the AA/FA ratio, alkali activator removable rod on the Vicat apparatus. The initial setting time was
ratio and W/B ratio. The alkali activator ratios were Na2SiO3-to-NaOH recorded when the Vicat needle penetrates less than 25 mm into the OPG
(SM/SH) ratio for MH-OPG and Na2SiO3-to-Na2CO3 (SM/SC) ratio for paste. The final setting time was recorded when the Vicat needle did not
MC-OPG. The binder (B) in this context refers to the combination of fly leave a circular impression on the specimen surface.
ash and solid alkali activators. Three levels for each factor were con­ Small cylindrical samples were used to measure the apparent
ducted to evaluate the significance of the factors on the strength per­ porosity and water. Three measurements were recorded and applied in
formance of OPGs, as well as to determine the mixing compositions for Eq. (1) and (2).
optimal performance. The assigned weight ratios were referred to rele­
MW − MD
vant research works (Erfanimanesh and Sharbatdar, 2020; Ishwarya Water absorption (%) = (1)
MD
et al., 2019) and the preliminary tests conducted.
The solid binders were dry mixed until homogeneous. Then, weighed MW − MD
water was gradually added into the dry binder and mechanically mixed Porosity (%) = (2)
MW − MS
for 3 min to obtain a geopolymer slurry. Upon completion of the mixing
process, a portion of the slurry was used to measure fresh properties, the Where MW (g) is the weight of wet samples, MD is the weight of samples
remaining slurry was cast into acrylic mould (50 mm × 50 mm × 50 dried in the oven at 80 ◦ C until a stable mass obtained (Saludung et al.,
mm) in accordance with ASTM C109/C109M-13. The casting was fol­ 2021), and MS is the weight of suspended samples in water. According to
lowed by a mechanical vibrating step for 1 min to remove air voids and Luo et al. (2022), the loss of free water from geopolymers occurred
further ensure homogeneity of the mixture. The samples were demoul­ between 80 and 150 ◦ C. Fly ash based-geopolymer was relatively stable
ded after 24 h. The samples were wrapped with cling film to prevent with minor porosity increment and minimal crack formation when
moisture loss during the ageing process at room temperature (30 ◦ C). subjected to temperature below 100 ◦ C.
The testing and analysis were carried out after 28 d. Before the compressive strength test, the mass and dimensions of all
cubic samples were measured. The bulk density was calculated by
2.3. Test methods dividing the mass by its volume in accordance with BS EN 12390-7.
For each mix design, three replications of the compression test were
Grout spread diameter was measured as per BS EN445 to determine done after 28 d in accordance with ASTM C109/C109M-13. The test was
the fluidity of the fresh OPG pastes. The fresh paste was poured into a carried out using a Universal testing machine (UTM Shimadzu US-
cylindrical cone measuring 39 mm in diameter and 60 mm in height. The 1000kNI) with a loading rate of 5 mm/min. The compressive strengths
filled cone was lifted vertically, allowing the fresh paste to flow freely on obtained were subjected to the one-way analysis of variance (ANOVA) at
a smooth flat surface. Two measurements of spread diameters a 5% significance level. The statistical analysis was used to determine
the significance and the percentage influences of the mix parameters on
Table 2 the compressive strengths of the OPGs.
Particle size of solid alkali activators in mm. The microstructural and mineralogical characterisation of the raw
materials and the aged samples were executed to understand the effects
Anhydrous Na2SiO3 NaOH Na2CO3
of different solid alkali activators on the geopolymerisation reaction.
1.0 5.0–7.0 0.25 The microstructures were determined through scanning electron

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O. Wan-En et al. Journal of Cleaner Production 378 (2022) 134370

