Cement and Concrete Composites 118 (2021) 103980

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Cement and Concrete Composites

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Waste-derived activators for alkali-activated materials: A review

Mohammed Fouad Alnahhal *, Taehwan Kim, Ailar Hajimohammadi
Centre for Infrastructure Engineering and Safety, School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW, 2052, Australia

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

Keywords: Alkali-activated materials (AAMs) are increasingly attracting attention as a promising sustainable alternative to
Alkali-activated materials Portland cement-based materials. This study presents the key advancements in the synthesis of alternative so­
Geopolymer dium silicate activators using silica-rich waste resources, such as rice husk ash, waste glass, nanosilica and
Sodium silicate
microsilica. Different silicate extraction methods, including fusion, hydrothermal, and thermochemical processes
Silica-rich wastes
Activators
were compared, and the roles of various parameters on the silica dissolution rate were deliberated. In addition,
the efficiency controlling factors of the synthesized activators were rigorously reviewed using the compressive
strength, setting time, and microstructural characteristics of the resulting AAMs. The extraction of silica was
shown to be effective using hydrothermal and thermochemical processes. Moreover, the recent studies showed
that the proper selection of the raw materials and the extraction conditions allow for maximizing the yield of
silica from the silica-rich wastes. Such proper selection provides mechanical and microstructural properties of
AAMs activated by the synthesized activators comparable to those from the commercially available activators.

1. Introduction classified as “geopolymers”, can be obtained through the alkali activa­

Concrete is the dominant material used in the construction industry
from simple-family houses to architecturally innovative skyscrapers [1].
Concrete production will continue to increase in the foreseeable future
due to the increased population and the economic growth in developed
and developing countries. As a result, there is an alarming increase in
the production of ordinary Portland cement (OPC) (4.10 billion tonnes
in 2017 [2]), which contributes to 5–8% of all human-made CO2 emis­
sions [3,4]. However, CO2 could be sequestered as a result of the carbon
uptake by concrete carbonation, resulting in a reduction of the net CO2
emissions during the concrete life cycle [5,6]. Besides the environmental
impact of OPC, other challenges such as significant consumptions of
energy and natural minerals have raised concerns about the ecological
imbalance and sustainability of OPC-based concrete [7]. Therefore,
engineers and scientists have dedicated significant efforts to make a
technological breakthrough in reducing reliance on OPC as a standalone
binder. The common methods to modify the main binder are i) the
incorporation of supplementary cementitious materials (SCMs) as a
partial replacement of OPC and ii) development of alternative binders
that entirely replace OPC.
One of the promising alternative binders is alkali-activated materials
(AAMs), and significant efforts have been made to increase the viability
and the effectiveness of AAMs in concrete [8–13]. AAMs, including those
tion process of aluminosilicate sources, such as metakaolin, fly ash, or
blast furnace slag. AAMs are activated using an alkaline source to
facilitate the transformation of solid aluminates and silicates in the
precursor into a synthetic aluminosilicate gel [14,15]. The formation of
the main bonding gel in low calcium fly ash-based AAMs, known as
N–A–S–H, requires temperatures exceeding 60 ◦ C to achieve high
early-age strength [16,17]. Heat curing has a significant effect on the
formation of a polymeric structure in the bonding gel, leading to a low
volume of permeable voids [16]. At ambient temperature, fly ash par­
ticles are not fully dissolved and the diffusion of hydroxide and silicate
ions occurs at higher curing temperatures [17]. This heat curing method
would not be a commercially viable process due to the difficulty of
in-situ applications and energy consumption. However, a small per­
centage of calcium-rich additives such as blast furnace slag can improve
strength development, and thus, allow AAMs to achieve a satisfactory
strength at ambient temperature [18,19]. The improved strength is
mainly the result of the formation of aluminium-modified calcium sili­
cate hydrate (C–A–S–H) gel [19,20]. Moreover, the use of AAMs pro­
vides several benefits, including lower CO2 emission and superior
performance when compared to OPC binders. For instance, previous
studies have reported that AAM-based concrete shows higher thermal
performance [21,22] and improves resistance against aggressive
chemicals [14,23]. Nevertheless, the large-scale commercial use of

* Corresponding author.
E-mail addresses: m.alnahhal@unsw.edu.au (M.F. Alnahhal), taehwan.kim@unsw.edu.au (T. Kim), ailar.hm@unsw.edu.au (A. Hajimohammadi).

https://doi.org/10.1016/j.cemconcomp.2021.103980
Received 3 November 2020; Received in revised form 5 February 2021; Accepted 8 February 2021
Available online 14 February 2021
0958-9465/© 2021 Elsevier Ltd. All rights reserved.
M.F. Alnahhal et al.
AAMs remains extremely small due to technological obstacles related to
the high energy and CO2 emission arising from the production process of
the alkaline activators. A recent study by Scrivener et al. [1] stated that
the CO2 footprint of the sodium silicate activator should be at least
halved to achieve a scalable technology of AAMs.
To promote the commercial viability of AAMs, it is essential to
reduce the production costs of AAMs while maintaining their superior
performance and environmental friendliness. The alkaline activator is a
key component in AAMs that has recently attracted notable attention.
The use of alkaline activator solutions is often considered as one of the
major practical shortcomings in AAMs because such activator solutions
are expensive, corrosive, and not environmentally friendly [24]. Large
amounts of sodium silicates are usually needed for the activation of
AAMs. Therefore, the embodied energy, carbon footprint, and the cost
associated with these activators are considerably high [25]. Conse­
quently, there is a pressing need for developing sustainable and
cost-effective activators that can substantially improve the prospects of
using AAMs. There is a growing body of research about the alternative
activators that are more sustainable, user-friendly, and cost-effective
[26]. To progress towards more sustainable alkaline activators, the
synthesis of alternative solutions based on a mixture of alkalis and
waste-derived silica has been promoted. These waste resources include
bottom ash [27], rice husk ash (RHA) [28,29], waste glass (WG) [26], fly
ash [30], microsilica [24], silica fume [31], green olivine nano-silica
[32] and precipitated silica [33]. The dissolved silica from these sour­
ces into an alkaline hydroxide solution yields an alkaline silicate acti­
vator comparable to the commercial one mainly produced from the
commercial sodium silicate. Moreover, the environmental footprint of
the alternative activators indicated a possible reduction in CO2 emis­
sions by up to 50% compared to the commercially available sodium
silicate, depending on the extraction method [34–37].
The synthesis of alternative sodium silicate would benefit not only
the formulation of AAMs but a wide variety of applications, including
fractured oilfields [38], drilling fluids [39–41], heat-resistant binders
[42,43], and in fire prevention and extinction in coal mines [44–46].
This paper reviews the current state-of-art in the development of alter­
native sodium silicate activator for AAMs using a combination of alka­
line and silica-rich waste resources. Different extraction methods have
been carried out by researchers to develop alternative activators using
silica-rich resources. However, no critical review of the performance and
efficiency of these different methods and the derived activators
currently exists. This paper is significant as it identifies the key param­
eters that impact the efficiency of the synthesized alkaline activators.
The reviewed factors include the extraction method along with the
mineralogical characteristics of silica and the effect of the alkali source.
The efficiency of the alternative activators was assessed by evaluating
the compressive strength, setting time, and microstructural character­
istics of the resulting AAMs.
2. Environmental concerns with alkaline activators
Soluble silicates and alkali ions in the activating solution have a
significant impact on the formation of a dense and compact micro­
structure in AAMs. Silicate species and OH− ions in the activating so­
lution can be obtained from several sources such as NaOH, KOH,
Na2SiO3, Na2Si2O5, Na2CO3, and Na2SO4 [47]. Commercial sodium sil­
icate solution is one of the most widespread alkaline activators used in
AAMs. Notably, conventional alkaline activators are manufactured by
an energy-intensive process that results in high carbon footprint [34].
For example, in the case of sodium silicate manufacturing, high energy is
required to melt sodium carbonate (Na2CO3) with silica sand (SiO2) in
the kiln at temperatures between 1400 and 1500 ◦ C [29]. Besides, the
decomposition process generates major emissions, where CO2 is directly
emitted from Na2CO3 to obtain Na2O. As a result, the use of conventional
activators would increase the overall embodied energy and greenhouse
gas emission, and this environmental impact must be considered when
2
Cement and Concrete Composites 118 (2021) 103980
analysing the benefits of AAMs. Still, it is generally well agreed that
AAM-based concrete has a lower environmental impact than OPC-based
concrete [48,49]. However, the environmental impact of AAMs varies
quite widely depending on the mix design, type of activator, curing
condition, source location, and the mode of transport [50]. For example,
the life cycle analysis of slag/fly ash-based AAM in one study showed
62%–66% reduction in the greenhouse gas emissions compared to OPC
concrete with a similar strength [51]. On the other hand, another study
[52] concluded that the CO2 footprint of fly ash-based AAM was only 9%
less than OPC concrete. In their research, Turner and Collins [52]
considered an additional CO2 emission related to heat curing of the
specimens as they used the heat-cured fly ash system, while the new
generations of slag/fly ash-based AAMs are ambient cured systems.
Despite this fact, the manufacturing process of alkaline activators is
responsible for about 60% of greenhouse gas emissions in AAM concrete
[52].
With increasing demand on the development of sustainable concrete
by incorporating a circular economy approach, waste-derived activators
can provide an effective way not only to reduce the greenhouse gas
emission of AAM concrete but also to reprocess wastes into valuable
activators that can substitute the conventional alkali-silicate activators.
The environmental impact of the alternative alkaline activators should
be assessed by estimating the level of contribution of the alternative
route in reducing the global warming potential. In one study, the CO2
emitted from the combustion of rice husks has been taken into account
[36]. In some other studies, only the environmental impact incurred
during the synthesis process of the alternative activators was considered
[34,35]. Some silica-rich resources are by-products of other life cycles,
and hence, the CO2 emissions arising from the combustion process can
be ignored. Hydrothermal process, which is commonly used to produce
an alternative activator in the liquid form, usually consumes less energy
compared to the other methods used to produce solid activators [53]. A
previous study [35] on soluble alkali-silicate activators showed that the
global warming potential impact can be reduced by 7–22% and 41–47%
for AAMs activated using commercial and RHA-derived solutions,
respectively, in comparison to Portland cement. For solid alkaline acti­
vators, the greenhouse gas emission arising from AAM made of
WG-derived activator was 2.5 times lower compared to the commercial
activator [37]. Based on the available studies, it can be concluded that
the development of alternative routes is feasible for formulating
low-carbon-footprint alkaline activators.
3. Alternative activators from silica-rich resources
The high silica availability in the activator plays an important role in
the conversion of solid precursors into a geopolymeric gel [54]. Silica is
essential for the polycondensation reaction (i.e., geopolymerization),
which in turn affects the overall performance of AAM concrete,
including the mechanical properties [55]. As previously explained, the
commercial alkaline silicates involve high energy consumption and CO2
emissions during the manufacturing process. The extraction of alterna­
tive activators from silica-rich resources is a viable solution to reduce the
environmental impact of alkaline activators. This section introduces
potential resources of silica-rich wastes and different extraction methods
from previous literature.
3.1. Silica-rich resources for alkali activation
The industrial activities around the world generate a wide range of
silica-rich by-products that have become a major environmental
concern. Hence, it was crucial to identify suitable waste management
techniques to reduce their environmental impact. Silica-rich wastes
have been utilized as SCMs for enhancing the performance of OPC
concrete [56–59]. More recently, considerable studies have been carried
out on AAM concrete incorporating silica-rich materials as both pre­
cursors and activators, including fly ash [60,61], blast furnace slag [62],
M.F. Alnahhal et al. Cement and Concrete Composites 118 (2021) 103980

