Review

A Comprehensive Review on Fly Ash-Based Geopolymer

Ismail Luhar 1, * and Salmabanu Luhar 2

1 Department of Civil Engineering, Shri Jagdishprasad Jhabarmal Tibrewala University,

Jhunjhunu 333001, India
2 Centre of Excellence Geopolymer & Green Technology (CEGeoGTech), Universiti Malaysia Perlis (UniMAP),
Perlis 01000, Malaysia; [email protected]
* Correspondence: [email protected]

Abstract: The discovery of an innovative category of inorganic geopolymer composites has gen-
erated extensive scientific attention and the kaleidoscopic development of their applications. The
escalating concerns over global warming owing to emissions of carbon dioxide (CO2 ), a primary
greenhouse gas, from the ordinary Portland cement industry, may hopefully be mitigated by the
development of geopolymer construction composites with a lower carbon footprint. The current
manuscript comprehensively reviews the rheological, strength and durability properties of geopoly-
mer composites, along with shedding light on their recent key advancements viz., micro-structures,
state-of-the-art applications such as the immobilization of toxic or radioactive wastes, digital geopoly-
mer concrete, 3D-printed fly ash-based geopolymers, hot-pressed and foam geopolymers, etc. They
have a crystal-clear role to play in offering a sustainable prospect to the construction industry, as
part of the accessible toolkit of building materials—binders, cements, mortars, concretes, etc. Conse-
quently, the present scientometric review manuscript is grist for the mill and aims to contribute as a
single key note document assessing exhaustive research findings for establishing the viability of fly
ash-based geopolymer composites as the most promising, durable, sustainable, affordable, user and
eco-benevolent building materials for the future.

Citation: Luhar, I.; Luhar, S. A Keywords: geopolymers (GP); geopolymerization; fly ash (FA); fly ash-based geopolymer (FGP);
Comprehensive Review on Fly ordinary Portland cement (OPC); greenhouse gas (GHG); setting time; drying shrinkage; efflorescence;
Ash-Based Geopolymer. J. Compos. alkali-aggregate reaction; hardening chemistry; three-dimensional (3D) structure; supplementary
Sci. 2022, 6, 219. https://doi.org/ cementitious materials (SCM); CO2 sequestration
10.3390/jcs6080219

Academic Editor:
Francesco Tornabene
1. Introduction
Received: 28 April 2022
Accepted: 18 July 2022
A burgeoning world population and the titanic development of global infrastructures
Published: 27 July 2022
have generated an exigency for colossal quantities of construction materials across the
planet. For these reasons, the manufacturing of concrete is estimated to reach greater
Publisher’s Note: MDPI stays neutral than one ton per annum per head [1]. This escalating demand for concrete, in turn, has
with regard to jurisdictional claims in resulted in an energetic demand for ordinary Portland cement (OPC), a primary binder of
published maps and institutional affil-
the concrete. Disappointingly, the existing course of action for the production of OPC is not
iations.
merely a costly, user-hostile and energy-intensive process of looking for calcinations, but it
is also not an eco-benevolent one, since it emits embodied CO2 (carbon dioxide), a primary
greenhouse gas (GHG), into the atmosphere, which is liberated from the decomposition
Copyright: © 2022 by the authors.
of fossil fuels and limestones—the chief raw material of OPC [2,3]. Unfortunately, 1 ton
Licensee MDPI, Basel, Switzerland.
of OPC production emits an almost equal quantity of CO2 into the environment [4]. In
This article is an open access article simple statistics, “more is the production of OPC, more will be the emissions of CO2 , and
distributed under the terms and at the same time, more will be the degradation of confined natural resources” [5–8]. By and
conditions of the Creative Commons large, CO2 emissions alone are answerable for 65% of global warming, out of which OPC
Attribution (CC BY) license (https:// production is single-handedly accountable for roughly 6% of the total emissions of carbon
creativecommons.org/licenses/by/ dioxide [9]. This has created a great dilemma for environmentalists and a red signal to the
4.0/). breathing communities on the earth [10].

J. Compos. Sci. 2022, 6, 219. https://doi.org/10.3390/jcs6080219 https://www.mdpi.com/journal/jcs

J. Compos. Sci. 2022, 6, 219 2 of 59

All these negative impacts have twisted the arms of researchers, concrete technologists
and scientists to search for alternate materials for construction, which must certainly be
user and eco-benign, durable, sustainable, affordable, essentially cost-effective, and can
lend a helping hand in the saving of limited natural resources [11–14]. These are the root
causes of the attraction by many researchers towards innovative geopolymer technology
and geopolymer composites such as GP-cements, GP-pastes, GP-mortars, GP-concrete, etc.
Geopolymers can be synthesized using low energy, a lower temperature, by expending
low cost and by utilizing diverse profuse wastes as either precursors or supplementary
cementitious materials (SCM), offering a solution to the systematic disposal of materials
such as fly ash, metakaolin, ground granulated blast furnace slag, etc. Of these, FA is the
key solid waste generated as a by-product from coal-firing power plants, for which thermal
electricity stations seek ways in which to dispose it in an economical and environmentally
beneficial way, along with CO2 sequestration [15,16]. A deeper understanding of the
physical–chemical and mechanical properties of the fly ash is, therefore, essential for its
review in both natural and modified forms.
Geopolymer is a novel production of inorganic alumino-silicate polymer with a net-
work structure that is similar to zeolite in three-dimensional (3D) form, which comprises an
Al and Si tetrahedral network and can be produced through the process of geopolymeriza-
tion. This means the activation of either material, geological or industrial origin in the form
of by-products, as a precursor that is rich in alumina and silica [17–21]—such as fly ash with
alkali activators, most commonly, silicate, carbonate and hydroxide of sodium, etc. [22,23].
Globally, researchers are inclined towards this novel technology on account of its key
benefits such as the simple process of production with lower energy consumption, and the
efficient use of industrial and other diverse wastes [24–26]. Consequently, geopolymer is
known for the mitigation of CO2 emissions and its brilliant engineering properties viz.,
resistance to sulphate [27–31] and acid attacks [30–34]; excellent freeze–thaw cycle [35];
resistance to chloride penetration [27,36,37], etc. These properties will establish it as a
potential substitute of OPC. By and large, the display of geopolymer performances is found
to be analogous or sometimes even better than OPC properties [38–44], on account of their
dissimilar products of hydration and microstructure [41–43]. Activator dosages and curing
conditions, along with the kind and attribute of raw material, have a momentous influence
on the microstructure and hydration attributes of geopolymers, making the study of them
thornier. Firstly, well-known past researchers of concrete [44–50] have summarized the
achievement of research in the context of investigating geopolymeric cement, as well as
geopolymer concrete, prior to 2005 quite methodically. The past couples of decades have
witnessed scores of scientific advancements in the technology of geopolymer, and insights
into the fly ash-based geopolymer performance. The rapidly developing knowledge of
this innovative technology has, in turn, resulted in several amendments of methods to
noteworthily enhance the performances and manufacturing of the geopolymer that is based
on fly ash. The wide-ranging application of fly ash-based geopolymer in the construction
and infrastructure industries has proved to be assuring. Preceding studies have revealed
that, in comparison to the conventional OPC, GP cement is a modern inorganic polymer
with a low carbon footprint [45], fewer energy necessities, as well as the low consumption
of resources [46,47]. Moreover, GP is a grouping of cement, ceramics and polymers, with
the characteristics viz., early higher strength, superior resistance to acid, sulphates, fire,
heat, ample raw material resources, a simple process of production, cost-effectiveness,
etc. [51,52]. Over the past three decades, these brilliant attributes have made GP viable
to be employed extensively as edifice materials, to immobilize nuclear wastes, for use in
aerospace fields, as emergency mends, for resource utilization and for the protection of
the environment, etc. [53–55]. Recently, emerged GP is viable to be employed extensively
as edifice materials. Based on the research papers on GP; a summary of the assessment
of the development of fly ash-based geopolymers; their benefits, properties, applications,
and existing challenges in the pathway of these novel construction composites, etc., a
scientometric review of them has endeavoured, besides essential future works, to promote
J. Compos. Sci. 2022, 6, 219 3 of 59