microscopy (SEM JEOL JSM-6010LV) with a secondary electron signal. due to the smaller particle size differences between Na2SiO3 and Na2CO3
The elemental compositions of the samples were determined through (Table 2). In return, the grout spread diameters were consistent.
energy-dispersive X-ray (EDX) analysis on 10 selected points. The X-ray Water acts as a lubricating element in the fresh paste. The OPG pastes
diffraction (XRD Bruker, D2-Phaser) was used to determine the binding showed a spread extension when the W/B ratio increased. An increase in
phases developed in the OPGs. The phase analysis was done with a scan water content permitted higher mobility of solid particles, thus reducing
rate of 1.0 s/step. The diffraction pattern was analysed using X’Pert particle aggregation in the paste. This feature has more potential in
HighScore Plus software. Furthermore, the functional groups present in engineering applications. The fresh paste of MC-OPG was more “liquefy”
the aged OPGs were also determined through Fourier transform infrared and had a better mouldability than the MH-OPG paste, as proven from
spectroscopy (FTIR PerkinElmer Spectrum RX1) with a resolution of 4 the larger grout spread diameters of the MC-OPG paste than the MH-
cm− 1. The powder specimens for phases and functional group analysis OPG paste at the same W/B ratio of 0.25 (Fig. 2). The result corre­
were prepared by grinding the fractured pieces of OPGs after the sponds to that of alkali-activated slag cement, where the workability was
compression test. Meanwhile, the solid specimens used for microstruc­ enhanced by 50% when Na2CO3 was applied in place of NaOH (Kovtun
tural analysis were fabricated separately to eliminate unnecessary et al., 2015). The finding also implied that Na2CO3 reduced the water
cracks. demand of MC-OPG. This could be attributed to the smaller kinetic
The environmental impact evaluation was analysed by evaluating friction of the solid matters in the MC-OPG since their particle sizes were
the embodied carbon (EC) of raw materials for geopolymer formation. finer than that of the MH-OPG. The finding is in good agreement with Li
EC is the CO2 emission associated with materials and construction et al. (2019) that found out the alkali-activation of slag by Na2CO3 has a
processes. The embodied carbon index (ECI, kg CO2/m3/MPa) was lower water requirement than by NaOH.
calculated to enumerate the sustainability of the OPGs in the context of
per unit strength based on Eq. (3) (Adesina, 2021). 3.2. Setting time
EC
ECI = (3) Setting time is one of the most important indices for cementitious
fc28
material. The viscosity of paste will increase with ageing time until it
Where EC (kg CO2/m3) is the embodied carbon of a cubic meter sample reaches the initial setting state. The paste gains green strength pro­
and fc28 (MPa) is the 28-d compressive strength. gressively and reaches the final setting state. In certain applications,
such as ready-mix concrete, paste with a longer setting time is necessary
3. Results and discussion to allow transport and placement. In other circumstances, such as pre­
cast cement and concrete, paste with rapid setting properties is more
3.1. Fluidity time and cost effective. The setting times of the OPGs are displayed in
Fig. 3. The setting time trends were similar for MH-OPG and MC-OPG.
Grout spread test was employed to determine the fluidity of the fresh The setting times were lengthened with the increase of the AA/FA and
OPG pastes. Fig. 2a shows significant changes in the fluidity of the MH- W/B ratios, but shortened with the increase of SM/SH and SM/SC ratios.
OPG pastes when the mix parameters were altered. The grout spread In two-part geopolymers, increasing AA/FA ratio raised the alka­
diameters extended by 45.3% when the AA/FA ratio increased from 0.15 linity of the paste, favouring the attack of the Si–O and Al–O bond by the
to 0.25. The spread diameter was doubled when the SM/SH ratio hydroxyl (OH− ) anions (De Weerdt, 2011). The rate of fly ash dissolu­
increased from 2.00 to 4.00. In the case of MC-OPG (Fig. 2b), it was tion was accelerated, promoting a greater extent of alkaline hydrolysis.
apparent that the AA/FA and SM/SC ratios had no significant effects on However, the scenario was slightly different when solid alkali activators
fluidity. The grout spread diameters ranged from 150.0 to 157.5 mm. were used. The solid alkali activators dissolved spontaneously when
The fluidity of the OPG fresh pastes is closely related to the initial water was added into the mix (with slight mechanical effort). The
reaction that occurred during OPG processing. When water was added to dissolution of solid solutes became progressively longer when the
the dry binder, solid alkali activators dissolved and released energy. The dosage increased as the paste was saturated with ions. The alkalinity of
increase in the spread diameters of MH-OPG along with the increasing the paste was maintained at a certain level even when more solid alkali
AA/FA ratio indicated that the solid particles experienced better activator was supplied. The solid alkali activators and aluminosilicate in
dispersion due to the higher kinetic energy of the materials. Increasing the OPGs with higher AA/FA ratios underwent progressive dissolution,
SM/SH ratio reduced the amount of NaOH pellets with larger particle resulting in delayed geopolymer network formation and prolonged
size. The sliding friction between the solid binders was minimised, setting time.
leading to the greater spread of the MH-OPG pastes. The MH-OPG with a low SM/SH ratio of 2.00 took more than 10 h to
On the other hand, the consistent spread diameters recorded for the reach the final setting. The slow hardening of paste with a low SM/SH
MC-OPG regardless of the AA/FA and SM/SC ratio, suggested that a ratio has also been reported in two-part geopolymer. For instance, Nath
similar or lower energy was generated during the dissolution of the solid and Sarker (2014) reported a final setting time of more than 10 h with an
alkali activators, which constrained the hyperactivity of the particles. SM/SH ratio of 1.50. Accelerated condensation was identified with
The change in SM/SC ratio did not incur a significant frictional variation increasing SM/SH ratio in MH-OPG, reducing the final setting time to 3 h
at an SM/SH ratio of 4.00. This was mainly contributed by the increased

Fig. 2. Grout spread diameters (mm) of the (a) MH-OPG and (b) MC-OPG.

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O. Wan-En et al. Journal of Cleaner Production 378 (2022) 134370

Fig. 3. Setting times of the (a) MH-OPG and (b) MC-OPG.