interest in the AAMs, possible reuse of WG in other ways serves as an

avenue in minimizing its harmful impact. For instance, a few studies
have dealt with the feasibility of using WG in the synthesis of alkaline
activators that can replace the standard activator in AAMs [78,105].
The other silica-rich resources covered in this study are microsilica
and silica fume. These are commercially available silica from silicon and
ferrosilicon alloy production that have been commonly used by the
concrete industry to enhance the mechanical and durability properties
of concrete [106]. Recently, microsilica has been also used for the
development of alternative sodium silicate activators [24]. Further
studies have been conducted to explore the potential use of silica fume in
the production of alternative alkaline activators [69–71,107]. Their
results showed that the alternative activator developed from a mixture
of alkalis and silica fume could be used in the production of AAMs.
To obtain an alternative activator for AAMs, silica needs to be
extracted at high temperatures within an alkaline medium [36,108].
Different silica extraction approaches commonly used in literature are
explained in detail in the next section.

3.2. Silica extraction methods

As can be seen from Table 1 and Fig. 2, different silica extraction

methods have been designed to produce sodium silicate activator from
Fig. 1. Ternary diagram showing the major oxides and LOI of amorphous silica
[55], silica fume [31,69–71], RHA [24,34,36,72–77], WG [26,37,78–81] and various silica resources. The resulting activators were mainly used for
bottom ash [27]. the activation of metakaolin, fly ash, slag, red mud, calcined kaolin
sludge, water treatment sludge, and fluid catalytic cracking catalyst.
Several extraction techniques were considered, including fusion, hy­
silica fume [31,63], RHA [36,64,65] and waste glass (WG) [66]. Among
drothermal and thermochemical methods. El-Naggar and El-Dessouky
several silica-rich wastes, this section briefly presents the sources that
[80] introduced a fusion process to extract the silica from WG. In this
usually contain more than 70% of silica. Such silica-rich materials are
technique, a mixture of WG and NaOH pellets was heated up to 550 ◦ C,
more favourable for extracting silicate than the other sources such as fly
and then the mixture was dissolved in distilled water. This method was
ash and slag in which silica contents are within the range of 30%–60%
found beneficial in terms of maximizing the extraction of reactive silica.
[67,68]. A ternary diagram (Fig. 1) is developed to present the layout of
However, the adverse effect of the high temperature (550 ◦ C) required
all major oxides and LOI of various silica rich wastes used in the previous
for fusion may not lead to a significant reduction in the environmental
literature to facilitate the understanding of their chemical composition
impact of the synthesized activator. Hence, a low-temperature synthesis
(especially the content of SiO2).
route was carried out by other researchers, which involves the dissolu­
RHA is one of the commonly used silica-rich wastes. Rice husk is
tion of the silica-rich source into an alkaline solution at temperatures
mainly used as a fuel for power generation in the biomass plants. The
between 20 ◦ C and 100 ◦ C [27,36]. Long processing time of up to 72 h
resulting ash after combustion, i.e. RHA, is approximately 20% by
was required to enhance the dissolution efficiency at a temperature as
weight of the husk and 4% of rice paddy [82]. The annual production of
low as 20 ◦ C. Therefore, Vinai and Soutsos [26] carried out a thermo­
paddy rice was estimated to be approximately 770 million tonnes
chemical process to optimize the processing time and temperature in the
around the world [83]. Hence, the potential production of RHA, con­
development of sodium silicate powder. This process consists of mixing
taining about 90% of amorphous silica is 26–34 million tonnes [84]. The
NaOH and silica-rich source at temperatures ranging between 150 and
use of RHA as SCM in the concrete industry has become increasingly
450 ◦ C. Their results indicated that heating the mixture for one hour at a
common [85–87]. Furthermore, researchers have applied various
temperature of 150 ◦ C was effective to obtain sodium silicate powder
methods to utilize RHA and produce alternative alkaline solutions for
that is suitable for one-part AAM casting. Another study showed that the
AAMs [36,88]. RHA has also been used as a silica-rich precursor for
heat treatment of WG with NaOH at 150 ◦ C is effective to achieve a
developing one-part AAM together with solid sodium aluminate acti­
conversion efficiency of ~70% of solid sodium silicate in the form of
vators [89]. One-part AAM mixes just require water to be added to a dry
Na2SiO3 [37]. The majority of these studies have used NaOH to extract
mixture of precursors and anhydrous activator for initiating the geo­
the silicates from the different silica-rich by-products. However, some
polymerization and hardening of AAM [90,91]. The development of
studies used different alkaline solutions to extract the silicate, i.e.,
one-part AAMs eliminates the risks of handling corrosive activating
NaOH/Na2CO3 [78], and KOH [33,109]. Hajimohammadi and van
solutions. However, the commercial trials of one-part AAMs have been
Deventer [89] and Sturm et al. [75] used RHA as both the binder and the
still very limited compared to several full-scale implementations of
activator source in developing one-part AAM mixes.
two-part AAMs that have been successfully made for structural purposes
The overall performance of these waste-derived alkaline activators
[92,93].
has been satisfactory as the resulting AAMs could achieve reasonable
Another silica-rich source is WG [94,95]. In the US in 2017, about
mechanical and microstructure performance, (which will be further
11.4 million tons of WG were generated, of which 60% landfilled, 13%
discussed in Section 4). However, no standard method was followed by
combusted with energy recovery, and only 27% recycled [96]. By
the researchers, and different parameters were used in each study,
contrast, similar amounts of WG were collected in the European Union,
including the particle size of silica sources, heating temperature, and
but the recycling rate reached a threshold of 74% [97]. Researchers have
mixing time. Also, most of the researchers have not measured (reported)
attempted to use WG in concrete with the main focus on fine aggregate
the amount of dissolved silica extracted from the silica-rich resources.
replacement [98–101]. However, one of the concerns about using WG as
The chemical compositions of extracted activators are critical for syn­
fine aggregates in OPC concrete is the alkali-silica reaction which causes
thesizing a feasible alkaline activator. The amount of silicate dissolved
excessive expansion and cracks because WG is mainly composed of
from the waste material would be a function of the alkaline to the waste
highly reactive silica [102–104]. Alternatively, with the growing
source ratio, amorphous content of the silica-rich resource, the amount