them as acceptable building composites, providing a reference for the potential advance in
research and utilization of this GP-material [56,57].
The current manuscript comprehensively reviews the fly ash-based geopolymers with
respect to the most recent advancements and developments in these most attractive, in-
novative, low-carbon footprint geopolymer composites, with their rheological properties,
setting behaviour, structural characterization, dimensional stability, durability, mineral-
ogy, chemistry of geopolymerization, hardening mechanism, classification, structure and
terminology; as well as their applications, advantages, opportunities, micro-structures,
Si/Al ratios, constituents, conditions of curing, setting time, strength attributes of their
compression, split tensile as well as flexural strength; and their durability properties, such
as chloride ion resistance, sulphate, thermal, acid, efflorescence freeze–thaw, drying shrink-
age, etc. All of the above, together with workability, flow ability water absorption, and
significant characteristics such as the immobilization of toxic or radioactive wastes, etc.;
micro-structures—namely, SEM images, XRD, EDS Spectrum, and FTIR, along with thermo-
gravimetric analysis and mercury intrusion porosimetry (MIP), are reviewed and discussed.
Not only this, but diverse scientific research on said composites (namely, digital geopoly-
mer concrete and 3D-printed fly ash-based geopolymers with its reaction kinetics and
compressive strength) has also been taken into account for the review. Moreover, inhibiting
efflorescence development on fly ash geopolymers, hot-pressed and foam geopolymers, be-
sides the acoustic attributes of fly ash-based geopolymers, has been assessed systematically.
All the existing insights into these materials have been included to create a complete, state-
of-the-art review in all respects, with greater focus on the most significant cutting-edge data
that have been obtained in the recent past, since these are draw increasingly more attention
as essential parts of the ‘toolkit’ of optional cementitious materials with eco-munificence.
Not only this, the benefits of geopolymer technology and its up-to-date status are taken
into consideration, and how more potential research can be employed to study their me-
chanical performance in much detail, in order to further expand production and explore
new applications. The review is grist for the mill to establish the viability of geopolymer
based on fly ash as a most promising, durable, sustainable, affordable, cost-effective, green,
user and eco-benevolent composite. It extends not merely a systematic solution for the
disposal of fly-ash wastes, meticulously protecting the environment, soils, and waters from
pollution, but also for conserving confined natural resources. Fly ash-based geopolymers
have a crystal-clear role to play in extending a sustainable prospect for global construction,
as part of the accessible toolkit of binders, cements, mortars, concretes, etc.

Research Methodology
A comprehensive literature review was conducted to identify and appraise the allied
available information on record, which are the pedagogic ideas and referenced examples
of the fusion work. Recently, one of the rapidly expanding study disciplines in recent
years has become a crucial sub-discipline of geopolymeric inorganic composites, polymers
of inorganic origin, or revolutionary geopolymer technology. To comprehend in-depth
the most recent and emerging drift of geopolymer as an edifice material, the keywords
“geopolymer”, “fly ash based geopolymer”, “fly ash in geopolymer”, “alkali activated
concrete” and “fly ash in concrete” were methodically recovered, using bibliographic
databases of “Springer”, “Elsevier”, “Taylor and Francis”, “Wiley” and “Hindawi”, as well
in the interest of congregating an absolute gathering of data. Furthermore, comprehensive
data analysis and categorization were carried out based on a thorough understanding of
titles, graphical abstracts, highlights, abstracts, keywords, entire texts, conclusions, and
impressions. Several synthesis procedures were depicted in figures, graphs, and tables,
which were used as references in the current study. The cited literature data represent
a comprehensive description of the progress, portrayal, and application of fly ash by
geopolymer composites. The present review text includes microstructural techniques
such as XRD, SEM, FTIR, and NMR. The aforementioned methodologies are useful for a
J. Compos. Sci. 2022, 6, 219 4 of 59

better understanding of the inherent linkages of structure, micro-, and pore-structures in

geopolymer building composites.

2. Geopolymers
The innovative geopolymer technology contributes a novel, excellent, as well as green
solution to the application of different wastes such as fly ash, GGBF Slag, meta-kaolin,
fibres [58], volcanic ash [59], glass wastes [60,61], farming wastes [62] etc., avoiding its
negative impact on the environment and ecosystem [58]. The materials that were employed
for the formation of geopolymers were of geological origin, and the course of action was
akin to the process of polymerization of organic compounds, validating its nomenclature.
Consequently, geopolymers are the results of geochemistry or the geological synthesis of
mineral polymers of rock-forming minerals with a geo-origin [53]. The referred to geo-
synthetics are similar to natural rocks on compaction, i.e., they are formed in the course
of a quite analogous synthesis, which is found to occur in nature for the formation of
natural rocks.
In 1978, the French scientist, Joseph Davidovits, unearthed that alternative binders
could be produced through the process of “Geopolymerization”. He invented a novel kind
of inorganic alumina silicate oxide through this exothermic chemical process, among the hy-
droxide and silicate of alkalis under an extremely alkaline medium at a lower temperature,
and just at atmospheric pressure. He termed this a “Geopolymer (GP)”. In other words,
geopolymerization takes place through alkaline activation, i.e., dissolution at high pH
under higher alkaline conditions and just by using atmospheric pressure, and at consider-
ably low temperatures, from room temperature to slightly elevated temperatures—usually
below 100 ◦ C or 150 ◦ C. Geopolymerization also occurs, significantly, with nine times fewer
emissions of primary GHG gas—CO2 [63–65], consuming up to a 60% smaller quantity
of energy in comparison with the present production method for OPC [66–69], making it
approximately 10–30% cheaper than OPC. This exothermic polymeric chemical reaction or
the alkali activation occurs between alkaline activators such as NaOH, KOH, Na2 SiO3 or
K2 SiO3 , and jointly or independently with alumina, plus silica-rich source material that
originates from either geological origins (such as meta-kaolin, etc.) or industrial origins
(such as fly ash, etc.) at a lower temperature and atmospheric pressure only.
Prof. Davidovits coined the resultant product as a geopolymer (GP)”, i.e., a mineral
polymer that was achieved from the geochemistry or geo-synthesis of abundant rock-
forming minerals, or wastes that were generated from industries analogous to natural
rocks formations. Principally, GP is the alkaline activation product, along with a three-
dimensional network structure of any aluminosilicates with an empirical form of Mn
[-(SiO2 )z-AlO2 ]n, wH2 O, wherein “z” is the Si/Al molar ratio, which may be equal to 1, 2,
3 or maybe higher; “M” is monovalent alkali cation viz., potassium (K+ ) or Sodium (Na+ );
“n” is the degree of polymerization (“n” is a degree of polycondensation or polymerization,
and the “-” symbol suggests the existence of a bond); and w is the content of water [70].
Significantly, this novel GP possesses the analogous binding performances, as in the case
of OPC. This means, unlike OPC, high energy or elevated temperature reactions are no
longer essential. The word “Geopolymer” implies their geological origin and the products
of geopolymerization [53] can efficiently be thought of as synthetic rock. Fly ash is a by-
product from the industry of thermal plants for electricity and is mainly found as a finely
grained powder in the form of a residue from burning pulverized coals. These pulverized
fuel ashes comprise the remnants of sands and clays, along with organic matters that are
present in the parent coal with higher alumina and silica.
Consequently, geopolymer is a pozzolan that is found in profusion in the form of
an industrial waste by-product. For these reasons, the production of fly ash appears to
remain momentous and, accordingly, the economical and green-concept technology of
fly ashes is highly desirable through their applications. Consequently, the application of
fly ash in geopolymer production has attracted engineers and researchers, owing to its
appropriateness and universal ubiquity as a redundant residue. Specifically, fly ash is more
J. Compos. Sci. 2022, 6, 219 5 of 59

preferable to other precursors on account of its massive accessibility [71], reasonably lower
down cost and higher reactivity, which is due to its finer particle size. In recent times,
research on fly ash-based geopolymers has evolved to mitigate the carbon footprint of
concrete, providing a simple way to dump a few of the several million tonnes of the fly ash
that is generated universally every year, filling useful lands and creating not only health
hazards, but also environmental crises.

2.1. Constituents of Geopolymers

Geopolymer production necessitates raw materials possessing plenty of silica and
alumina content viz., fly ash, slag, kaolinite, clays, silica fume, spinel, andalusite, micas,
rice husk ash, red mud, etc., as precursors. Commonly, alkali activators such as hydroxide
and silicates of Na and K are also used for activation. It is a notorious fact that calcined
precursors such as fly ash and slag demonstrate more enhanced compressive strength than
non-calcined materials [53,72]. Barbosa et al. [73], and Xu and Deventer [74], accounted
that calcined fly ash and non-calcined materials could be combined for the enhancement in
their compressive strength, and for mitigating the reaction time. The potential use of fly
ash to manufacture geopolymers was also identified by Van Jaarsveld et al. [75].

2.2. Mineralogy
Geopolymers are similar to feldspathoids and zeolites with respect to their miner-
alogical characteristics, and they are largely found in amorphous to semi-crystalline form
with three-dimensional (3D) structures of silico-aluminate, i.e., a poly sialate (-Si-O-Al-O-)n
and poly sialate siloxo (-Si-O-Al-O-Si-O-)n kind of chemical bonding that results from
conditions of hydrothermal setting. “Sialate” is a short form of “Silicon-Oxo-Aluminate”,
in accordance with Davidovits [53], and a glassy or an amorphous structure symbolizes
their hardening at ambient temperatures. Despite their exceedingly smooth surfaces and
glassy look with a semi-vitreous to vitreous lustre, geopolymers are competent enough
to exhibit a hardness of 4 to 7 on the Mohs scale of hardness [53]. They are mostly found
with a non-crystallised form, and this is the reason for the X-ray diffraction outcomes in
a wide diffuse halo, as well as for the sharp shape peaks of diffraction [53,76]. This is
also why XRD or FTIR spectroscopy alone is not proficient to investigate their structures.
This ceramic sort of material not only reveals thermal stability, but also a precise mould
capability, justifying its utilization to a great extent as an essential building material.