soluble silica (from Na2SiO3) that enhanced the polymerization rate of higher than 0.30. A buildable 3D printing geopolymer mixture is ex­
the dissolved substances and promoted the early precipitation of reac­ pected to have a lower fluidity and rapid setting properties (Şahin and
tion product. Mardani-Aghabaglou, 2022). Guo et al. (2020) suggested that the
For MC-OPG, a longer setting period (4 h) was observed with a lower appropriate initial setting time for 3D printing applications is 30–50
SM/SC ratio of 0.50. The incorporation of Na2CO3 cultivated moderate min, and the final setting time is approximately 1 h. The MC-OPG could
initial pH condition of the mixtures, causing slower alkaline hydrolysis, be developed for 3D printing applications considering the appropriate
which postponed the generation of gelation products. Despite that the setting times (15–30 min initial setting time and 60–240 min final
particle size of the Na2CO3 was smaller than Na2SiO3, the OPG with setting time) and a modest fluidity (Fig. 2).
higher content of Na2CO3 (i.e., low SM/SC ratio) demonstrated delayed
setting time. This justified that the Na2CO3 has a slow-dissolving char­
acteristic. The increasing SM/SC ratio up to 1.50 reduced the final 3.3. Bulk density, apparent porosity and water absorption
setting time to 1 h. The finding was akin to that of Wang et al. (2021)
where the final setting time was shortened when the SM/SC ratio was The bulk density, apparent porosity and water absorption of OPGs
increased from 1.10 (1.8 h) to 4.60 (0.2 h) in fly ash/slag blend OPG. are illustrated in Fig. 4a and b. The effects of AA/FA and W/B ratio on
Even though the W/B ratio used by Wang et al. (2021) was higher bulk density, porosity and water absorption were alike. The increase of
(0.36), the fly ash/slag blend OPG had a shorter setting time than AA/FA ratio from 0.15 to 0.25 raised the bulk density of MH-OPG and
MC-OPG due to the use of ground-granulated blast furnace slag, which MC-OPG by 3.4% and 4.2%, respectively. The increase of the AA/FA
accelerated the reactivity of geopolymer. ratio of MH-OPG reduced the porosity and water absorption by 44.6%
The increase of the W/B ratio while keeping other mix variable and 41.1%, respectively. Meanwhile, the increase of the AA/FA ratio of
constant inevitably prolonged the setting times. The dissolution of solid MC-OPG reduced the porosity and water absorption by 34.3% and
alkali activators and geopolymerisation reaction is an exothermic pro­ 36.9%, respectively. The increase of the W/B ratios reduced the bulk
cess. At a high W/B ratio, the large amount of water normalised the heat densities of MH-OPG by 4.7% and MC-OPG by 8.6%. Concurrently, the
generated in the systems, thereby leading to a gradual geo­ porosity and water absorption showed upward trends.
polymerisation reaction. The setting times are affected by the types of The porosity and water absorption of all the hardened samples were
solid alkali activator, rate of dissolution and heat of reaction. At a W/B reduced with increasing solid alkali activators (increasing AA/FA ratio).
ratio of 0.25, the initial and final setting times of MH-OPG were shorter As mentioned earlier, the dissolution of NaOH generated a consequen­
than the MC-OPG. Na2CO3 has a lower dissolution ability than NaOH tial amount of heat, favoured water evaporation. The evaporable water
due to the lower alkalinity of Na2CO3 (Ma et al., 2019). The dissolution that eventually transformed into pores in the OPG structures was
of Na2CO3 induced less heat of reaction, slowed down the alkaline hy­ reduced, produced a denser OPG structure. This behaviour was also
drolysis, coagulation and hardening of geopolymer matrix and length­ observed in two-part geopolymer (Ishwarya et al., 2019). Correspond­
ened the setting time of MC-OPG. ingly, the higher water content (higher the W/B ratio) yielded more free
Based on ASTM C881/C881M-02, the minimum initial setting time water accessible for evaporation, forming more pores and voids. The
required for repair binder was 30 min. This can be fulfilled by the MC- scenario has driven a higher porosity and water absorption of the OPGs.
OPG with W/B ratio higher than 0.25 and MH-OPG with W/B ratio The lower solid content with increasing W/B ratio and water evapora­
tion led to OPGs with lower density.

Fig. 4. Bulk density, apparent porosity and water absorption of the (a) MH-OPG and (b) MC-OPG.

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O. Wan-En et al. Journal of Cleaner Production 378 (2022) 134370

The change of SM/SC ratio in MC-OPG caused a significant impact on dissolution of solid alkali activators was implausible during the mixing
the bulk density, porosity and water absorption. The porosity and water process. The dissolution progressed via moisture ingression, while the
absorption first dropped with increasing SM/SC ratio up to 1.00, but precipitation of reaction products progressed via diffusion during the
increased when the SM/SC ratio changed to 1.50. A highly porous ageing period (Garcia-Lodeiro et al., 2013). This justified that the initial
structure was developed at an SM/SC ratio of 0.50 due to the moderate dissolution of solid alkali activators could not be a definite measure of
pH of Na2CO3 which hampered efficient alkaline hydrolysis. The trend the 28-d compressive strength of OPGs.
was similar to the slag-based, as well as fly ash-and-slag blended OPG The compressive strength of MH-OPG with a W/B ratio of 0.35
(Ma et al., 2019), wherein the cumulative porosity decreased when the outperformed other mixtures that have lower W/B ratios, ascertaining
SM/SC ratio increased. The Na2CO3 encourages voids formation in the the importance of water in the geopolymerisation reaction. Water fa­
OPG microstructure, regardless of the types of aluminosilicate cilitates the dissolution of solid alkali activators during mixing, yielding
precursor. OH− ion and favouring a higher degree of reaction to achieve higher
compressive strength. Suitable water content is vital for optimising the
3.4. Compressive strength geopolymerisation reaction. It is believed that the compressive strength
would not be increasing indefinitely with water dosage because of the
The compressive strengths of MH-OPG are plotted in Fig. 5a. All the pH dilution.
OPGs showed excellent compressive strengths (ranging from 31.6 The MC-OPG had compressive strength ranged from 22.3 MPa–99.2
MPa–77.7 MPa) after 28 d of ambient ageing. The compressive strength MPa (Fig. 5b). The small increment in the AA/FA ratio from 0.15 to 0.20
of MH-OPG was reduced by 56.3% when the AA/FA ratio increased. resulted in a substantial increase in the compressive strength by 333.1%.
There was no significant enhancement in the compressive strength as But a further increase of the ratio caused strength deterioration by
SM/SH ratio increased (72.3 MPa–73.8 MPa), due to marginal variation 29.8%. A fourfold increase in the compressive strength was recorded as
in the bulk density and porosity (Fig. 4a). The compressive strength the SM/SC ratio increased from 0.50 to 1.50. The increase of the W/B
increased by 37.3% when the W/B ratio increased. The MH-OPG with an ratio caused a linear reduction in the compressive strength, from 99.2
AA/FA ratio of 0.15, an SM/SH ratio of 3.00 and a W/B ratio of 0.30 that MPa to 47.7 MPa. Based on the compressive strength and the fresh
demonstrated a workable fresh paste and satisfactory compressive properties, the ideal mix design for MC-OPG was achieved with an AA/
strength (72.7 MPa) is the optimum design. A similar AA/FA ratio of FA ratio of 0.20, an SM/SC ratio of 1.0 and a W/B ratio of 0.20.
0.16 and W/B ratio of 0.23 was reported by Nematollahi et al. (2015) for An excellent compressive strength (75.1 MPa) achieved by the MC-
low calcium fly ash OPG with a compressive strength of 29.3 MPa after OPG with an AA/FA ratio of 0.20 due to the suitable amount of so­
28 d. This indicated that the high calcium fly ash performed better than dium oxide (Na2O) supplied. The role of Na2O was to supply alkali metal
the low calcium fly ash, even in case of higher water content. cation (Na+) for the formation of geopolymer networks. A lower SM/SC
Interestingly, it was found that the MH-OPG with the highest ratio (higher Na2CO3 content) resulted in a lower compressive strength.
compressive strength contained the highest apparent porosity and water A similar trend has been reported by Ma et al. (2019) in slag-based OPG.
absorption (Fig. 4a). The current finding agreed with Ma et al. (2021), The incorporation of Na2CO3 restrained comprehensive geo­
stating that a geopolymer sample with the highest compressive strength polymerisation reaction due to the relatively lower pH. This can be
has the maximum cumulative pore volume. As mentioned earlier, supported by the reduced total reaction heat of fly ash and slag blended
increasing the AA/FA ratio slows down the dissolution of solid alkali OPG when the amount of Na2CO3 increased (Wang et al., 2021), which
activators, which potentially caused undissolved solid alkali activators indicated a poorer dissolution and reaction rate.
to remain in the structure. During the 28 d of ageing, the solid alkali The increasing W/B ratio in MC-OPG led to a compressive strength
activators could be dissolved through moisture ingression, resulting in reduction. The outcome was in good agreement with the increased
coarse voids in the structure (Dong et al., 2020). These coarse pores apparent porosity and water absorption when the W/B ratio (Fig. 4b)
could be a stress concentration points when a load is applied, leading to was increased. The high water dosage also diluted the alkalinity of the
structural failure. On the contrary, the MH-OPG with lower alkali acti­ mixture, inhibited the hydroxylation of the fly ash particles, which
vator content (at a lower AA/FA ratio) produced smaller pores even reduced the degree of geopolymerisation reaction and deteriorated the
though the total porosity was increased, yielded a stronger structure. compressive strength. Similar to the fly ash and slag activated with
Although the change in SM/SH ratio caused significant differences in Na2CO3 and Na2SiO3 solutions, increasing the W/B ratio from 0.20 to
fluidity (Fig. 2a) and setting time (Fig. 3a), the 28-d compressive 0.29 caused compressive strength reduction (Ishwarya et al., 2019).
strength attained was analogous. The compressive strength result pre­ Comparatively, an opposing compressive strength trend was observed in
sented correlations neither with the fluidity nor the setting time. The MH-OPG and MC-OPG with the increasing W/B ratio. Even though the
fresh properties were influenced by the initial dissolution of the raw W/B ratios of MH-OPG (0.25–0.35) were higher than that of the
materials, while the 28-d compressive strength depended on the reaction MC-OPG (0.15–0.25), the way the OPGs fostered their strength was
among the elements present in the mixture during ageing. A complete dissimilar. For this reason, the optimization study is paramount for OPGs