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M.F. Alnahhal et al. Cement and Concrete Composites 118 (2021) 103980

Table 1
Summary of different extraction methods to produce sodium silicate activator from various silica sources.
Reference Silica characteristics of raw material Extraction conditions Remarks
a
Silica source SiO2 (%) LOI (%) Average Alkaline Molarity of Temperature Duration
particle source alkaline (◦ C)
size (μm) solution
(mol/L)

Tchakouté et al. RHA and WG 83.05 and 0.55 <90 NaOH NRb 100 2h RHA contained a higher
[105] 68.70 pellets amount of amorphous silica
than WG. The extracted
activator was filtered to
separate the undissolved
particles.
Tchakouté et al. RHA 93.49 NR NR NaOH NR 80 2h Pure silica was obtained from
[112] pellets RHA by leaching rice husk in
HCl. After that, waterglass was
prepared using the purified
RHA.
Tong et al. [36] RHA 90.5 3.8 6.82 NaOH 1.0, 2.0, Room temp., 1, 3, 5, 7 The activator was extracted
pellets 3.2, 4.9, 60, 80, 90 and and 15 h using a hydrothermal process
and 6.5 100 (heating and stirring). The
yield of silica from RHA was up
to 95%.
Kamseu et al. [29] RHA NR NR <45 μm NaOH 8, 10 and Room temp. 40 min RHA and NaOH solution were
granules 12 ball-milled in a porcelain jar
(1200 rpm) for 40 min. The
extracted activator was kept
for at least 24 h before being
used in casting.
Passuello et al. [35] RHA 97.3 NR 9.87 NaOH NR 100 1h The dissolution was carried out
in a refluxed system to avoid
the escape of water. The SiO2/
Na2O weight ratio of the
filtered activator was 2.2
compared to 2.5 in the
commercial one.
Bernal et al. [31] RHA and silica 68c and <2 9.2 and NaOH NR Room temp. 10 min The derived solution was
fume 95.51 64.1 stored for 24 h at room
temperature (25 ◦ C) before
mixing with the precursors.
Only the amorphous silica
content was considered in the
calculation to obtain the
desired SiO2/Na2O ratio.
He et al. [73] RHA 91.5 6d 25 and 32 NaOH 2, 4 and 6 Room temp. 15 min A dry mixing was conducted
first for the RHA and red mud
followed by dissolving and
stirring the mixture in NaOH
solution for at least 15 min.
Mejía et al. [74] RHA 90.91 5.10 4.6 NaOH NR Room temp. 24 h The amorphous silica content
was 36%. RHA dissolved in
NaOH solution under constant
stirring.
Mejía et al. [72] RHA ~94 2.8–3.5 36.9–39.5 NaOH NR Room temp. NR RHA and NaOH solution were
mixed, and the resulting
activators were kept in closed
containers at room
temperature for 1-day prior to
use. Solubility of silica was
>90%.
Geraldo et al. [76] RHA 89.51 6.95 20.4 NaOH NR Room temp. 30 min Two solutions containing RHA,
and 90 NaOH, and water were
produced: 1) treated solution,
which was exposed to heating
and stirring for 30 min; and 2)
untreated solution. The
dissolved silica in the treated
solution was 50% higher than
the untreated one.
Bouzón et al. [88] RHA 85.58 6.99 20.3 and NaOH NR 100 5–240 The aqueous mixtures were
62.3 min boiled in a reflux system for
different durations. ~80% of
silica was dissolved within 60
min.
Luukkonen et al. RHA and 88.46 and 9.22 23, 30, 172 NaOH 0.1, 1 and Room temp. 4h Up to 35% and 10% of Si was
[24] microsilica 94.25 and and 199 10 dissolved after 4 h from
2.31
(continued on next page)

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M.F. Alnahhal et al. Cement and Concrete Composites 118 (2021) 103980

Table 1 (continued )
Reference Silica characteristics of raw material Extraction conditions Remarks

Silica source SiO2 (%)a LOI (%) Average Alkaline Molarity of Temperature Duration
particle source alkaline (◦ C)
size (μm) solution
(mol/L)

microsilica and RHA,

respectively.
Hajimohammadi RHA 56.22 40.42 8 NaAlO2 N/A Room temp. N/A Solid sodium aluminate was
and van Deventer mixed with high carbon RHA,
[89] e and subsequently water was
added to synthesize one-part
mix geopolymers.
Sturm et al. [75] e RHA 88.49 2.48 11.1 NaAlO2 N/A Room temp. N/A One-part geopolymers were
synthesized by mixing solid
sodium aluminate with RHA
and subsequently adding
water.
Başgöz and Güler RHA 85.14 NR NR NaOH 1 95 NR RHA was mixed with 1 M
[77] NaOH solution at 95 ◦ C. the
mixture was then filtered to
remove the undissolved
residues.
El-Naggar and El- WG 82.52 0.41 <38 and NaOH NR 550 NR A mixture of 30 g of NaOH
Dessouky [80] 38–125 pellets pellets and different amounts
of WG (1, 3, 7, 10, 15, and 30
g) was heated at 550 ◦ C
followed by mixing with 25.5 g
of distilled water. The non-
dissolved residues were
separated by centrifugation.
Torres-Carrasco WG 69.9–71.4 NR <45, NaOH and 4 22 and 80 10 min A hydrothermal process was
et al. [110] 45–90 and NaOH/ and 2, 4 carried out to dissolve 1 g of
> 125 Na2CO3 and 6 h glass per 100 mL of solution.
~60% of silica was dissolved at
80 ◦ C.
Torres-Carrasco WG 70.71 0.83 <45 NaOH 10 80 6h NaOH solution mixed with 10,
and Puertas 15, and 25 g of glass per 100
[111] mL of solution. 28%–44% of
silica was dissolved in the
solution.
Torres-Carrasco WG 72.1 0 <45 NaOH/ NR Room temp. 24 h 25 g of waste glass was
et al. [79] Na2CO3 dissolved in 100 mL of NaOH/
Na2CO3 solution by magnetic
stirring.
Puertas and Torres- WG 70.71 0.83 <45 NaOH/ NR 80 6h NaOH/Na2CO3 solution mixed
Carrasco [78] Na2CO3 with different amounts of glass
(1, 10, 15, 20, and 25 g per
100 mL of solution). The
dissolved silica ranged
between 26% and 59%.
König et al. [81] WG 72.37 NR <90 NaOH 10 120 4 h and Bottle glass waste was mixed
flakes 24 h with 10 M NaOH solution at
powder mass to volume of 10
M NaOH of 0.025 g/mL and
0.1 g/mL. The system was
mixed and heated at 120 ◦ C for
either 4 h or 24 h. Silicon and
aluminium concentrations
were then determined in the
filtered solution.
Vinai and Soutsos WG 71.51 0.27 12 NaOH NR 150, 250, 330 1, 2 and 4 Heat treatment was applied on
[26] and 450 h a dry mix of WG and NaOH
with SiO2/Na2O mass ratio
varied between 1 and 4 to
produce sodium silicate
powder.
Rodríguez et al. Nanosilica NR NR NR NaOH and NR NR NR The activator was prepared by
[109] KOH the dissolution of nanosilica in
NaOH or KOH solution to
obtain a molar oxide ratio
SiO2/M2O of 1.16, where M
corresponds to Na+ or K+.
Alam et al. [27] Incineration 58.8 2.7 <125 NaOH NR 20, 75 and 90 24, 48 The bottom ash was initially
bottom ash and 72 h treated with nitric acid. ~55%
of silica was dissolved within
48 h of dissolution at 75 ◦ C.
(continued on next page)