2.3. Chemistry of Geopolymerization, Hardening Mechanism, Classification, Structure and Terminology

Geopolymers are the novel, inorganic class of solid inorganic complex materials and a
product of green chemistry through “Geopolymerization” [53,77]. Contrasting the OPC
process of production, this exothermic progression liberates very little (about 90% less)
CO2 , providing evidence that it is an eco-benevolent yield. This simply means that nine
times more manufacturing of geopolymer cement is feasible for the sake of the equal
amount of of CO2 emissions in comparison with OPC production. Not only this, the
reaction kinetics of geopolymerization are also possible, even starting at room temperature
to up to 150 ◦ C at only atmospheric pressure, as well as autoclaving pressure [78] in
extremely alkaline conditions, confirming that geopolymers consume lower energy (yet
again contradicting OPC production, whereby the restricted natural mineral coals are
burnt to attain an elevated temperature for limestone calcinations). For this reason, highly
energy intensive and higher temperature reactions are no longer necessary. It is known
that geopolymerization necessitates reactive precursors with plenty of alumina and silica,
as well as a higher concentration of the reagent activators—particularly, of the alkali
hydroxide (OH2− ) group [79]. In other words, it is a yield of a chemical reaction among
alkali-polysialates and alumino-silicate in the presence of a highly alkaline medium, i.e.,
at an elevated pH. The attributes and structure of geopolymers are identical to ceramics
and can polycondense at a temperature of less than 100 ◦ C [80], akin to organic polymers.
Geopolymers are “polymers,”; therefore, they can be rapidly polycondensed, transformed,
J. Compos. Sci. 2022, 6, 219 6 of 59

and formed at lower temperatures (i.e., at 30 ◦ C, for just a few hours, at 85 ◦ C for only a few
minutes, and with microwave ovens for only a few seconds). Accordingly, geopolymers
are hard and weather-resistant mineral materials with enough capacity to resist elevated
temperatures. They are utilized just like thermo-setting organic resins and are steady
up to 1000 ◦ C to 1200 ◦ C, which is suggestive of their nature to resist high thermal and
catastrophic fire conditions [80]. Geopolymerization produces the formation of a disordered
alumino-silicate gel phase of alkali, which is called the geopolymer gel binder phase. In
this phase, non-reacted solid particles of source materials can be found, and the structure
of the gel pore encloses the water, which is used in mixing the precursors. In contrast,
water does not become an integral component of a geopolymer binder’s chemical structure,
as in the case of a calcium silicate hydrate (C-S-H) gel. Apart from the negative charge
due to Al3+ ’s four-fold coordination in one or more of the bridging oxygen particles in
every aluminium tetrahedron, the fundamental framework of the gel is closely connected
to three 3D setups of the silicate and the aluminium tetrahedra, and balanced by cations
of alkali metal that are provided by the activator solution. Geopolymer gel binder shows
structural similarities with zeolites on an atomic scale to a nanoscale. This is occasionally
extended to the point where the formulation of the nano-crystallites within the geopolymer
gel becomes obvious, especially in the presence of abundant water, high temperature for
synthesis and a lower Si to Al ratio [81]. The geopolymer structural analysis is simple,
since it covers a mix of amorphous X-ray phases and is developed under corrosive reaction
conditions that make an in situ analysis complicated. Joseph Davidovits coined three types
of geopolymers based on their kinds of chemical bonding, which result from the conditions
of a hydro-thermal setting [29,53,82–85]:
I. “Sialates” (-Si-O-Al-). This is a short form of the chemical title that is provided to
“Silicon-Oxo-Aluminate”;
II. “Poly sialate” (-Si-O-Al-O-)n. This is a contraction of the chemical heading for “Silico-Aluminates”;
III. “Poly -sialate siloxo” (-Si-O-Al-O-Si-O-)n
The poly sialate has been categorized into three kinds—namely, poly(sialate) (-Si-O-
Al-O-) or “PS”; poly(sialate-siloxo) (-Si-O-Al-O-Si-O-) or “PSS”; and poly(sialate-disiloxo)
(-Si-O-Al-O-Si-O-Si-O-) or “PSDS”. Poly (sialates) are polymers of the chain and ring type
Si4+ and Al3+ , which show a discrepancy in shape from amorphous to semi-crystalline, with
four co-ordinations with oxygen. One hardening mechanism among others encompasses
the alumino-silicate oxides chemical reaction (Al3+ in four-fold coordination) [83–85].
Poly (sialates) can be symbolized chemically by employing a tetrahedral configuration
with a form of empirics [86]:

Mn [-(SiO2 )z-AlO2 ]n, wH2 O,

wherein “z” is equal to 1, 2, 3 or maybe higher;

“M” is a cation monovalent viz., potassium (K+ ) or sodium (Na+ );
“n” is a degree of polycondensation or polymerization; and
the “-” symbol suggests the existence of a bond.
The alumino-silicate set-up consists of AlO4 and SiO4 tetrahedral structure units that
link with each other by sharing their oxygen atoms. The negative charge of “Al” is balanced
by positive ions viz., Na+ , Li+ , K+ , Ba2+ , NH3+ , Ca2+ , and H3 O+ [53,77,82].
A supposition is made that the fusions are carried out by the oligomers (dimer, trimer)
that compose the specific unit 3D structures with macro-molecular edifices. While under
acidic conditions, the alumino-silicates do not interreact or are disgraced, under alkaline
conditions, they alter to form tremendously reactive silico-aluminates, which polycondense
with each other to develop a 3D framework. It is possible that iron polycondensation, i.e.,
ortho-sialate and ortho(sialate siloxo), is caused by hypothetical monomers.
Currently, only the sodium-poly(sialate); potassium-poly(sialate); (sodium, potassium)-
poly(sialate-siloxo); and potassium-poly(sialate-siloxo) are employed for geopolymers.
J. Compos. Sci. 2022, 6, 219 7 of 59

Precisely, the chemistry of geopolymerization forms geopolymers through alkali dis-

solution by the hydrolysis of dissolved units Al3+ and Si4+ , with the resultant condensation
of aluminium and silicate [87]. The complications of the referred reaction kinetics need a
model compound to be used to make clear the mechanisms that are involved. An alkaline
aluminium silicone gel—in which the aluminium and silicone ions are joined in a 3D
tetrahedral gel frame, which is relatively resistant to water dissolution—constitutes the
distinctive feature of a geopolymer [88,89].
Looking at the terminology of geopolymers, Davidovits introduced the ‘sialate’ classifi-
cation to depict the structure of alumino-silicate [83]. The kind of link “Si-O-Al” was termed
as a “Sialate” bonding, with “Si-O-Si” as a “Siloxo” bond. This provides a way of portray-
ing the chemistry of geopolymers as per their ratio of Si to Al, with a ratio of 1.0 being a
“Poly-Sialate”, while 2.0 is a “Poly-Sialate-Siloxo”, and 3.0 is a “Poly-Sialate-Disiloxo”.

Binder Amorphous Poly(Sialate-Siloxo) (-Si-O-Al-O-Si-O-)

The chemical precursor reaction for geopolymers such as aluminosilicate oxide (Al3+
in four-fold coordination) with polysilicates from polymer-produced Si-O-Al bonding is
one of the hardening mechanisms. In order, the four-fold co-ordination of Al, commonly
represented as (Si2 O5 , Al2 O2 )n should be highlighted for the particular, meticulous oxides
of alumino-silicate, in place of (2SiO2 , Al2 O3 ).
A production of (Si2 O5 , Al2 O2 )n is made through:
(i) Aluminium–silicate hydroxide calcination (Si2 O4 , Al2 (OH)4 ), or;
(ii) SiO and Al2 O vapours condensation [90]:
(a) 2(Si2 O5 , Al2 (OH)4 ) → 2(Si2 O5 , Al2 O2 )n + 4H2 O;
(b) 4SiO (vapor) + 2Al2 O (vapor) + 4O2 → (Si2 O5 , Al2 O2 )n
Also, by forming:
2SiO + O2 → 2SiO2 (silica fume condensed form)
Al2 O + O2 → Al2 O3 (corundum product)
The exothermic process of geopolymerization can be schematized as follows:
It might be considered as the upshot of the poly-condensation of hypothetical monomers,
including the ortho-sialate ions [90,91].
The synthesis is performed throughout oligomers (dimers, trimers) that represent the
exact unit structures of the 3D macro-molecular formation.