Fig. 5. 28-d compressive strength of (a) MH-OPG and (b) MC-OPG.

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O. Wan-En et al. Journal of Cleaner Production 378 (2022) 134370

with varying raw materials. marginal change in the compressive strength after 28 d (<1 MPa) when
The optimal compressive strengths achieved by MH-OPG (72.7 MPa) the modulus increased from 0.79 to 0.98. Dissimilar to two-part geo­
and MC-OPG (75.1 MPa) were excellent, which were higher than the polymers, this mixing factor influenced the mechanical strength (Morsy
requirement set by ASTM C150/C150M-18 (22.0–28.0 MPa). When et al., 2014). The suitable SM/SH ratio for the MH-OPG may rely on
Na2SiO3 was used as the sole solid activator, a less alkaline condition other performances, such as fluidity and setting time. Apart from that,
was cultivated due to the lower OH− ions (Pacheco-Torgal et al., 2008). the F-values from MH-OPG were lower than that of the MC-OPG, indi­
While the silicate species (Si–O-) released from the Na2SiO3 contributed cating that the modification of these mixing factors within the range of
to the formation of oligomers, condensation and geopolymer network study imposed a great impact on the compressive strength of the
formation. A higher Na2SiO3 content was used in order to achieve MC-OPG than the MH-OPG.
satisfactory mechanical properties. Mohammed et al. (2019) acquired a The influence of each factor on the compressive strength of the OPGs
compressive strength of 50 MPa for OPG based on class C fly ash. An is illustrated in Fig. 6. This statistical analysis is valuable for future
even lower compressive strength (8.8–20.6 MPa) was obtained by research and field applications as mixing factors with significant influ­
Nematollahi et al. (2015) for OPG based on class F fly ash with the ence makes performance control difficult. The higher influence per­
addition of slag and calcium hydroxide. On the other hand, an excellent centage of a factor implies that the ratio variation would result in more
compressive strength after 28 d was reported by Wan-En et al. (2021) significant changes in the compressive strength. The influence of the
(83.6 MPa) and Wang et al. (2017) (80.1 MPa) for OPG based on high three factors on the compressive strength of the MH-OPG in ascending
calcium fly ash and slag, respectively. The compressive strength ach­ order: SM/SH ratio (0.1%) < W/B ratio (22.6%) < AA/FA ratio (77.3%).
ieved depends on the types of Na2SiO3 adopted (anhydrous, nano­ The MC-OPG are influenced by all the three factors in ascending order:
hydrate or pentahydrate), the types of aluminosilicates, the curing W/B ratio (26.9%) < AA/FA ratio (28.2%) < SM/SC ratio (44.9%).
regime as well as the mixing proportion. If the amount of Na2SiO3 was According to Yuan et al. (2017), the W/B ratio was more influential in
reduced to achieve sustainable OPGs, it would affect the mechanical the mechanical performance of slag-based geopolymer activated solely
performance. This is because the hydration level of the aluminosilicate with Na2CO3, compared to the alkali content. This implied that the in­
materials strongly correlates with the Na2O content, especially when fluence of mixing parameters varies with the type of alkali activator
only Na2SiO3 was used. As proven by Yang et al. (2008), a low AA/FA used.
ratio of 0.08 yielded an OPG with only 0.57 MPa of compressive strength
due to insufficient alkali.
An analysis of variance (ANOVA) was performed to statistically 3.5. Microstructural analysis
determine the significance of mixing factors towards the compressive
strength of the MH-OPG and MC-OPG as tabulated in Table 4. A P-value Figs. 7 and 8 present the SEM images of the MH-OPG and MC-OPG.
higher than 5% and an F-value less than F critical value (F < Fcrit) sig­ The microstructures consisted of gelatinous hydrated products and
nifies an insignificant difference among the compressive strengths. The unreacted particles. The hydrated products were the dense matrices. The
result showed that the influences of the factors were significant except unreacted fly ash particles can be identified by the bright-toned and
for the influence of alkali activator content (SM/SH ratio) on the round morphology.
compressive strength of MH-OPG. The negligible variation in the Progressively larger crack lines were observed in the MH-OPG
compressive strength (1.5 MPa) confirmed that the SM/SH ratio did not (Fig. 7) as the AA/FA ratio increased from 0.15 to 0.25. Cracks were
incur a significant impact (Fig. 5a). The results concurred with Yang and likely to form along the pores and the gel-particle interface. This may be
Song (2009), where the increase of the SM/SH ratio of the slag-based attributed to the excessive solid alkali activators that remained
OPG from 2.8 to 7.9 caused a minor compressive strength increment unreacted in the structure even after 28 d. The crack lines could also be
(2.3 MPa). The statement was further supported by Ye et al. (2016) with accounted for larger voids developed in the structure. The exothermic
dissolution of the solid alkali activators induced water evaporation,
which yielded dry shrinkage and formed cracks. The higher AA/FA ratio
Table 4 also induced more profound drying shrinkage and adversely impacted
ANOVA result of the 28-d compressive strength. the volume stability of OPGs. The drying shrinkage might be due to the
Factors Statistical parameters MH-OPG MC-OPG mesoporous matrix as Sadeghian et al. (2022) suggested.
No significant change in microstructures was seen in MH-OPG when
AA/FA ratio DF 2.00 2.00
SS 2491.89 4171.66
the SM/SH ratio was altered. A small amounts of unreacted fly ash
MS 1245.95 2085.83 particles and pores with subtle crack lines were observed. The
F 70.90 140.66
P 0.00 0.00
Fcrit 5.14 5.14
Significant difference Yes Yes