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M.F. Alnahhal et al. Cement and Concrete Composites 118 (2021) 103980

Table 1 (continued )
Reference Silica characteristics of raw material Extraction conditions Remarks

Silica source SiO2 (%)a LOI (%) Average Alkaline Molarity of Temperature Duration
particle source alkaline (◦ C)
size (μm) solution
(mol/L)

Autef et al. [55] Amorphous 99.9 and NR 0.14 and KOH NR Room temp. NR The alkaline silicate was
silica and 98.6 90 pellets prepared by dissolving the
crystallized silica in KOH solution at the
quartz ratio of Si/K = 0.7.
a
Total SiO2 (amorphous and crystalline).
b
Not reported.
c
This value represents the amorphous silica in the final RHA.
d
This value represents the residual carbon as indicated by the XRD analysis.
e
In this study, RHA was used as a source of silica and binder to produce one-part mix geopolymers.

Fig. 2. Comparison between (a) hydrothermal [27,36,81,110] and (b) thermochemical [26,37] methods with different processing parameters (temperature and
time) for the production of sodium silicate activator.

mentioned, there were limited studies to report the yield of silica from
the silica-rich wastes and those values were varied widely from as low as
12% [24] to as high as 80–95% in other studies [36,88]. Fig. 3 sum­
marizes the yield of silica from different sources of silica-rich materials
using different extraction methods. The possible factors that lead to this
variation will be discussed in the following sections.

3.3. Factors affecting the dissolution rate of silica

Despite using the same silica-rich waste, the optimum process may
vary widely due to the effect of various factors in the dissolution process
such as the amorphous SiO2 content, temperature, processing time, so­
lution alkalinity, and the solution/solid ratio. This section summarizes
the effect of various factors on the dissolution rate of silica.

3.3.1. The processing time and temperature

Fig. 3. The yield of silica from different silica-rich sources. The figure shows
the highest value obtained in each study [24,27,36,78,81,88,110,111].
of unburnt carbon, and the extraction method. As shown in Fig. 1, the
silica-rich wastes have the silica content greater than 80% (waste glass
has generally less silica content than others) and LOI is less than 10%
(RHA has typically have a higher carbon content). As previously
The processing time and temperature are important factors to affect
the dissolution of silica. It is expected that the heating and stirring
process generally enhances the dissolution rate of silica as the kinetics of
chemical reactions usually increase with the temperature and the
external stimulus. Different processing times ranging between 5 min and
72 h, and temperatures ranging between the room temperature and
120 ◦ C were used to synthesize alkaline activators using the hydro­
thermal process (see Fig. 2). In one study, an optimum amount of soluble
silica from RHA was obtained using a processing time of 60 min at
100 ◦ C, where approximately 80% of the ash was dissolved during this
time [88]. The remaining undissolved portion indicates the presence of
unburnt carbon and small quantities of other insoluble residues. Other

6
M.F. Alnahhal et al.
studies showed that longer stirring time between three and six hours is
required to achieve the highest amount of dissolved SiO2 [36,110]. The
variation in the optimized processing time could be attributed to the
different nature and reactivity of the silica source.
Generally, the increased temperature accelerates the dissolution of
silica in a given alkaline solution [27]. At high temperatures, the water
evaporation may change the concentration of the alkaline solution.
Therefore, it is recommended that the process is conducted in an
enclosed system to prevent the escape of water during the silicate
extraction [35]. It was found that the amount of dissolved RHA in the
solution treated by heating and stirring for 30 min at 90 ◦ C ± 5 ◦ C was
50% higher than that obtained from the unheated solution (i.e. mixed
for 30 min but without heating) [76]. Still, the high temperature would
not be an efficient process in terms of energy consumption. Comparing
two different temperatures (22 ◦ C and 80 ◦ C ± 2 ◦ C), Torres-Carrasco
et al. [110] concluded that the dissolution of WG was higher when
using 80 ◦ C. Their results provided useful solubility information about
different types of WGs. However, the significantly low ratio of the solid
mass to the solution volume (1 g/100 mL) may not be suitable for
synthesizing silicate-rich activator that can be used for AAMs casting.
Temperatures as low as 20 ◦ C were also used but a long processing time
of 72 h was needed to achieve 45% extraction efficiency [27]. Increasing
the temperature from 60 to 80 ◦ C was found to be effective for increasing
the yield of silica, and no further significant dissolution was recorded at
higher processing temperatures [36]. Amorphous silica is known to have
a relatively high value of activation energy [113]. Consequently, tem­
peratures as high as 80 ◦ C are essential in the hydrothermal process to
achieve the activation energy of silica in alkaline solutions, which is
required to enhance the dissolution rate. When RHA and microsilica
were dissolved in 10 M NaOH at room temperature, the low solubility of
silicon (<35%) [24] was reported indicating that the dissolution is a
temperature-dependent process, and high alkaline source concurrent
with low temperature did not impose a sufficient activation energy to
enhance the dissolution rate of silica.
Temperatures of up to 450 ◦ C were used in the thermochemical
process to transform the solid alkaline and silica sources into reactive
sodium silicate powder [26]. A temperature between 150 ◦ C and 330 ◦ C
was found to be effective to produce powder sodium silicate in the form
of Na2SiO3, which is preferable for AAM casting, while temperatures as
high as 450 ◦ C were not preferable as the final product consisted of
Na-rich silicates [26]. Mixing the NaOH, silica powder and water in the
form of paste before heating facilitates the use of temperatures below the
melting point of NaOH (318 ◦ C) due to the enhanced precipitation of
dissolved Na ions on the surface of silica particles [26,37].
Fig. 4. Relative compressive strength of specimens made of waste-derived ac­
tivators compared to the commercially available activator. The value represents
the highest strength achieved from the alternative activator in each study [24,
26,35–37,74,78,79,88,109,111,118].
7
Cement and Concrete Composites 118 (2021) 103980
3.3.2. The particle size of the silica source
Although some previous studies concluded that finer silica-rich
sources dissolve faster than their bulk analogues, contradictory results
from other studies suggest that the dissolution is independent of particle
size. For instance, a higher dissolution rate of silica was achieved using
the finer WG, which was attributed to the higher specific surface area
[110]. Another study also revealed that the amount of extracted SiO2 is
remarkably affected by WG particle size [80]. The findings showed a
greater solubility of WG with particle sizes <38 μm than those obtained
from the other WGs with larger particle sizes (between 38 μm and 125
μm). Conversely, Bouzón, et al. [88] observed a similar solubility for
ground (mean particle of 20 μm) and as received (mean particle of 62
μm) RHA. In addition, Luukkonen, et al. [24] pointed out that the par­
ticle sizes of RHA and microsilica have an insignificant impact on the
amount of silica dissolved by providing the appropriate extraction
method. This contradiction can be explained by the fact that the
particle-related factors that influence the dissolution rates of particles
can be the degree of aggregation, surface area, particle shape, and
particle size [114]. The insignificant effect of the particle size on silica
solubility could be due to the reaggregation effect [115] of very fine
RHA and microsilica particles. On the other hand, WG may have less
aggregation, which in turn enhanced the dissolution of the finer
particles.
3.3.3. The mineralogical properties of the silica source
The mineralogical properties of silica-rich materials would also
affect the dissolution of silica in the extraction process. Two types of
RHA were used by Mejía et al. [72] as a source of silica to produce so­
dium silicate. The first RHA (94.4% SiO2 of which 94.7% was amor­
phous) was produced under laboratory-controlled incineration at 600 ◦ C
for 3 h, while the other RHA (94.1% SiO2 of which only 27.7% was
amorphous) was a by-product collected from the rice mill. They pointed
out that both types of RHA exhibited good solubility when mixed with
NaOH irrespective of amorphous silica content if the alkalinity was
suitably adjusted for each RHA. However, the RHA with higher amor­
phous content required less time and heating temperature for dissolu­
tion than the RHA with low amorphous content [72]. Başgöz and Güler
[77] burnt rice hull at 600 ◦ C in a controlled laboratory environment. As
a result, they obtained highly amorphous RHA, which facilitates the
production of sodium silicate compared to the production using crys­
talline ash. When comparing RHA containing low amorphous content
with highly amorphous materials such as silica fume, the higher release
rate of silica is expected in silica fume systems, which influences the
quality of the final extracted solution [31]. Hence, the mineralogical
data helps to identify the suitable processing time and temperature, and
thus, optimising the energy use.
3.3.4. The alkaline source and concentration
WG showed similar solubility in NaOH and NaOH/Na2CO3 solutions,
where 28% and 25% of WG was dissolved in 10 M NaOH and 50/50
molar NaOH/Na2CO3 solutions, respectively [78,111]. The yield of sil­
ica from RHA and microsilica was noticeably increased when the NaOH
concentration increased from 1 M to 10 M [24]. This could be attributed
to the enhanced release of silica at high alkaline concentrations [116].
Tong et al. [36] also reported that low NaOH concentrations (smaller
than 2 M) are not suitable for maximizing the amount of dissolved silica
and suggested the optimum molarity of 3 M to effectively dissolve most
of the available silica.
Various studies in this section have shown promising potentials to
synthesize the activators using silica-rich by-products. However, there is
neither consensus on the optimized extraction process nor the compre­
hensive understanding of various parameters affecting the dissolution of
silica-rich materials, which is mainly due to the variety of factors that
affect the dissolution of silica-rich by-products. Further studies should
eliminate this uncertainty in future.
M.F. Alnahhal et al. Cement and Concrete Composites 118 (2021) 103980