2.4. Properties of Geopolymers

Geopolymers demonstrate excellent characteristics, such as high early strength; bril-
liant thermal stability at elevated temperatures [92,93]; little shrinkage; excellent resistance
against freeze–thaw cycles, corrosion, fire, sulphate and acid attacks; autoclave curing,
etc., proving them to be eye-catching alternatives to conventional concrete technology.
Moreover, they offer a noteworthy cost-effectiveness of 10% to 30% in comparison to the
cost of a traditional concrete system [94,95]. They are non-combustible and non-flammable,
and that is why they exhibit exceptional resistance to fire and heat. Not only this, but the
CO2 that is emitted per volume unit of geopolymer cement is roughly nine times lower
than the OPC system, endorsing it as an eco-benign material. This simply means that
developing countries can have nine times more cement for constructional developments for
the same quantity of CO2 emissions [94]. Moreover, the enhanced polymerization augments
the amorphous content and relatively escalates the fly ash-based GPC strength [68]. At
a room temperature of only 20 ◦ C, geopolymer cement toughened fast and provided a
20 MPa compressive strength after four hours, while testing as per the norm used hydraulic
binder mortars, in accordance with Badami et al. [96]. The ultimate compressive strength
28 days later was found between 70 and 100 MPa [96]. As stated earlier, geopolymeric
cement performs similarly to feldspathoids and zeolites [97]. This is why they are capable
enough to immobilize even radioactive hazardous wastes into a matrix of geopolymer
and perform as a binder to alter partially solid wastes to the adhesive solids. Zeolites are
hydrated crystalline aluminosilicates [97]. Zeolites that are suitable for use can be either
J. Compos. Sci. 2022, 6, 219 8 of 59

naturally occurring or synthesized. Natural zeolites that are preferred include, but are
not limited to, analcime, chabazite, gmelinite, mordenite, natrolite, faujasite, phillipsite,
sodalite, nepheline, scapolite, cancrinite, erionite, and clinoptilolite [97]. Feldspathoids are
chemically and structurally similar to Zeolites, with open holes inside the aluminosilicate
structure that are capable of containing alkali metals [97]. Feldspathoids are pozzolanic
and have exchangeable alkali ions, making them comparable to zeolites. Examples of
feldspathoids include, but are not limited to, nepheline and leucite [96,97]. Feldspathoids
are chemically related to clay minerals. Zeolites, on the other hand, differ in their crys-
talline structure. Unlike many clays, which have a layered crystalline structure and are
subject to shrinking and swelling as water is absorbed and removed between the layers,
zeolites have a rigid, three-dimensional crystalline structure consisting of a network of
interconnected tunnels and cages [97]. Although water flows freely through these holes, the
zeolite structure stays stiff. Another interesting feature of this structure is that the pore and
channel diameters are essentially consistent, allowing the crystal to function as a molecular
filter [96,97].

2.5. Applications of Geopolymers

Geopolymers are useful in many industries such as automobiles, aerospace, non-
ferrous foundries, metallurgy, plastic industries, and especially in civil construction en-
gineering because of their sustainability under violent environmental conditions and the
unique properties that they possess. Their applications include fixing carbon fabrics to
the surface of structural concrete beams [98];the development of sewer pipeline products,
railway sleepers, masonry units, and high performance fibre-reinforced laminates; building
parts, together with chemical and fire-resistant coatings and wall panels [99,100], fire-
resistant wood panels, high-tech resin systems, and insulated panels and walls; fibre-proof
high-tech applications; interiors; decorative stone art; low-energy ceramic tiles; fireproof
composites; infrastructure repair; foamed geopolymer panels for thermal insulation; ther-
mal shock refraction and refractory items; and the manufacturing of geopolymer paste,
mortar, cement and concrete, etc.
Davidovits categorises a variety of applications based on the silicon and aluminium
atomic ratio of a low Si to Al atomic ratio of 1, 2, or 3, demonstrating a 3D network which
is very stiff (whereas Si to Al atomic ratios beyond 15 designates a polymer nature).
Geopolymers are attractively useful as they exhibit properties of self-binding for
concrete, improved durability, enhanced performance, cost-effectiveness [86], a mitigated
negative impact on the environment, lower energy consumption, user and eco-friendliness,
excellent resistance to fire, outstanding hardness, and toxic chemical, radioactive and
industrial mining wastes immobilization, since their capacity to absorb water, like zeolites,
shows a stability of up to 1000 to 1200 ◦ C.
Geopolymer technology is more advanced in precast applications because of the
relative simplicity of regulated requirements in handling delicate materials, as well as
the controlled high-temperature curing environment, all of which are advantageous to
geopolymers. As a result, geopolymer concrete was previously used to make railway
sleepers and sewage pipes. Geopolymer concrete may be used to make structural elements
such as columns, beams, and even tunnel segments. High durability and resilience to
harsh environments, which are typical of geopolymer concrete, are highly required in the
manufacturing of sewage pipes. Many soils are rich in corrosive acids. These acids are
corroding concrete and steel members that are installed underground.
Geopolymer concrete, according to Dawczynski et al. [101], is an excellent alterna-
tive to Portland cement concrete, especially in situations where steel reinforcements are
employed. Geopolymer concrete has been found to meet the concrete requirements in
hostile conditions such as sulphate soils. Thus, geopolymer concrete may be utilized as a
sustainable option in the construction of long-lasting structures, as well as in a variety of
maintenance applications. Since geopolymer concrete is resistant to chloride, it sustains
less damage during the winter months when salt is used to melt the ice layer. Geopolymer
J. Compos. Sci. 2022, 6, 219 9 of 59

concrete, because of its strong resistance to chloride corrosion, can be utilized for concrete
structures such as piers, coastal bridges, and undersea concrete supports that are constantly
attacked by seawater.

2.5.1. Application of GP Binder as a Sustainable Repair Material

The use of GP binder has been widely researched due to its low shrinkage, high
early strength, resistance to sulphate attack and corrosion, and high resilience to thawing
and freezing. When used in civil engineering, it may significantly reduce stripping time,
accelerate the template operation cycle, and increase building speed. A novel form of
geopolymeric binder, one-part GP mixes, can be utilized to ease the process of activating
GPs in silicate solution. Thermally treated low-quality kaolin at 950 ◦ C, and the strength of
the associated binders is up to 47MP, which is equivalent to the strength of two-part mix
systems [102].

2.5.2. Application of GP as Multi-Layer Walls

Ma et al. [103] presented an analytical model based on the finite variations approach to
predict the thermal impact of buildings with multi-layer walls, composed of a phase change
materials layer and a layer of geopolymer concrete that was mixed with microencapsu-
lated phase change materials. Geopolymer concrete GPC was chosen as an ecologically
benign material with minimal CO2 emissions, as well as suitable mechanical and thermal
qualities [104,105]. Furthermore, it is ideally suited for integration with microencapsulated
phase change materials (MPCM) to provide concrete with a massive heat storage capability,
and that meets the mechanical strength requirements for building operations [106,107].

2.5.3. Application of GP as a Coating Material

The GP may be linked into the network structure of film material via the aluminium
tetrahedral and silicon tetrahedral, resulting in a type of inorganic coating with non-
toxic environmental protection, low cost, fireproof and waterproof properties, and so
on. A. Khosravanihaghighi prepared GP-type paints with various amounts of -SiC, and
the findings revealed that increasing the fraction of nano-SiC reduced porosity, while
improving corrosion and wear resistance. Furthermore, a reflective heat insulation GP
coating was created using metakaolin and sodium silicate solutions as the primary starting
materials, with talcum powder, hollow glass microspheres, and sericite powder added as
fillers [108,109].

2.5.4. Application of GP as a Self-Cleaning Material

Severe air pollution is mostly the result of industrial output, natural disasters, engi-
neering construction, and automotive emissions, among other things. As a result, when
exposed to polluted air, building amenities become filthy. This issue has compelled in-
dustry to find alternate materials to aid in sustainable development. Due to their unique
qualities, GP-based self-cleaning concrete materials provide a green solution to the problem.
In addition, the self-cleaning capability of GP-based concrete is being investigated using
photocatalytic elements such as ZnO and TiO2 [110].