Alkali activator content DF 2.00 2.00

SS 3.61 6638.38
MS 1.80 3319.19
F 0.13 233.11
P 0.88 0.00
Fcrit 5.14 5.14
Significant difference No Yes

W/B ratio DF 2.00 2.00

SS 730.03 3988.68
MS 365.01 1994.34
F 12.62 92.66
P 0.01 0.00
Fcrit 5.14 5.14
Significant difference Yes Yes

Total SS 3225.53 14798.72

DF = degree of freedom; SS = sum of square; MS = mean square; F = F-value; P=

P-value; Fcrit = F critical value. Fig. 6. The influence of each factor to the compressive strength of the OPGs.

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O. Wan-En et al. Journal of Cleaner Production 378 (2022) 134370

Fig. 7. SEM images of MH-OPG with varying AA/FA ratio, SM/SH ratio and W/B ratio.

observation supported the insignificant influence of the SM/SH ratio discontinuous hydrated gel. Conversely, increasing the SM/SC ratio to
(Table 4). The MH-OPG with a W/B ratio of 0.25 showed traces of 1.0 and 1.5 resulted in the formation of denser and smoother matrices.
partially reacted fly ash particles conglomerated under the reaction The progressively compact structure with an increasing SM/SC ratio
products. The reaction product was deposited on the surface of fly ash showed that the lower Na2CO3 dosage improved the dissolution of fly
particles. This was a sign of water deficiency as the water was only ash and promoted the polycondensation of aluminosilicate gels.
sufficient for mild hydration of the solid binders. The water shortage in For the MC-OPG, the mixture with a W/B ratio of 0.15 demonstrated
the mixture inhibited the extensive diffusion process and formation of a dense and homogeneous microstructure. Increasing the W/B ratio
hydrated gels. Visible cracks were also present in the microstructure at caused more unreacted fly ash to remain in the specimens because of the
the W/B ratio of 0.25. Superficial cracking was also noted by Oderji et al. low pH condition as a result of the addition of Na2CO3 and the increase
(2019b) on a sample with the lowest W/B ratio (0.28) due to potential of water dosage. The optimal reaction was not encouraged when the W/
self-desiccation in the geopolymer matrix that induced autogenous B ratio increased, justifying the lower water requirement of MC-OPG.
shrinkage. Comparatively, the sample with a W/B ratio of 0.35 has a The opposing evolution of the MH-OPG and MC-OPG microstructures
smooth matrix due to the extensive dissolution of solid alkali activators under the influence of the W/B ratio highlighted the importance of the
and fly ash. types of alkali activators in the development of OPGs. Angular-
The influence of the AA/FA ratio on the microstructure was rela­ structured crystals that represents calcium carbonate particles
tively significant for the MC-OPG (Fig. 8). The AA/FA ratio of 0.15 (Assaedi et al., 2020) was found in some of the MC-OPGs as displayed in
yielded an inhomogeneous microstructure. The formation of hydration Fig. 9. The geopolymerisation reaction led to the formation of a new
product was less favourable with less amount of solid alkali activators (i. compound around the dissolved particles. These particles were not seen
e., low pH). Increasing the AA/FA ratio for MC-OPG induced denser and in MH-OPG. The formation of calcium carbonate particles was rarely
smoother microstructure because of the increased formation of the observed in the traditional geopolymers as the alkaline activators sup­
geopolymer matrix. Similar to the MH-OPG, crack lines were found in plied were in liquid form. The finding amplifies the differences between
the MC-OPG with an AA/FA ratio of 0.25, limited the strength perfor­ the traditional geopolymer and OPGs.
mance (Fig. 5). Substantial improvement of geopolymerisation reaction An EDX analysis was performed on the optimal MH-OPG and MC-
was attained in this work in comparison to that of Oderji et al. (2019a), OPG at the hydrated products to identify the approximate element
where a significant amount of unreacted fly ash and slag particles were compositions of the hydration products (excluding unreacted precursor
present in the microstructure of OPG with only 7% of solid alkali acti­ particles). The Ca, Al, and Si atomic percentages were renormalised to
vators applied. 100%, and are illustrated in the CaO–Al2O3–SiO2 ternary diagram
The MC-OPG with an SM/SC ratio of 0.5 depicted plenty of undis­ (Fig. 10a). The clustered region of points by MH-OPG (dashed blue
solved particles embedded within the structure, which adversely circle) corresponded to the sodium calcium aluminosilicate hydrate ((N,
impacted the formation of hydrated gel. The inter-connectivity of the C)-A-S-H) gel (Abdalqader et al., 2016). This phase had a compositional
aluminosilicate networks was restrained as can be seen from the range of 0.27 < Ca/Si < 0.68 and 0.42 < Al/Si < 0.69. Points in the