Table 2
Summary of the effect of synthesized activators on compressive strength and setting time.
Reference Paste, Precursor Alkaline activator Mix design Curing Outcome
mortar or condition
concrete
Derived Standard SiO2/ Activator/ Water/ Compressive Remarks
from Na2O in binder solidb strength at 28
the days
activator

Tchakouté Paste Metakaolin RHA and – 1.5 0.83 – Room 30–36 MPa Superior strengths for
et al. [105] WG temp. WG-derived activator
compared to RHA-
derived one.
Tchakouté Paste Metakaolin RHA – 0.31–1.25 0.87 – Ambient 3.6–36 MPa Enhanced strengths for
et al. [112] temp. the higher SiO2/Na2O
molar ratios.
Tong et al. Mortar Fly ash/slag RHA SSa+NaOH 1.0 – 0.37 Room ~60 MPa - The strength of the
[36] blend temp. RHA-derived activator
was similar to the
commercial activator.
- Shorter setting times
for the RHA derived
activator
Passuello Paste Calcined RHA SS+NaOH – – 0.40 50 ◦ C for 47–68 MPa - Comparable
et al. [35] kaolin 24 h strengths for the RHA-
sludge derived and
commercial activators
at SiO2/Al2O3 = 3.5
- The amount of
unburnt carbon from
RHA may affect the
strength.
Bernal et al. Paste Slag RHA and SS 2.4 – 0.23 Ambient ~100 MPa Higher compressive
[118] silica fume temp. strength for silica fume
and RHA derived
activator compared to
the commercial one.
Mejía et al. Paste Fly ash/ RHA SS+NaOH 5 0.35 and – 60 ◦ C for ~28 MPa - Compressive strength
[74] metakaolin 0.42 24 h of 28 MPa was
blend recorded for an RHA-
derived activator at 28
days, which was less
than half of that
achieved by the
commercial one.
- Longer setting times
for the RHA derived
activator
Bouzón et al. Mortar The fluid RHA SS+NaOH 1.17 – – 65 ◦ C for 30–42 MPa at Similar compressive
[88] catalytic 24 h 1-day strength was recorded
cracking for the control mortar
catalyst compared with that
prepared using a
refluxed RHA
activator.
Luukkonen Mortar Slag RHA and Anhydrous SS – – 0.35 Room ~30 MPa - The low silica
et al. [24] microsilica temp. availability in
microsilica and RHA
derived activators
produced lower
compressive strengths
compared to the
commercial one.
- Longer setting times
for the RHA derived
activator
Samarakoon Paste Fly ash/slag WG SS powder 1.0 – 0.5 Room ~30 MPa Slightly higher
et al. [37] blend temp. strength and longer
setting time were
recorded for the WG-
derived activator
compared to the
commercial one.
Torres- Concrete Slag WG SS or 1.2 0.30 – Ambient ~30 MPa Higher strengths were
Carrasco NaOH+Na2CO3 temp. recorded when a
et al. [79] supplementary source
of silica from WG was
(continued on next page)

8
M.F. Alnahhal et al. Cement and Concrete Composites 118 (2021) 103980

Table 2 (continued )
Reference Paste, Precursor Alkaline activator Mix design Curing Outcome
mortar or condition
concrete
Derived Standard SiO2/ Activator/ Water/ Compressive Remarks
from Na2O in binder solidb strength at 28
the days
activator

present in the
activator.
Puertas and Paste Slag WG SS or 0.08–1.2 0.40 and – Ambient ~48–66 MPa Higher strengths for
Torres- NaOH+Na2CO3 0.44 temp. the activators with
Carrasco higher WG content.
[78]
Vinai and Mortar Fly ash/slag WG SS+NaOH 0.80 and 0.39 – Room ~44–58 MPa Compressive strength
Soutsos blends 1.00 temp. of WG-derived
[26] activator produced at
150 ◦ C was 40%
higher than the
commercial one.
Rodríguez Mortar Fly ash Nano silica SS 1.16 – – 65 ◦ C for ~91 MPa Slightly lower
et al. [109] 48 h strengths were
obtained for
nanosilica-derived
activator.
a
SS = sodium silicate.
b
The water/solid ratio = the mass ratio of total water over the mass of solids from the binder and chemical activator.

4. Performance of the synthesized activators addition, the compressive strength development found to be affected by
side reactions during geopolymerization due to the presence of impurity
The overall performance from the studies showed the general elements from silica-rich wastes [73]. The silica structure (crystallinity)
viability of different silica sources for the production of alternative ac­ would influence the soluble silica content in the synthesized activators,
tivators. The precursor type and silicate availability in the solution were which in turn affects the strength development. One study showed that
found to be the most important factors that affect the hardened per­ the SiO2/Na2O molar ratio below 0.78 in the synthetic activator has a
formance. The following sections review the impact of alternative acti­ negative effect on the compressive strength development, and this seems
vators on the compressive strength, setting time and microstructural to be the result of the lack of sufficient soluble silica in the activator
characteristics of AAMs. [112]. On the other hand, the strength was enhanced drastically from
~9 MPa to ~36 MPa when SiO2/Na2O molar ratio in the derived acti­
vator increased from 0.78 to 1.25. This could be due to the effect of
4.1. Compressive strength
increased soluble-silicate that can facilitate the polycondensation reac­
tion [112]. Comparable 28-day compressive strengths of 68.4 and 72.3
Numerous studies have investigated the effect of the synthesized
MPa were reported when calcined kaolin sludge was activated by
activators on the compressive strength of AAMs [26,36,78]. However,
RHA-derived and commercial sodium silicate activators, respectively
the tests in some other studies were limited to the specimens containing
[35]. However, a reduction of about 34% was observed in the strength
alternative (waste-derived) activators without a comparison with
when the amount of unburnt carbon from RHA was increased.
commercially available activators produced using typical sodium sili­
Increasing the dissolution time seems to have a significant impact on the
cates [76,105,112]. In this section, the authors focus on the effect of
strength due to the increased amount of the dissolved silica. Increasing
physical and chemical properties of silica source as well as the extraction
the dissolution time of RHA from 5 min to 60 min led to an improvement
process on the compressive strength development. As can be seen from
in the compressive strength from ~30 MPa to ~42 MPa, which was
Fig. 4 and Table 2, the comparison of the compressive strength of AAMs
comparable with the value of 40.9 MPa obtained from the commercially
containing alternative activators and that of similar composition of
available activator [88]. Moreover, there were no differences in
AAMs using a commercially available activator has been reported in
compressive strength between activating solutions prepared with the
limited studies, where the strength was lower in some cases [24,74,117],
ground and non-ground RHA.
and higher in another report [118]. Also, some studies reported a
A few studies have dealt with the compressive strength development
comparable compressive strength for AAMs containing standard or
of AAM paste and concrete activated using a WG-derived activator. The
alternative activators [31,35–37,88].
soluble silica extracted from WG facilitates the dissolution of the pre­
As shown in the previous Section 3.3.3, the amorphous silica in the
cursor particles and consequently affects the compressive strength
RHA has high reactivity, and thus, shows considerable effect in con­
[105]. Puertas and Torres-Carrasco [78] investigated the effect of the
trolling the quality of the RHA-derived activators. Mejía et al. [72]
amount of silica dissolved from WG in an activator on the compressive
synthesized activators using two RHAs: i) an industrial by-product RHA
strength of alkali-activated slag. They prepared 7 different types of
containing a low amorphous content of SiO2 and ii) a
alkaline activators: i) NaOH/Na2CO3 (SiO2/Na2O = 0), ii) NaOH/­
laboratory-controlled RHA containing high amorphous silica content.
Na2CO3 + commercial waterglass (SiO2/Na2O = 1.2), and iii) 5 different
The fly ash/slag pastes using the former activator (synthesized from low
types of WG derived activators (NaOH/Na2CO3 + different amounts of
amorphous RHA) had a 7-day compressive strength of about 10 MPa less
dissolved WG from 1, 10, 15, 20 and 25 g per 100 mL of NaOH/Na2CO3
than the paste made of the later activator (obtained from the high
solution). The corresponding SiO2/Na2O of 5 different types of
amorphous RHA). Another study [74] also used RHA with a poor
WG-derived activators were 0.08, 0.54, 0.63, 0.85, 0.86, respectively.
amorphous phase of SiO2 that formed during the combustion process
The 28-day strength increased from about 48 to 66 MPa when the
(90.93% SiO2, of which 36% was amorphous). It was found that the fly
SiO2/Na2O ratio for preparing an activator increased from 0.08 to 0.86.
ash/metakaolin geopolymer activated by this RHA-derived activator has
This increase in the compressive strength was a result of the increased
half of the compressive strength compared to the control mix. In