2.5.5. Application of GP as a Geopolymer Foam

Geopolymer foams have various uses in industries and construction because of their
light weight. TROLIT was the brand name of one of the earliest reported materials of this
sort. TROLIT was a type of inorganic geopolymer foam that was composed of three main
components: solid silicon and aluminium sources that were obtained as by-products of
industrial processes involving high temperatures; a liquid activator that was composed of
alkali metal aqueous solutions; and expanding agents such as peroxides and perborates.
This substance had unusual features that few scientists had before achieved, and then only
on a laboratory scale. The thermal conductivity of the material was 0.037 W/mK, which is
comparable to polystyrene.
J. Compos. Sci. 2022, 6, 219 10 of 59

2.5.6. Application of 3D Printed Geopolymer

The explorations of the attributes of geopolymer products through innovative 3D
printing processes are quite promising and are the reason why the field is growing signifi-
cantly, and why relevant various studies are also focused on the topic contemporarily in
the construction and infrastructure industries. For instance, Panda et al. [111], shed light
on the development and examination of the processes’ directional influence on the com-
pressive strengths of geopolymer mortar based on fly ash, as well as some other industrial
by-products viz., silica fumes, slag, etc. The mechanical characteristics and the reaction
kinetics of the mixtures that exhibited a good-quality recovery aptitude were reviewed
before the 3D printing process in the context of concrete. The heat of the reaction, produced
through isothermal calorimetry, was regarded as an indicator of the overall reaction of
hydration inside the pastes that were made [112].

2.5.7. Application of Porous Geopolymer

To adapt their use to diverse practical applications, fly ash-based porous geopolymers
are often manufactured in a variety of forms such as bulk, membrane, and spherical. This
section discusses both the fabrication of bulk/membrane and sphere-shaped components,
with bulk and membrane components grouped together, since their preparation processes
are typically identical. Previous studies have well detailed the manufacturing processes for
geopolymer mortar, concrete, and composites with porous structures that are made from
fly ash [113,114].

2.6. Advantages and Disadvantages of Geopolymers

• An innovative, noble and revolutionized material which cuts carbon footprint by
mitigating GHG emissions, providing relief from global warming;
• Thermal and fire-resistant materials [115];
• Can immobilize the hazardous, radioactive wastes [116];
• Exhibit excellent strength and durability [117,118];
• High early strength contributing to sustainable composites [119];
• Excellent resistance to chemicals and freeze–thaw conditions [120], etc.;
• No water curing, because water is released during the chemical reaction in the geopoly-
merization process of geopolymer concrete, and this water tends to evaporate as the
specimens are heated during the curing phase. Similarly, drying shrinkage in stiff
specimens is low due to the little amount of water in the pores [18,116–121];
• Several studies have been conducted [122,123] to determine the effect of curing condi-
tions on the physical and mechanical characteristics of geopolymer paste and concrete.
Curing temperatures ranged from 40 ◦ C to 85 ◦ C for near-perfect geopolymeriza-
tion [18];
• Hardening mechanism is quicker and at low temperatures [124];
• Much lower creep, as well as shrinkage [116–121];
• Low permeability [125,126];
• User and eco-friendly [125,126];
• Systematic disposal of diverse waste is possible through their consumption in their
manufacturing, otherwise, filling land spaces and pollutes the environment, soils,
surface, sub-surface and supply waters, etc [125,126];
• Structurally a stable and intact material even under severe conditions because of the
special 3D network structure of aluminosilicate [7,116];
• Brilliant mechanical properties on account of typical structure and framework of
[–Si-O-Al-O]n bonding, since this structure does not depend upon lower strength
bonds, as found with the OPC system, and thus results in comparatively higher
strength [125,126];
• Excellent durability because geopolymers are inorganic materials and generally con-
tain massive minerals of zeolite nature viz., sodalite, analcime, etc. [118,119];
J. Compos. Sci. 2022, 6, 219 11 of 59

• Noteworthy resistances to chemical, fire and thermal conditions. Mostly, the Si-O
and Al-O bonding of geopolymers hardly ever react with other acids, except for
hydrofluoric acid (HF). Moreover, the structure of the oxide network of geopolymers is
stable at high temperatures, and the lower thermal conductivity of 0.24 to 0.38 W/(m·K)
altogether prove it as an exceptional heat-insulated material [127];
• Faster curing rate and higher force for internal binding with the quicker forma-
tion of gel and rapid dehydration enable its high early strength as compared to
the OPC system;
• Contrary to different cement structures, the geopolymer is found to be strongly bonded
to aggregate, enabling it to be employed as a possible mend for a concrete product;
• Lower cost in addition to a widespread source for natural and industrial precursors
that are available in plenty to synthesize geopolymer. The requisite elements for
geopolymer are silicon, oxygen and aluminium, which exist in the earth’s crust in a
proportion of 26.3%, 48.6% as well as 7.73%, respectively, in that order. The precursors
are kaolinites and industrial wastes such as fly ashes [128,129].
• Potential applications of special kind of geopolymer structure of silicon tetrahedral
and aluminium tetrahedral form ring chain structures such as the cage cavity are
favoured its utilization as a building material for immobilization of heavy metals, the
disposal of nuclear waste, as well as novel making of inorganic membranes [30,69,70].

Disadvantages of Geopolymers
While geopolymer concrete looks to be the superior concrete to replace regular Port-
land concrete, it has numerous drawbacks, including:
• Geopolymer concrete needs specific handling and is exceedingly difficult to produce.
It necessitates the use of potentially hazardous chemicals such as sodium hydrox-
ide [129];
• Due to the hazards that are connected with its production, geopolymer concrete is
only available as a pre-cast or pre-mix material [129];
• The geopolymerization process is sensitive—research in this sector has been inconclu-
sive and exceedingly volatile. There is no consistency [129];
• Transporting the primary material, fly ash, to the needed site;
• Excessive cost of alkaline solution [115];
• Safety concern linked with high alkalinity of activating solution [115];
• Practical challenges in implementing steam curing/high-temperature curing proce-
dure [115].
Significant research is being conducted to build geopolymer systems that can overcome
these technological challenges.

3. Coal Fly Ash

Coal fly ash, together with the flowing gas in coal-fired power plants, is the fine
particulates residue that is expelled by the boiler. It may typically be extracted by any
suitable action; for instance, through electrostatic precipitation, cyclone separation, or
other particulate filtration equipment before the flue gases reach the chimneys, from flue
gasses of sprayed or crusher-powdered coal and lignite-fired boilers [130,131]. According
to the projections of the Energy Information Administration (EIA), U.S.A., the quantity
of electricity generation will rise with a growth rate of 2% per annum up to 2040, which
implies that coal will constitute a major portion in the development [132]. The incessant
exigencies for coal as fuel will pilot a generation of more coal ash (CA) production. During
coal combustion, 80% coal fly ash (CFA) and 20% coal bottom ash (CBA) are produced as by-
products, and disposal from sites will have a hazardous impact on health and, in particular,
on eco-systems. In 2016, the planet generated around 1.143 billion tonnes of fly ash. China
generated approximately 600 million tons, with a utilization rate of 68–70 percent; the
United States produced approximately 44 million tons; and Japan produced approximately
12 million tons, with a utilization rate of nearly one hundred percent. The European Union
J. Compos. Sci. 2022, 6, 219 12 of 59

produced 40 million tons (all coal-fired solid wastes in the 15 European Union nations),
and the utilization rate was ninety percent (completion of 36 million tons); India consumed
169 million tons, with a usage rate of sixty-three percent [133]. The quality of CFA depends
mainly on the chemical constitution of the coal that is used for burning, as well as the
combustion conditions, i.e., the rate of pulverization and oxidation. CFA not only contains
a variety of trace elements (such as As, Se, Cd, Cr), but also encloses oxides of Ca, Si, Fe,
Al, Na, K, Mg, and Ti [134,135], which make it potentially toxic. Consequently, the direct
application of CFA leads to perilous effects on the environment [136]. The mineralogical
and chemical constituent of CAF permits its use in plenty of fields. The utilization rates of
50% of CFA in the US, 60% in India, 67% in China, and 90% for the EU, were estimated [137].
Other developed nations, such as the United States and Europe, have substantially greater
usage rates. It is a fundamental reality that fly ash is no longer seen as trash, particularly in
the industrialized world. It is presently a very popular and frequently utilized raw material
in building [138]. According to the European Coal Combustion Products Association,
Europe generated about 40 million tonnes of CCW in 2016 and reused more than ninety
percent of it in the building and reclamation industries [138]. In the same year, the United
States generated over 107 million tonnes of CCW, of which nearly sixty percent was re-
used [139]. By 2020, their entire CCW had been decreased to 40 million tonnes, with
over fifty-eight percent being re-used [140]. Since CFA is used directly as a raw resource
or additive material in the building and construction sector, it contributes considerably
to CFA recycling. The volumes that are disposed of, however, continue to be a serious
management problem. CFA is also a potentially low-cost adsorbent material, either directly
or by functionalized production [141,142]. It has also been discovered as a potential source
for the metallurgical recovery of high-purity products such as alumina [143,144]. In the field
of building materials, its future is frequently debated, as developed European countries are
currently dealing with the cessation of coal combustion in power plants and its replacement
by other raw materials, raising concerns about the possibility of construction without coal
ash, confirming the fact that fly ash is currently very desirable as a raw material.
Interestingly, CFA is a pozzolanic material, and this is the core reason for its prevalent
application as a supplement in manufacturing cement, in order to save the natural resources
that are used to produce cement. The upshots of research also indicate its capability to
adsorb metal ions from solutions, because of its alkaline attributes with the negatively
charged surface. Moreover, the application of CFA as a low-priced source of alumino-
silicate has become the centre of attention for scientists in the last couple of years, who
have successfully transformed this waste by-product material to zeolitic geopolymers for
diverse uses [145,146]. In addition, the implementation with CFA of synthetic products has
succeeded in removing toxic elements from both contaminated soil and water [147–149]. If
not adequately controlled, the enormous volume of fly ash that is created by municipal solid
waste incineration plants might fast become one of the country’s major sources of heavy
metal pollution [150]. By 2020, their entire CCW had decreased to 40 million tonnes, with
over fifty-eight percent being re-used [140]. Since CFA is used directly as a raw resource or
additive material in the building and construction sector, it contributes considerably to CFA
recycling. The volumes that are disposed of, however, continue to be a serious management
problem. Table 1 shows the chemical composition of fly ash from past studies. Although
fly ash is a popular source material for geopolymer, there are certain drawbacks to using
it. For example, the quality of fly ash can impair the quality and strength of geopolymer
concrete. Poor quality fly ash can increase the permeability of geopolymer concrete and
cause structural damage. The use of fly ash causes a slower strength increase and can
prolong the time it takes for geopolymer concrete to cure.
There are several forms of fly ash produced by the coal supply and combustion method.
They are classified into two types: high-temperature fly ash and fluidized bed combustion
ash. Fluidized bed combustion ash is a by-product of coal-fired power stations that must
decrease air emissions cheaply in order to fulfil Clean Air Act regulations. The concept
of fluidized bed combustion technology is the burning of coal with sorbent, which is
J. Compos. Sci. 2022, 6, 219 13 of 59