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O. Wan-En et al. Journal of Cleaner Production 378 (2022) 134370

Fig. 8. SEM images of MC-OPG with varying AA/FA ratio, SM/SC ratio and W/B ratio.

The major difference between MH-OPG and MC-OPG was the use of
varying solid alkali activators. The MC-OPG generally exhibited a higher
Ca/Si ratio and Al/Si ratio than the MH-OPG (Fig. 10b). This indicated
that using Na2SiO3 + Na2CO3 reduced the Si contribution in the hy­
dration product of MC-OPG. Note that the bond strength in an ascending
order is: Ca–O (134 kJ), Al–O (221–280 kJ), Si–O (444 kJ) (Li et al.,
2017). The breakdown of the Si–O bond is the hardest. It is important to
provide sufficient dissolved OH− ions to break down the Si–O bonds. The
use of Na2CO3 reduced the alkalinity of the mixture, resulting in a poorer
dissolution of Si–O bonds and limited the precipitation of Si species in
hydration products. Although the geopolymerisation reaction of the
MC-OPG was less ideal, the optimal MC-OPG attained a slightly higher
compressive strength (75.1 MPa) than the MH-OPG (72.7 MPa). This
was due to the lower water requirement attribute of the MC-OPG, which
yielded a more compact microstructure than the MH-OPG, leading to a
higher strength.

3.6. Phase analysis

Fig. 9. SEM image of the optimum MC-OPG. The XRD diffractograms of the fly ash, optimal MH-OPG and MC-
OPG are shown in Fig. 11. The raw fly ash and OPGs consisted of a
dashed red circle anticipated by the MC-OPG were distributed across the halo region attributed to the amorphous phase and minor crystalline
calcium aluminosilicate hydrate (C-A-S-H, green shaded region) towards peaks. The broad hump in the fly ash was located between 10◦ and 40◦
sodium aluminosilicate hydrate (N-A-S-H, yellow shaded region) gel 2θ. After the geopolymerisation reaction, the broad hump skewed to the
composition (Garcia-Lodeiro et al., 2011; Ismail et al., 2014). The in­ right (20◦ –40◦ 2θ) in OPG, denoting the generation of amorphous re­
termediate compositions between these two regions suggested a binding action products (Ishwarya et al., 2019). The fly ash mainly consisted of
phase of N-A-S-H and C-A-S-H, or (N,C)-A-S-H and C-A-S-H were formed. quartz, mullite, anhydrite and hematite, whereby anhydrite is the main
The formation of these phases was also observed by Ismail et al. (2014), source of calcium in the fly ash. After alkali activation, some quartz and
in the alkali activation of fly ash and slag. The MC-OPG had a wide hematite peaks originated from fly ash remained in the OPGs (Criado
compositional range of 0.44 < Ca/Si < 4.57 and 0.33 < Al/Si < 1.43. et al., 2007), indicating that these minerals were relatively inert. This
was consistent with the SEM micrographs (Figs. 7 and 8) showing fly ash

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O. Wan-En et al. Journal of Cleaner Production 378 (2022) 134370

Fig. 10. (a) Ternary plot of CaO–Al2O3–SiO2, and (b) atomic ratio of Al/Si versus Ca/Si of the optimal MH-OPG and MC-OPG.

incorporation of Na2CO3 introduced CO2− 3 which reacts with Ca2+

released from the high calcium fly ash to produce calcium carbonate.
This reaction occurred at the initial stage of the reaction, prior to the
precipitation of hydrate gels (Bernal et al., 2015). Concurrently, the
CaO-deficient condition favoured the development of N-A-S-H gel
because Na+, Si4+, Al3+ and OH− ions were available for precipitation.
As ageing progressed, the concentration of CO2− 3 reduced, leaving
available Ca2+ ions in the system that promoted the precipitation of
C-A-S-H gel. There were three possible explanations for the formation of
C-A-S-H gel instead of (N,C)-A-S-H gel: (1) the Na+ ion was exhausted at
the later stage of the reaction; (2) the use of a moderate alkaline com­
pound (Na2CO3) encouraged the formation of C-A-S-H gel (Garcia-Lo­
deiro et al., 2016); and (3) the Ca2+ ion has a stronger polarizing power
(Garcia-Lodeiro et al., 2011). The stress-bearing calcium carbonate and
C-A-S-H gel phase make amends to the negatively affected geo­
polymerisation reaction caused by the less alkaline Na2CO3.