9
M.F. Alnahhal et al. Cement and Concrete Composites 118 (2021) 103980

amount of dissolved silica. These strength values were still lower than
the control mix (83 MPa) that was prepared using a standard commer­
cial activator (SiO2/Na2O ratio of 1.2). The solubility of WG and the
strength development could also be affected by the alkaline solution
used to dissolve WG [119].

4.2. Setting time

The setting time is an important factor to determine transport,

workability, and practical use of final AAM products. It was found that
the additives, mixing method, SiO2/Na2O ratio in the activator, amount
of water in the system, and the reactivity of the precursor play an
essential role in controlling the setting time of AAMs [120–122].
Mejía et al. [74] showed that the setting time of AAM activated using
commercial sodium silicate solution was shorter than that of AAM using
alternative RHA derived activator, with a difference of approximately 19
and 16 min for the initial and final setting times, respectively. On the
other hand, Tong, et al. [36] found that the mortars containing RHA
derived activator have shorter setting times compared to those of the
Fig. 5. XRD patterns of AAM activated using standard sodium silicate, RHA-
commercial activator. These contradictory results from two studies seem
and spent diatomaceous earth (SDE)-derived solutions at 28 days [74].
to be the content of amorphous phases in the RHA used. A lack of
amorphous phase was observed in the RHA used by Mejía et al. [74],
whereas the RHA used by Tong et al. [36] was almost entirely in an
amorphous state. These results from the literature show that the setting
time seems to be dependent on the quality of the silica source as well as
the concentration of the aqueous silicates in the solution. Low dissolu­
tion of silica from RHA with low amorphous content, which in turn re­
sults in lower availability of silicate species in the solution than that
from the standard one. Still, extracting more silicate species from RHA
with low amorphous content is possible using longer processing times
and temperatures. Geraldo et al. [76] observed that the metakaolin
based AAM activated using RHA-derived activator had a final setting
time of 194 min, which is longer than the general range of 60–120 min
obtained from other researchers for the conventional AAMs [60].
However, such delay of setting time can be controlled by the mix
composition [123]. For example, the incorporation of calcium-rich ad­
mixtures can lead to a rapid setting of the conventional AAMs due to the
effect of Ca ions in accelerating the formation of geopolymer gel [6,122,
124].
The mixing method also significantly affects the setting times. For
instance, the dissolution of solid activators in one-part AAMs usually
releases rapid heat, which in turn shortens the setting time [125]. Using
solid RHA derived activator for one-part alkali-activated slag, Luukko­
nen, et al. [24] reported initial setting times within the range between
27 and 72 min while AAM using commercial sodium silicate showed an
initial setting within the range of 19–57 min. They found that the setting
time can be easily adjusted based on the Na2O/SiO2 ratio. These ranges
of the initial setting time of one-part AAM are in line with previously
reported values between 23 and 150 min [90].
In summary, the studies presented in this paper show that the setting
time cannot be solely determined by the type of activator. Still, it is a
function of various factors but it seems to be controllable by developing
the proper mixture. Thus, the activators derived from different types of
silica-rich by-products can be surely implemented in casting AAMs.

4.3. Characteristics of AAMs using synthesized activators

4.3.1. Crystallographic characterization

It was reported that the crystallographic characterizations obtained
from AAMs using the synthesized activator have a similar trend to those
Fig. 6. XRD patterns for the unreacted slag and 7-day pastes activated using
obtained from AAMs using conventional activators. No crystalline re­
WG-NaOH/Na2CO3, waterglass and NaOH/Na2CO3 [78].
action products were identified in the XRD pattern of AAM samples
investigated by Tong et al. [36] suggesting an amorphous nature of the
geopolymerization products. The activator synthesized from RHA with discussed, the quality of a synthetic activator is a function of the
high amorphous content of SiO2 would produce AAMs similar to the extraction process, and the amorphous SiO2 content in the RHA used.
AAMs using conventional activators [118]. However, as previously Mejía et al. [74] observed broad humps (the indication of the