introduced to the combustion chamber based on the sulphur level of the coal. Ground
limestone is commonly used as a sorbent, which is why these ashes have a greater CaO
concentration. The combustion process begins at around 850 ◦ C [151,152]. Although the
physical and chemical composition of fluidized ashes is comparable to that of Portland
cement, the resultant materials have poor compressive strengths and are thus employed
exclusively as pozzolan in concrete applications. The primary distinctions between these
kinds are increased SO3 concentration, highly reactive free CaO, and potentially larger
loss on the ignition of ash, following fluidized bed combustion. While standard high-
temperature FA primarily contains pozzolanic action, fluidized ash may set and harden
by just combining it with water, without the any additional additives or chemicals. The
binding capabilities of fluidized ash are primarily determined by the quantity of present
anhydrite and free lime, which is gently burned during the coal combustion process and is
thus highly reactive [151–154].
Currently, nitrogen oxide reduction strategies that allow meeting NOx emission stan-
dards include methods that are based on the injection of ammonium compounds [155–157].
This procedure is often carried out in one of two ways: selective catalytic reduction (SCR)
or selective non-catalytic reduction (SNCR). The authors Michalik et al. [158] concentrated
on the properties of fly ashes that were produced by the SNCR process of flue gas denitri-
fication. The study focused on silica fly ash from flue gas denitrification and ash from a
traditional boiler that did not go through the flue gas denitrification process. The research
focused on the physicochemical and structural properties of ashes, as well as slurries and
cement mortars containing ashes. Research has shown that fly ash from flue gas deni-
trification is characterized by a higher value of losses on ignition and ammonia content
in comparison to ashes without denitrification; it has also been shown that the ammonia
content in the analyzed range does not limit the use of fly ash as an additive to cement
and concrete. Procházka et al. [159] explained the influence of fly ash denitrification on the
properties of hybrid alkali-activated composites. The purpose of this study was to evaluate
the effect of SNCR denitrification on fly ash for usage in hybrid alkali-activated materials
that were based on blast furnace granulated slag. In the experiment, a potassium water
glass with a silicate modulus of one was utilized as an activator. So far, the results sug-
gest that using fly ash after denitrification in hybrid alkali mixtures does not significantly
impair the reported attributes when compared to using standard fly ash without denitrifi-
cation. The experiment findings demonstrated that there was no significant change in the
characteristics of the mixes that were formed from fly ash after and without denitrification.
The alkali activation of waste material is a chemical method that allows the user
to convert glassy structures into highly compact well-cemented composites. The major
reaction result of fly ash alkali activation is an amorphous, three-dimensional alkaline
inorganic polymer known as NASH (Na2 O-Al2 O3 -SiO2 -H2 O) gel. Na-chabazite, zeolites
A and P, and faujasite are examples of secondary reaction products [160] Fly ash alkali
activation is a unique process in which this powdered grey material is blended with alkaline
activators and then cured at a moderate temperature to generate solids. The FA’s glassy
ingredient turns into a well-compacted cement. The major reaction product that was
generated in alkali activated fly ash was discovered to be an amorphous alumino-silicate
gel with zeolite precursor characteristics.

Table 1. The chemical composition of fly ash in previous research.

SiO2 +
Type of Al2 O3 +
Reference CaO SiO2 Al2 O3 Fe2 O3 Na2 O K2 O MnO MgO SO3 TiO2 LOI
Fly Ash and
Fe2 O3
[161] Class F 0.87 61.89 28.05 4.11 94.05 0.4 0.82 - 0.38 1.32 - 0.49
[162] Class F 2.24 57.2 24.4 7.1 - 0.38 3.37 - 2.4 0.29 - 1.52
[163] Class F 2.38 50.7 28.8 8.8 88.3 0.84 2.4 - 1.39 0.3 - 3.79
[164] Class F 5 49 31 3 83 4 1 - 3 0 2 0
J. Compos. Sci. 2022, 6, 219 14 of 59

Table 1. Cont.

SiO2 +
Type of Al2 O3 +
Reference CaO SiO2 Al2 O3 Fe2 O3 Na2 O K2 O MnO MgO SO3 TiO2 LOI
Fly Ash and
Fe2 O3
[167] Class F 10.58 17.57 36.37 12.43 66.37 - 1.77 - 3.05 1.39 0.88 1.19
[168] - 3.6 58.0 29.08 3.58 - 2.0 0.73 - 1.91 1.8 1.75 2.0
[165] Class F 1.55 53.5 28.8 7.47 89.77 - - - 0.81 0.14 - 3.11
[166] - 3.05 52.3 28.0 6.32 - - 2.51 - - - - -
[169] - 5.41 27.35 50.85 2.01 80.21 0.04 0.33 0.02 0.28 - 2.12 7.74
[170] Class F 5.31 54.72 27.28 5.15 87.15 0.43 1 0.1 1.1 1.01 1.82 6.8
[171] Class F 0.2 57.6 28.9 5.8 92.3 - 0.9 - 0.9 0.2 - 3.6
Class F and
[172] 14.14 50.67 18.96 6.35 75.98 0.69 - - 3.12 0.74 - 0.17
Class C
[173] Class F 1.64 66.56 22.47 3.54 92.57 0.58 1.75 – 0.65 0.1 0.88 1.66
[174] Class F 2.58 63.13 24.88 3.07 91.08 0.71 2.01 0.05 0.61 0.18 0.96 1.45
[175] Class F 3.81 47.87 28 14.09 89.96 0.41 0.62 0.21 0.93 0.27 1.99 0.43
[176] Class F 4.3 51.1 25.7 12.5 89.3 0.8 0.7 0.2 1.5 0.2 1.3 0.6
[177] Class F 12.92 52.75 18.05 5.92 76.72 1.11 2.09 0.14 3.86 1.76 1.01 1.6
Class F and
[178] 1.29 54.48 27.72 8.14 90.34 0.67 - - - 0.11 - 4.11
Class C
[179] Class C 17.16 35.86 15.05 17.31 68.22 1.58 3.12 - 2.34 5.94 - 0.1
[180] Class F 7.32 58.4 23.8 4.19 86.39 1.43 1.02 - 1.11 0.44 - 0.5
[181] Class F - 50.83 23.15 6.82 80.8 1.29 2.14 - 1.7 1.24 1.01 0.55

3.1. Sources of Fly Ash:

Electricity and heat production in power plants contribute a titanic quantity of minerals
matters, which are associated with the original coals that are brought for combustion as a
waste by-product in most areas of the world [182]. Nearly 80% of by-products from coal
combustion are represented by fly ash. Bottom ash is also found to be associated with
the pulverized fuel ash that accumulates at the bottom of the boiler through some proper
practices. However, the bottom ash from the boilers is not mixed with the fly ash. The fly
ash that is collected in the beginning is coarser than the fly ash that is later gathered in the
stages of electrostatic precipitators. Flue gas desulphurization material is a residue from a
coal-fired boiler, resulting from the falling emits of SO2 (sulphur dioxide). It is a wet sludge
or a dry powder consisting of CaSO3 or CaSO4 sulphate (calcium sulphate). As a hazardous
solid waste, municipal solid waste incineration fly ash includes harmful compounds such
as heavy metals and dioxin, making its disposal a global public health problem. With the
growth of urbanization and the improvement of people’s living conditions, the amount of
municipal solid waste (MSW) that is created grows year after year.