3.7. Functional group identification

Fig. 12 displays the FTIR spectra of the fly ash, optimal MH-OPG and
MC-OPG. To ease the comparative analysis of the key structural network
bonding, the wavenumbers of all data were normalised to the region of
Fig. 11. XRD diffractograms of fly ash, optimal MH-OPG and MC-OPG. 650–2000 cm− 1. Traces of carbonates with asymmetric stretching vi­
bration bands of O–C–O (Ishwarya et al., 2019) were observed at 1503
remnants in OPGs. The disappearance of anhydrite and mullite signified cm− 1 in fly ash and at 1484, 1415 and 1412 cm− 1 in the OPGs. The
that these phases had partaken in the development of reaction products. bands indicated that atmospheric CO2 might diffused into the fly ash and
The MH-OPG revealed the formation of boggsite (sodium calcium the OPGs. Meanwhile, the more intense bands shown in the MC-OPG
aluminium silicate hydrate), which can also be denoted as (N,C)-A-S-H spectra justified the formation of carbonates or possibly the undis­
gel phase. The result was consistent with the elemental composition solved activator of Na2CO3. This is in good agreement with the XRD
analysis as shown in Fig. 10. The participation of NaOH favoured the
attack of Si–O and Al–O in fly ash, releasing high concentration Ca2+,
Na+, Al3+, Si4+ and OH− ions required for the reaction product pre­
cipitation. The formation of (N,C)-A-S-H gel was anticipated as both Na+
and Ca+ ions act as the charge balancer in the tetrahedral SiO4 and AlO4-
linked chain structure (Davidovits, 2005). As the reaction progressed,
the solid alkali activators and fly ash dissolved concurrently, leading to a
consistent proportion of the local ions’ concentration. The binding phase
of N-A-S-H or C-A-S-H gel was unlikely to constitute in the OPG based on
high calcium fly ash, Na2SiO3 and NaOH. The finding was assured by
Garcia-Lodeiro et al. (2016) who stated that NaOH was a highly alkaline
activator that prompted the formation of (N,C)-A-S-H gel in the
Ca-containing mixtures.
The formation of calcium carbonate hydrate was identified in the
MC-OPG, supporting the angular crystals observed in Fig. 9. It was also
detected in the Na2CO3-activated slag-based OPG (Wang et al., 2021).
The chabazite-Ca and sodium aluminium silicate hydrate were also
identified in MC-OPG. The co-existence of N-A-S-H and C-A-S-H gel is
feasible in geopolymers (Soutsos et al., 2016). The precipitation kinetics
relies on the ionic species present in the mixture. The MC-OPG was
saturated with Ca2+, Na+, Si4+, Al3+, CO2− 3 and OH− ions. The
Fig. 12. The FTIR spectra of the fly ash, optimal MH-OPG and MC-OPG.

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O. Wan-En et al. Journal of Cleaner Production 378 (2022) 134370