10
M.F. Alnahhal et al.
Fig. 7. FTIR spectroscopy of standard and RHA derived sodium silicate solutions. Sil std = standard sodium silicate. Sil 8 M, 10 M and 12 M are sodium silicates
derived by dissolving RHA in 8 M, 10 M and 12 M NaOH [29].
amorphous phases) between 22◦ 2θ and 33◦ 2θ for all AAMs activated by
standard sodium silicate, RHA- and spent diatomaceous earth (SDE)-­
derived solutions (Fig. 5). They found that the AAM activated by stan­
dard sodium silicate had slightly higher hump than those from the other
two AAMs, which indicated an increase in the geopolymer gel formation
as a result of the higher reactive silica in the activator. Another study
showed that the XRD patterns for AAM samples prepared using activator
derived from high amorphous RHA have typically broad hump structure
between 18◦ 2θ to 40◦ 2θ centred at 29◦ 2θ [112]. The intensity of this
hump increased with the SiO2/Na2O ratio in the mix. This result well
agreed with the result obtained from Mejía et al. [74] because the higher
soluble silica content in the silica-rich resource resulted in a higher
SiO2/Na2O ratio in the activator. Some crystalline phases were found in
the slag-based AAM activated by RHA-derived activator, which is the
Fig. 8. FTIR of metakaolin geopolymers made of RHA derived activator with
SiO2/Na2O molar ratio varying between 0.31 and 1.25 [112].
11
Cement and Concrete Composites 118 (2021) 103980
result of the crystalline raw RHA used (27.7% amorphous) [72].
Some of the studies have focused on the activators derived from WG.
Again, the structure of the reaction products is influenced by the nature
of the alkaline activator used. Consequently, the chemical reaction be­
tween WG derived activators and precursors could affect the phase di­
agrams of the resulting N–A–S(–H) and C–(N–)A–S–H gels [47,126].
Puertas and Torres-Carrasco [78] reported that the alkali activation of
slag using WG-NaOH/Na2CO3 yields a C–A–S–H gel along with hydro­
talcite and CaCO3, as shown in Fig. 6. They found a similarity in the XRD
pattern of the 7-day pastes containing standard and WG derived acti­
vators. In addition, Torres-Carrasco and Puertas [111] showed that,
when WG was used in the activation, the halo representing the amor­
phous content in the raw fly ash was shifted to slightly higher 2θ angles
suggesting the aluminosilicate (N–A–S–H) gel formation. The resulting
diffractogram was also similar to the pastes activated using commercial
waterglass. Tchakouté et al. [105] showed a broad hump centred around
28◦ 2θ in the XRD patterns of geopolymer pastes containing WG-derived
activator. The presence of unreacted metakaolin particles can also be
observed at the early ages represented by a peak structure with higher
intensity between 21◦ 2θ and 27◦ 2θ.
Overall, considering the wide range of the quality of activators
derived from different types of RHA, the extent of dissolution of RHA in
the solution mainly determines the property of RHA-derived activator,
and thus, affects the geopolymerization of the matrix. Moreover, it
appeared that the residual RHA particles seem to affect the final geo­
polymer products as observed from the XRD patterns, especially when
using the un-filtered RHA-derived solutions [72,74].
4.3.2. Chemical bonding structure
The nano-structural evolution of geopolymer systems has been
widely studied using Fourier transform infrared (FTIR) spectroscopy.
Several FTIR techniques have been applied in the analysis of geo­
polymerization [127], in situ early age gel formation [128,129] as well
as the geopolymer interface with aggregates [101]. Moreover, FTIR
spectroscopy has been applied to predict the reactivity of different types
of fly ash by studying the relative intensities of the Al–O and Si–O bonds
[127,130]. FTIR has also been used to determine the role of the silica
source in the activator on the polycondensation rate of the AAMs [55].
M.F. Alnahhal et al.
Fig. 9. TG/DTG for pastes containing commercial and RHA-derived activators at (a) 7 days and (b) 28 days (Control 1: NaOH-sodium silicate sol. and Control 2:
NaOH sol.) [36].
This facilitates the understanding when analysing the silica condensa­
tion in the waste-derived activators [29]. In general, the low-frequency
band at approximately 1000 cm− 1 can be assigned to the asymmetric
Si–O stretches in the sodium silicate solution, while the high-frequency
band around 1600 cm− 1 represents the binding of water molecules.
Fig. 7 shows the FTIR spectra obtained from a commercial sodium sili­
cate activator and three different activators derived from RHA [29]. For
the asymmetric stretching of Si–O–Si bonds, a shift was observed from
962 cm− 1 for the standard solution to 950 cm− 1, 946 cm− 1 and 943 cm− 1
for the RHA-derived solutions with 8 M, 10 M and 12 M NaOH,
respectively. The shift of Si–O–Si bonds to lower wavenumber values
reflects the high silica concentration in the solution [131]. This increase
in silica concentration could be attributed to the higher solubility of
RHA when the NaOH molarity was increased up to 12 M. In another
research, NaOH solution and WG sodium silicate were used for the
activation of fly ash [111]. The Si–O–Si bonds in the raw fly ash at 1060
cm− 1 was shifted to 1010 cm− 1 and 1004 cm− 1 when NaOH only and
WG sodium silicate were used, respectively. The WG sodium silicate
shifted the Si–O–Si bonds to lower frequencies suggesting reaction
products with higher contents of Si as a result of the higher availability
of silica in the activator. Tchakouté et al. [112] conducted an FTIR
analysis on alkali-activated metakaolin made of RHA-derived activator,
as shown in Fig. 8. When the SiO2/Na2O molar ratio was in the range of
0.93–1.25, distinct intensity bands were observed near 1007–1012
cm− 1, which implies the presence of effective amounts of soluble silica
in the alkaline activator. This observation suggested more dissolution of
metakaolin particles when using the activators derived from high ratios
of SiO2/Na2O in the synthesis process. These main bands are comparable
to those obtained by other researchers for metakaolin activated using
standard activator [31,132,133]. The high concentration of NaOH at
SiO2/Na2O molar ratio of 0.31–0.78 leads to the formation of Na2CO3 as
a result of the reaction between the CO2 from the atmosphere and the
excess ions of Na+ and OH− . This phenomenon was confirmed from the
bands at around 875 and 1456 cm− 1 which are pertained to the CO2- 3.
Similar bands for CO2− 3 were observed for the slag activated by
WG-derived solution [78].
In general, the location and intensity of Si–O–Al and Si–O–Si asym­
metric stretching vibrations may indicate the degree of geo­
polymerization [105,134]. For instance, the high-intensity bands
12
Cement and Concrete Composites 118 (2021) 103980
suggest a highly crosslinked geoplymerized gel framework [31]. More­
over, a higher dissolution of precursors could be inferred from the shift
of these broad bands toward lower wavenumbers. Therefore, the in­
tensities and positions of the AAM product bands were dependent on
both SiO2/Na2O ratio and/or concentration in the synthetic activator. In
addition, the presence of insoluble Si from RHA was also found to shift
the Si–O–Si asymmetric stretching vibrations to a slightly higher
wavenumber [31].
4.3.3. Thermogravimetric characterization
Bouzón et al. [88] investigated the thermogravimetric (TG) behav­
iour of the raw RHA and the insoluble residues from the reflux of RHA
with NaOH. At 350–600 ◦ C, carbon oxidation process took place, and a
significant loss of mass (41.7%) occurred for the insoluble residue, but
the raw RHA showed only 6.3% of the mass loss at the same range of the
temperature. This indicates the increased concentration of carbon in the
residues due to its insolubility when the raw fly ash was refluxed with
NaOH. Fig. 9 illustrates the mass loss obtained by Tong et al. [36] for
pastes containing RHA-derived activator against the commercially
available activators. They observed main mass losses between 40 and
160 ◦ C due to the removal of physically bound water. The progressive
decomposition of chemically bound water between 200 and 400 ◦ C led
to a similar mass loss of 3.25% and 3.06% for both samples activated by
RHA-derived solution (RHA sol in Fig. 9) and NaOH-sodium silicate
solution (Control 1 in Fig. 9), respectively. This result might suggest a
similar structure. Other researchers reported similar behaviour for slag
activated with RHA-derived activator [118]. However, Bernal, et al.
[31] reported that the metakaolin activated using RHA-derived acti­
vator showed a slightly higher mass loss at 52 ◦ C than the mass loss
obtained from the metakaolin activated by standard sodium silicate.
They suggested that the metakaolin activated by RHA derived activator
may have a coarser microstructure of the aluminosilicate mixtures that
can accommodate a larger amount of evaporable water.
High content of crystalline SiO2 in RHA leads to a decrease in the
soluble silica in the synthetic solution, which in turn increases the alkali
dosage and decreases the silicate modulus (SiO2/Na2O) in the activator.
At higher silicate modulus, more mass loss is expected due to the higher
chemically bound water content associated with C-(A)-S-H phases,
especially at late ages [135]. This was obvious as can be seen from
M.F. Alnahhal et al.
Fig. 10. SEM images at 28 days for fly ash/metakaolin geopolymer made with
a) commercial sodium silicate and b) RHA derived activator [74].
Fig. 9b, where more mass loss was observed for the sodium silicate
activated samples (Control 1, silicate modulus = 1) compared to those
activated using NaOH only (Control 2, silicate modulus = 0).
Fig. 11. Backscattered electron microscopy/EDS images of (a) alkali-activated slag with NaOH/Na2CO3; (b) alkali-activated slag with standard waterglass; (c) alkali-
activated slag with WG-derived solution [78].
13
Cement and Concrete Composites 118 (2021) 103980
4.3.4. Microstructural characteristics
Mejía et al. [74] stated that the silica dissociation in the commercial
sodium silicate by the attack of OH− ions from NaOH is faster than the
dissociation in the RHA-derived activator, resulting in faster bonding of
SiO2 and Al2O3 species. As a result, a more homogenous and denser
matrix for fly ash/metakaolin-based AAM containing commercial so­
dium silicate was observed compared to the one activated using RHA
derived activator through the images shown in Fig. 10. A non­
–homogeneous matrix with more voids observed in AAM activated using
RHA-derived activator (Fig. 10b) would be correlated with the higher
amount of evaporable water found in TGA analysis. In addition, a higher
amount of bound water observed in the control AAM (using the com­
mercial activator) indicates a higher degree of reaction, resulting in a
greater volume of hydration products and a denser matrix. The material
porosity, gel formation, and compressive strength development can be
affected by the silica availability in the activator (the dissolved silica in
the activator) [136].
The SiO2/Na2O molar ratio in the activating solution plays an
essential role in the depolymerization of metakaolin and the formation
of more homogenous microstructure. The micrographs in the study
conducted by Tchakouté et al. [112] of AAMs containing RHA derived
activator with 0.93–1.25 SiO2/Na2O molar ratio showed a denser
microstructure compared to the one with the ratio of 0.78. At low
SiO2/Na2O ratios, unreacted metakaolin particles were detected along
with more pores in the structure. The geopolymer matrix formed in the
presence of only NaOH activator had higher porosity due to the faster
reaction that leads to rapid precipitation of products around the pre­
cursors during the very early age [135]. Consequently, the formation of
reaction products in the empty pores at later ages would not be sufficient
to fill the voids in-between particles [137]. This led to a less homoge­
neously distributed microstructure. On the other hand, a well distrib­
uted reaction products formed in the presence of high amounts of silicate
species along with NaOH in the synthetic activator because the slower
reaction of precursors allows the reaction products to be dispersed ho­
mogeneously. Consequently, this activator contributes to develop a
higher compressive strength at later ages [138,139]. When RHA parti­
cles dissolved in NaOH solutions with different molarity, Kamseu, et al.
[29] found that increasing the NaOH concentration from 8 M to 12 M
resulted in an enhancement in the geopolymer microstructure. They
observed a coarser and porous microstructure along with unreacted
metakaolin and non-dissolved RHA particles at NaOH concentration of
8 M. On the other hand, in the case of 10 M and 12 M, more soluble silica
was formed, allowing further densification of those matrices. Hence, the
dissolution level of the amorphous silica in the alkaline solution
M.F. Alnahhal et al. Cement and Concrete Composites 118 (2021) 103980