3.2. Properties of Fly Ash

3.2.1. Chemistry and Morphology
Fly ash is industrial by-product dust from thermal coal plants of a fine-grained nature
and comprises mostly spherical to subrounded melted vitreous particles that range in size
from 0.5 to 300 µm with a smooth surface [183]. As mentioned earlier, the key component of
most of them is silica (SiO2 ), ferric oxide (Fe2 O3 ), calcium oxide (CaO) and alumina (Al2 O3 ),
along with minor quantities of Na2 O, MnO, SO3 , MgO, K2 O, TiO2 and non-burnt carbon,
which are present in some of the fly ash. Fly ash with properties such as low calcium, a
high vitreous phase, 80 to 90% of particle sizes that are less than 45 µm [184], unburned
material at less than 5%, reactive silica of 40% to 50%, and less than 10% Fe2 O3 results in
the optimal binding characteristics [184]. A momentous amount of calcium can hinder the
polymerization setting rate resulting from an alteration of the microstructure [185]. For this
reason, low calcium fly ash is preferable for making fly ash-based geopolymers. The value
of a loss on ignition depends on the kind of working regime and the type of power station.
An immense discrepancy in the key composition of silica (25 to 60%), ferric oxide (5 to 25%)
and alumina (10 to 30%) was found [186]. Fly ash is technically considered as siliceous
when the three key constituents total 70% or more and the reactive calcium oxide is less
J. Compos. Sci. 2022, 6, 219 15 of 59

than 10%. This sort of fly ash is a product that is obtained through the burning of anthracite
coal or bituminous coal, which possesses pozzolanic attributes [187]. If the combination of
these three constituents is equivalent to or greater than 50% and the reactive calcium oxide
is not lower than 10%, then calcareous fly ash generates the types of sub-bituminous or
lignite characteristics of coal and has both hydraulic, as well as pozzolanic characteristics.
The chemical composition of the fly ash is consistent with natural pozzolans, such as
volcanic ashes, whereas the calcareous ashes include hydraulically active mineral phases
and pozzolanic materials. The pozzolanic reactivity is a unique characteristic of siliceous
fly ash, i.e., its aptitude to act in response with water and lime at ambient temperature
to formulate strength-furnishing mineral phases that are analogous to OPC. Other than
Si, Al, Fe and Ca, fly ash is customarily found to be associated with many other trace
elements of metal, such as Ti, Cr, V, Mn, As, Co, Sr, Pb, Mo and Hg [188,189]. Fly ash could
produce 4–10 times more toxic trace elements than those in coal [187–189]. Moreover, it
may possess smaller dioxins concentrations, along with organic compounds of polycyclic
aromatic hydrocarbon [190,191]. Therefore, fly ash is regarded as a perilous material, and
this is why offensive fly ash disposal will not only merely accelerate the land occupation,
but also pollute the environment, ecology, soils, surface and subsurface waters. Concerning
its particle size distribution, fineness and the reactivity of pozzolan, CFA is frequently
utilized in cement composites to enhance their technical attributes and substitute OPC. The
glassy materials that are present in fly ash are found to be reactive with the hydroxides of
alkali and Ca, which are obtained from fly ash cement systems and develop a cementitious
gel that contributes supplementary strength.

3.2.2. Morphology
Looking to the morphology and its impact on the reactivity of fly ashes, the size of their
spherical to subrounded particles and their fineness are the key factors [192] deciding the
appropriateness of their use in the manufacturing of concrete, because they significantly in-
fluence the attributes of ultimate fly ash-based products [193]. Chindaprasirt et al. [194–196]
exhaustively investigated the impact of fineness on chloride penetration [194], drying
shrinkage, strength, sulphate resistance [196], etc., and improved compressive strength,
mitigated shrinkage, and expansion, etc. by employing finer fly ashes. On the other hand,
coarse fly ash is less reactive and requires more water from more porous mortar with a
greater vulnerability to sulphate attack. However, the negative effects of coarse fly ash
are often referred to as the reason for reduced strength, accelerated drying shrinkage and
excellent sulphate resistance, etc. [196]. On the other hand, a diminution in the particle size
of fly ash accelerates the content of amorphous SiO2 and tends to reduce the quantity of
SO3 , which can hinder the hydration of dangerous ions in mortar or concrete [197]. The
positive impact of fly ash fineness on the mechanical characteristics of the concrete on
improving the compressive strength is repeatedly accounted [198]. The finer fraction of
lesser than 63 mm of fly ash particles in manufacturing concrete and cement can improve
the pozzolanic reactivity. Nevertheless, the removal of coarser particles may suppress
certain cementitious characteristics [199]. Finer particles of fly ash are greatly desirable
for the development of strength because they contribute more hydration nucleation sites.
However, coarser particles of fly ash cannot be eradicated totally as they possess defi-
nite positive performances when employed in diverse composites. This is why both fine
and coarser particles of fly ashes, employed in the proper ratio, would display improved
outcomes concerning the strength and durability of ultimate composite.

3.3. Types or Chemical Classification of Fly Ashes

As stated earlier, the contents of fly ash differ significantly depending on the coal
source being fired. By and large, the components of fly ash characteristically include SiO2 ,
Al2 O3 , CaO and Fe2 O3 , which are found in amorphous and crystalline form as oxides or
a variety of minerals. In accordance with the American Society for Testing and Materials
(ASTM) standard C 618 [200], chemically, fly ashes can be classified as Class C fly ash, as
J. Compos. Sci. 2022, 6, 219 16 of 59

well as Class F types, on the basis of their contents of calcium oxide (CaO), which generally
decides how fly ash performs when it is employed. Fly ashes are classified primarily
according to the EU Standard (EN-450—1) standard or the American Society for Testing
and Materials (ASTM—C-618) standard. The American Test and Material Society (ASTMs)
has two classes of fly ash, “C” and “F” fly ash [200].
A. Class C fly ash:
It possesses a higher content of calcium, which is chiefly found in the burning of
sub-bituminous or inferior quality coal, i.e., lignite deposits from coal sources. It contains
an overall content of SiO2 , Al2 O3 and Fe2 O3 ranging from 50% by weight to 70% by weight,
whereas the content of CaO is greater than 20% by weight.
B. Class F fly ash:
It has a lower content of Ca, which is produced from the burning of superior quality
coal, namely, anthracite or sometimes bituminous—the second highest quality of coal. It
has a total content of SiO2 , Fe2 O3 and Al2 O3 beyond 70% by wt. and less than 10% by
weight of CaO content [201,202]. It is classified as a normal type of pozzolan, i.e., a silicate
glass material that is altered by Al and Fe.
The above-referred Standards govern the physical and chemical characteristics of the
fly ash that is employed. The key dissimilarity among these standards depends upon their
chemical composition, fineness and loss on ignition (LOI). Commonly, non-burnt residues
of carbon are described as LOI. Consequently, the chemical constituent of the fly ash that is
employed influences the performance of the ultimate composites [203].
Fly ashes that contain low calcium slowly react, especially during the early hydration
stages, because of the presence of more crystalline, chemically inert phases. Due to the
progress in characterization techniques, the hydration products that are developed at
various stages can be analyzed. The images of SEM are more helpful to recognize the
chemical constituents, as well as the morphology of developed hydrated products. SEM
images of fly ash-based composites, along with a dispersive energy spectrum, exhibit the
composition of a variety of hydrated products in the alike image at dissimilar spots. On the
other hand, high-calcium fly ashes are less sensitive to insufficient curing and react more
swiftly to contribute an improved early-age strength.
Nevertheless, fly ashes with a high calcium content are commonly less competent
in suppressing the distribution because of sulphate attack [204] and alkali-silica reaction
(ASR) [205], in comparison with those containing low-calcium. In addition, calcium re-
placement during the glass phase is believed to usually speed up the reactivity of high
calcium-possessing fly ash. For this reason, it enables the development phases of the silicate
and aluminate of calcium without an outside source of lime.
Furthermore, fly ashes of Class C differ from those of Class F concerning the content
of lime and the lime depolymerized glass phase. The content of CaO in the glass phase
of fly ashes with high calcium shows higher reactivity because of the condensed degree
of SiO4 polymerization [206]. Diamond [207] accounted that the pore solution alkalinity
was on account of the presence of hydroxide of calcium, which was developed from the
hydration of cement, beside ions of Na and K in cement, as well as fly ash. The fly ash-based
composites augment the resistance to corrosion through densification of concrete when
appropriately proportioned and sufficiently cured [208].