analysis as shown in Fig. 11. et al., 2018), accounting for relatively high EC (0.83 kg CO2/kg) (Ade­
Another significant difference was the disappearance of the absorp­ sina, 2021). Although the EC of Na2SiO3 was higher than that of OPC,
tion band at 1129 cm− 1 in the MH-OPG and MC-OPG that were origi­ the amount of Na2SiO3 required for OPG production was relatively
nally present in the fly ash. The band corresponded to the asymmetric lower. Hence, the cementitious product incorporated with Na2SiO3 was
stretching of the (Si,Al)–O–Si band that originated from mullite greener than other cementitious products involving OPC. The cement
(Al6Si2O13) (Zhang et al., 2012). The finding also in line with the XRD concretes have lower ECI due to the incorporation of aggregates with
analysis (Fig. 11), whereby the mullite mineral is present in the fly ash lower EC (0.007 kg CO2/kg for coarse aggregates and 0.001 kg CO2/kg
but not in the optimal MH-OPG and MC-OPG. This justified that the Si for river sand (Long et al., 2015)). Thus, the OPG concrete carbon
and Al species in the fly ash have participated in the geopolymerisation footprint was lower. In short, OPG contributed the lowest carbon foot­
reaction. The absorption band between 990 and 970 cm− 1 in the fly ash print and possessed relatively excellent compressive strength among the
and the OPGs was the characteristic asymmetric stretching vibrations of various types of cementitious materials, especially those incorporated
the Si–O-T (T = Si or Al) bond. These bands showed the amorphous with Na2CO3, confirming that OPG is the potential solution against
nature of the raw materials and the reaction products. As a consequence global warming.
of geopolymerisation reaction and the increasing degree of crosslinking
of the products, the bands shifted towards a lower wavenumber (Ismail 4. Conclusions
et al., 2014). The position of this band in MH-OPG was lower (974 cm− 1)
than the MC-OPG (981 cm− 1), suggesting the higher crosslinking degree This work evaluated and compared the performances of greener
of the (N,C)-A-S-H gel than the N-A-S-H and C-A-S-H gels. The minor OPGs based on high calcium fly ash activated using anhydrous Na2SiO3,
peaks at around 685 cm− 1 in all samples corresponded to the symmetric NaOH and Na2CO3. Two sets of OPGs were developed. The MH-OPG was
stretching vibration of Si–O-T (T = Si or Al) (Panias et al., 2007). activated with Na2SiO3 and NaOH, while the MC-OPG was activated
with Na2SiO3 and Na2CO3. In the effort of moving towards greener
environment, it was found that the types of solid alkali activators and
3.8. Environmental impact evaluation varying the mixing parameters significantly affected the properties of
the OPG. The following noteworthy conclusions can be made:
The environmental impact in the building sector has come under
scrutiny. EC is one of the measurements for the carbon footprint. EC is (i) The MH-OPG achieved a compressive strength of 72.7 MPa with
the total carbon emitted to convert the raw material into a product. an AA/FA ratio of 0.15, an SM/SH ratio of 3.0, and a W/B ratio of
Since the production flow of the OPGs was the same, the raw materials 0.30, while, the MC-OPG achieved a compressive strength of
with a lower EC should result in OPGs with a lower carbon footprint. The 75.1 MPa with an AA/FA ratio of 0.20, an SM/SC ratio of 1.0 and
EC of the raw materials utilised in this study are listed in Table 5. a W/B ratio of 0.20. These optimal mix designs were selected
Anhydrous Na2SiO3 was the main contributor of EC. Even though based on the fluidity, setting time and compressive strength. The
anhydrous Na2SiO3 resulted in OPG with better workability and higher AA/FA and SM/SC ratios were the most influential factors
compressive strength than Na2SiO3 pentahydrate or unspecified hydrous affecting the compressive strength of MH-OPG and MC-OPG,
Na2SiO3 (Luukkonen et al., 2018), the extensive CO2 emission of the respectively. The influence of the SM/SH ratio was not
anhydrous Na2SiO3 encouraged research in reducing its reliance on significant.
OPGs synthesis. The EC contributed by the raw materials in one cubic (ii) The use of various solid alkali activators drove different reaction
meter of optimised OPGs is graphically represented in Fig. 13. The total mechanisms and yielded distinctive reaction products. The
EC of MC-OPG was 15.4% lower than that of MH-OPG because Na2CO3 consistent proportion of the local ions’ concentration in the MH-
has a lower EC value and replaced more Na2SiO3 than NaOH. In this OPG drove (N,C)-A-S-H gel formation. The incorporation of
study, the Na2SiO3 could not be omitted fully due to the mechanical Na2CO3 changed the pace of compound formation and yielded
strength concern. sodium carbonate hydrate, N-A-S-H and C-A-S-H binding phases
ECI is an indicator for an environmentally beneficial product. A low in the MC-OPG.
ECI value is more desirable. Aside from emphasizing environmental (iii) The ECI of the optimal MH-OPG and MC-OPG were 81.3% and
sustainability (low EC), the mechanical strength of the geopolymer shall 84.7% less than that of OPC products, indicating a successful
not be compromised. The ECI of OPGs in this study and other cemen­ development of greener OPGs. The EC of MC-OPG was 15.4%
titious materials are summarised and compared in Table 6. The ECI of lower than the MH-OPG because MC-OPC allowed a greater
the OPGs incorporated with Na2CO3 was the lowest among the cemen­ substitution amount of anhydrous Na2SiO3 with Na2CO3.
titious materials and could potentially be used to develop cleaner (iv) Although the optimal OPGs had similar compressive strengths, a
cementitious products. Based on the current study, with almost similar better fluidity and longer setting time were attained by the MC-
strength achieved, the ECI values of MC-OPG were lower than the MH- OPG due to the incorporation of Na2CO3 that reduced water de­
OPG. This implied that substituting Na2SiO3 with Na2CO3 instead of mand. Yet, the MH-OPG was less sensitive towards the alteration
NaOH has better mechanical performance and higher sustainability of mixing factors, indicating easier performance control and more
value. favourable for field applications.
Compared to the OPC paste, the ECI values of the MH-OPG and MC-
OPG were 81.3% and 84.7% lower, indicating that geopolymer mate­ The study justified that the effect of mixing parameters on the
rials were more environmentally friendly. The manufacturing process of compressive strength was different for OPG and traditional geopolymer.
OPC involved the calcination of limestone to ~1450 ◦ C (Luukkonen The compressive strengths achieved by the optimal OPGs greatly exceed
the minimal requirement (>28.0 MPa) of the ASTM C150/C150M-18 for
Table 5 construction binder application. With a good balance of fresh, physical
EC (kg CO2/kg) of raw materials. and mechanical properties, the developed OPGs are suitable for a wide
Fly ash Anhydrous NaOH Na2CO3 Water arrange of applications, such as load-bearing structures, precast blocks,
Na2SiO3 grouting, cement floor, concrete beams, repair and maintenance pur­
0.0001 1.86 0.86 0.11 0.005 poses or 3D printing applications for structures.
(Abdelmonim (Abdelmonim (Adesina, (Adesina, (Adesina,
and Bompa, and Bompa, 2021) 2021) 2021)
2021) 2021)

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O. Wan-En et al. Journal of Cleaner Production 378 (2022) 134370

Fig. 13. The EC distribution of the optimised (a) MH-OPG and (b) MC-OPG.

Table 6
Environmental impact evaluation of various cementitious materials.
Type of products Raw materials 28-d compressive strength EC (kg CO2/ ECI (kg CO2/ Reference
(MPa) m3) m3/MPa)

One-part geopolymer Fly ash, Na2SiO3, NaOH, water 72.72 325.54 4.48 TS
One-part geopolymer Fly ash, Na2SiO3, Na2CO3, water 75.08 275.44 3.67 TS
One-part geopolymer GGBFS, Na2SiO3, Na2CO3, water 65.80 234.91 3.57 Ma et al. (2019)
One-part geopolymer GGBFS, Na2SiO3, water 76.30 381.50 5.00 Ma et al. (2018)
One-part geopolymer Lithium slag, GGBFS, Na2SiO3, water 57.00 625.86 10.98 Shah et al. (2021)
Cement concrete OPC, sand, coarse aggregates, superplasticizer, water 88.30 462.44 5.24 Kumar et al. (2021)
Alkali-activated slag GGBFS, Na2SiO3, NaOH, water 56.00 347.86 6.21 Long et al. (2019)
Cement concrete OPC, fine aggregates, coarse aggregates, water 51.80 440.00 8.49 Adesina (2021)
Engineered Cementitious Cement, limestone-calcined clay, silica sand, water, 64.50 580.50 9.00 Yu et al. (2020)
Composite superplasticizer, PVA fiber
Self-compacting concrete OPC, river sand, crushed limestone, superplasticizer, 43.10 409.45 9.50 Long et al. (2015)
viscosity modified agent
High volume fly ash cement Fly ash, OPC, water 24.30 472.88 19.46 Kulasuriya et al.
(2021)
Cement OPC, water 65.00 1555.45 23.93 Kulasuriya et al.
(2021)

TS = this study; PVA = polyvinyl alcohol.

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