the polymerization of AAM and consequently, the product compactness

[140]. Torres-Carrasco et al. [79] carried out a similar analysis, and they
detected some micro-cracks in the pastes, which could be attributed to
the shrinkage experienced during hardening. These micro-cracks affect
the interfacial transition zone, where the aggregate/matrix bond is ex­
pected to be weaker in the system containing more cracks.
Torres-Carrasco and Puertas [111] found that the elemental analysis
using energy-dispersive X-ray spectroscopy (EDS) of fly ash geopolymer
gel showed mainly phases of Si, Al and Na, with smaller portions of Ca,
Mg, K and Fe. Moreover, a higher Si/Al ratio in the N–A–S–H gels was
found for the solution containing higher amounts of dissolved silica.
The micrographs of one-part geopolymer made of standard and
alternative activators showed phases of smooth grey, light grey, and
textured grey areas representing the aggregate particles, unreacted slag
particles, and C–A–S–H gel, respectively [24]. The incomplete dissolu­
tion of slag particles was observed through the SEM image in Fig. 12, in
which these particles act as micro-fillers in the geopolymer system. In
addition, micro-cracks were detected in the sample made of standard
sodium silicate as a result of water escaped during curing.
A similar observation was found by Rodríguez et al. [109] for fly ash
geopolymers made of nano-silica derived activator. Remnant particles of
unreacted fly ash can be identified due to its partial dissolution during
the geopolymerization reaction, as shown in Fig. 13. When
NaOH-nanosilica derived activator was used, needle-like phases rich in
Al and Si were detected on the fly ash surface indicating the presence of
mullite crystals, as shown in Fig. 14b. Moreover, the EDS spectra in
Figs. 13 and 14 show a similar chemical composition for the geopolymer
gel containing standard and NaOH-nano silica derived activator. Like­
wise, Fig. 15 shows that the samples prepared with KOH-nanosilica
derived activator also contains mullite crystals originally embedded
within fly ash particles.
The microstructural characteristics were shown to be affected by the
availability of silica species in the solution [141]. A porous structure was
observed by Aydın and Baradan [142] for the slag activated using NaOH
only, and a well-packed and homogeneous structure was achieved by
increasing the SiO2/Na2O ratio from 0.4 to 1.2. This suggests that the
amorphous content in the silica source used in the synthetic activators is
crucial in increasing SiO2/Na2O ratio, which in turn has a significant
effect on the gelation process during geopolymerization.

5. Conclusions and future work

AAMs have been considered as one of the promising low-carbon

binders. However, their industrial viability for large-scale structures
has been questioned due to the reliance of this technology on alkaline
activators that require high embodied energy. Less expensive and more
sustainable pathways to low-carbon AAMs have emerged through the
synthesis of eco-efficient alkaline activators. This paper provides key
advancements to produce synthetic alkaline activators from silica-rich
Fig. 12. Micrographs of hardened geopolymer mortars made of standard and
waste materials. With this review, researchers can understand the
alternative activators at 1000× magnification [24].
prior development and preliminary findings of waste-derived activators.
The use of a combination of alkaline and silica-rich waste resources,
influences the densification and the polycondensation of the geopolymer
such as rice husk ash, waste glass, and microsilica, is feasible in the
matrix [138]. The dissolution of RHA was greatly improved by
preparation of alternative alkaline activators. The hydrothermal process
increasing the alkalinity of NaOH, suggesting an enhancement in the
was shown to be effective for the extraction of silica that can be used in
geopolymerization. However, the excessive use of NaOH solution affects
two-part AAMs. Moreover, anhydrous alkaline activators (solid sodium
the gel precipitation, which in turn hinders the degree of geo­
silicate) were also synthesized from silica-rich resources for developing
polymerization [73].
one-part AAMs, and a satisfactory strength has been achieved using such
Puertas and Torres-Carrasco [78] conducted SEM/EDS analysis on
activators. Numerous examples showed that the mineralogical charac­
alkali-activated slag pastes made of standard and WG-derived activators.
teristics, particularly the content of reactive (amorphous) silica, play an
As shown in Fig. 11, they found that the use of NaOH/Na2CO3 alone as
effective role in the quality of the extracted activator, which in turn
activator results in an uncompacted microstructure with a significant
reflects on the strength development and the overall performance of
amount of anhydrous slag particles. On the other hand, a denser and
AAMs. The other factors that affect the solubility of silica were found to
more uniform C–A–S–H gel can be seen in the pastes activated using
be the processing temperature, processing duration, and nature and
standard waterglass and NaOH/Na2CO3-WG. These findings revealed
molarity of the alkaline solution. On the other hand, some studies
that the dissolved SiO2 in the activator solution significantly improved
showed an insignificant effect of the particle size on the silica

14
M.F. Alnahhal et al. Cement and Concrete Composites 118 (2021) 103980

Fig. 13. SEM-EDS of fly ash geopolymers activated with standard sodium silicate solution showing (A) heterogeneous gel structure, (B) smooth spherical particles
and (C) agglomerations of rectangular crystalline particles [109].

Fig. 14. SEM-EDS of fly ash geopolymers activated with NaOH-nanosilica derived activator showing (A) geopolymer gel structure and (B) mullite crystals on fly ash
surface [109].

dissolution. Therefore, the careful selection of the alkaline solution,
silica source and silica reactivity is critical to optimize the energy use
during the extraction process. FTIR, XRD, TG, and SEM-EDS analyses in
the existing studies point out that the AAMs activated using alternative
activators have similar behaviour to the one activated using commer­
cially available activators. This suggests the formation of identical re­
action products. However, a careful design of mix components is
essential to manipulate the geopolymerization process.
The current knowledge gaps have to be filled to widely accept
alternative activators. Since the quality and the property of the syn­
thesized activator highly rely on the extraction method, the systematic
approach to properly design the extraction method for any type of silica-
rich resource should be further investigated. The durability (various
chemical attacks and time-dependent properties) of AAMs activated by
alternative activators must be well understood to enable its commercial
use. Moreover, further research is recommended on the temporal
rheological behaviour, which may provide a viewpoint about the
structural build-up and reaction process “geopolymerization”. There­
fore, the effect of the composition of the alternative activator on the
geopolymerization reaction should be well investigated. Furthermore,
research on the contribution of non-traditional activators on greenhouse
gas emissions and their effect on the economic aspect is also
indispensable.

15
M.F. Alnahhal et al.
Fig. 15. SEM-EDS of fly ash geopolymers activated with (A) standard potassium silicate solution and (B) KOH-nanosilica derived activator [109].
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
This work was supported by the Australian Government Research
Training Program Scholarship. The authors would like also to
acknowledge the support provided by the academic start-up fund from
the faculty of engineering at the UNSW Sydney.
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