3.4. Nature of Fly Ash—Crystalline or Amorphous

Fly ashes are the by-product that is derived from coal-combustion, possessing an
intrinsic heterogeneous property. In general, it contains three dissimilar kinds of con-
stituents such as crystalline minerals, non-burnt particles of carbon and non-crystalline
alumino-silicate glass—each one with exceptional reactivity while employed. The process
of eliminating this non-burnt carbon through calcination [209] partly converts the amor-
phous phases that exist with fly ashes into crystalline phases. This contains the distinctive
crystalline phases such as quartz, hematite, mullite, ferrite anhydrite, spinels, melilite,
J. Compos. Sci. 2022, 6, 219 17 of 59

periclase, merwinite, lime and tricalcium aluminate [210]. Mostly, fly ashes are comprised
of glassy shape material possessing a weak atomic structure. On account of the amor-
phous nature, the ingredients, by and large, take part in the chemical reaction [211]. As a
result, highly amorphous fly ashes are more effectual in improving the pozzolanic reaction.
Sakai et al. [212] accounted for the impact of the amorphous-type content of fly ashes on the
pozzolanic reaction at later stages. Moreover, in the case of fly ash containing lower calcium,
an alkaline environment favours less reactivity because of the inert nature of most of these
crystalline phases. Further, because of a few reactive crystalline phases, fly ash containing
higher calcium is more reactive. Tkaczewska [213] added the benefit of employing a finer
sized particle of fly ash in accelerating the grade of SiO4 depolymerization, which escalates
the pozzolanic reactivity.

3.5. The General Applications of Fly Ashes

The applications of coal-fired fly ashes have drawn the attention of vast numbers of
researchers in recent years. The most significant fields for the applications of fly ashes that
are accounted are concrete production, road basement, waste solidification/stabilization,
cement clinkers, asbestos, the construction of roads and embankments, mine reclamation,
the recovery of precious metals, ceramics and glass ceramics, the synthesis of zeolites,
low-cost adsorbents for waste removal, soil amendment, nutrients, a silica and alumina
source for producing zeolites, etc. [214–220], and quite recently for geopolymer binders,
pastes, mortars and concretes [221]. Its significant use has also recently been found in
the production of diverse fly ash-based geopolymers with a state-of-the-art binder or
cement, which is more or less comparable to hydrated cement in appearance, properties
and reactivity, as either raw or as a supplementary cementitious material (SCM) [221,222].
The reusing of coal ash has been considered by the United States Environmental
Protection Agency [132], which has resulted in moves to save the environment and economy,
besides product gains such as mitigated emissions of greenhouse gas CO2 , the lowered
necessity of dumping them in landfills, along with the conservation of restricted natural
resources. The declined costs of coal fly ash have enabled cheaper construction materials
on one hand, while on the other hand, the escalated revenue from the sale of coal fly ash
substituting costly cement has altogether benefited the economy. The enhancement of the
strength, durability, and workability of fly ash-based construction materials has proved
them to be the ultimate product of quality. Therefore, it can be noted that economic values
and the improvement of the environment do not undermine the quality of the final finished
geopolymer products, indicating the sustainability of industrial production that uses coal
fly ashes.
The fly ash application strategies can be classified into three major groups based on
their usefulness and economic value, i.e., non-advantageous, advanced and straightfor-
ward [223]. The best fly ash utility rate is based on their simple use for construction and
building objectives. Although, their use for the production of building materials necessitates
very cautious consideration of global levels of environ-safety and financially reasonable
standard parameters, based on cost gain calculations and socio-economic aspects entailing
the GDP of particular nations [224]. However, industrial technologies are not available for
the advanced use of fly ash. In accordance with the European Coal Combustion Products
Association, 51.7% of the entire by-products of coal combustion viz., fly ash, bottom ash,
fluidized bed combustion ash, boiler slag, FGD-gypsum, etc., are employed for building,
agricultural and road pavements, while 39.8% are used for restoration and reclamation. The
rate of total use is 91.5%. As per ASTM standard, the potential end application of fly ash
entails soil amendment; waste treatment, as well as stabilization; hazard waste treatment;
and the production of slurry walls, mineral fillers, pozzolanic liners, cement, concrete, as
well as gypsum products.
J. Compos. Sci. 2022, 6, 219 18 of 59

3.6. Opportunities of Coal Fly Ash

Researchers investigate the possible transformation of CFA into a sequence of effective
products such as geopolymers, catalysts, zeolites, and photo-catalysts. Since the CFA
contains aluminosilicate, it is preferably used for the manufacturing of more competitive
cost-effective products than the costly commercial types of products. Processes of physical,
chemical, quality control, packaging and final distribution can be used for the manufactur-
ing of CFA-based adsorbents. A golden prospect for both the coal-fired power plants and
the coal factories is their employment and support of lucrative plans by instituting a lateral
or autonomous unit for the production of value-added products from CFA.

4. Fly Ash Based Geopolymers

In the last couple of years, greater than ever attempts have been made for the utilization
of profuse fly ashes in a competent way—particularly, with green concept. The application
of the profuse waste of fly ash for the production of fly ash-based geopolymer is found
with nine times lower CO2 emissions as compared to the OPC system [225,226]. These
up-to-date composites largely demonstrate closely equivalent durability and mechanical
strength as with hydrated Portland cement, and they can be used to preserve natural
resources as a class of inorganic green cement [227]. The use of fly ash as either a precursor
or SCM not only enhances the workability and mitigates hydration heat, as well as thermal
cracking in concrete at early periods, but also increases the mechanical and durability
attributes of concrete (particularly at later stages) [228].

4.1. Production of Fly Ash based Geopolymers

The manufacturing of fly ash-based geopolymers is possible through an exothermic
and complex chemical process that was coined by Davidovits as geopolymerization, which
includes stages such as dissolution, precipitations, restructuring, gelation and eventually
poly-condensation [229]. The genetic mechanism of fly ash-based GP can be explained in
three steps [229,230]. The initial step includes the dissolution of the alumino-silicate of fly
ash, which takes place by an alkaline activation at a low temperature and at atmospheric
pressure, and hydrolysis, which forms the monomers of aluminate and silicate. Then, the
Al3+ and Si4+ ions are transformed into oligomers that generate a gel with comparatively
big networks through condensation. Lastly, the emergent gel continues to restructure, and
the amorphous structure gives rise to the development of an alumino-silicate network via
poly-condensation reactions. However, the reaction kinetics that occur in the series, of
course, are much more complicated and remain hard to pin down. The reactions that occur
among fly ash, as well as alkali activator solutions, include Na2 SiO3 , NaOH, KOH, K2 SiO3 ,
etc., whereby Si-O-Si- or Si-O-Al- bonds of alumino-silicate break and liberate active Si4+
and Al3+ ions. Subsequently, the condensation of these released Si4+ and Al3+ ions takes
place, which is followed by other complex reactions such as nucleation, oligomerization,
and polymerization, which finally lead to a novel polymer that is based on aluminosilicate
with a novel amorphous 3D network structure with a SiO4 and AlO4 tetrahedra. For testing
or applications, the geopolymer paste that is produced with fly ash is additionally cast into
a mould and placed into an oven at a necessary temperature, or it can be left to cure for
a certain time to develop geopolymers based on fly ash. The chains of alumino-silicate
oligomers can be a form of polysialate –Al-O-Si- chain, polysialate disiloxo –Al-O-Si-Si-Si-
chain and polysialate siloxo –Al-O-Si-Si- chain, depending on the Si: Al ratio. In alumino-
silicate monomers, Si4+ is partly replaced by Al3+ , and the negative charge results in the
alumino-silicate chain being balanced with alkali cations such as K+ or Na+ [231,232].
In this framework, the Si: Al ratio derives notably from the ultimate structure of the
resultant geopolymers [233]. For instance, it was found that the Si to Al ratio in the fly ash
reactant had a noteworthy effect on porosity, which is one of the significant parameters for
controlling geopolymer mechanical strength [234,235].
In addition to the Si/Al ratio, the alkaline solution strongly influences the microstruc-
ture of the produced fly ash geopolymer. When fly ash comes into contact, it starts to be
J. Compos. Sci. 2022, 6, 219 19 of 59

discharged and transferred with alkaline activators such as NaOH, KOH, Si4+ , Al3+ and
other ions. For illustration, the amount of Si4+ and Al3+ that is released is affected by NaOH
concentration. A high concentration of about 10 mol/L of NaOH solution is advantageous
for the decomposition of the alumino-silicate of the fly ash, and then the discharge of Si4+
and Al3+ takes place. For instance, the solubility of Al3+ and Si4+ that are present in NaOH
liquid is more than in KOH activator liquid with an identical concentration [236].
Moreover, the transfer of Al3+ and Si4+ ions and the poly-condensation of alumino-
silicate oligomers could also be escalated by an alkaline liquid with a higher concentra-
tion [237].
Furthermore, diverse alkaline cations have dissimilar charge density and sizes, and
they also hydrate differently. This has a definite impact on the alumina silicate chain
nucleation, the charge density of the chain, the chain development, the degree, and the
polymerization process rate [238]. The leaching rate of Al3+ and Si4+ ions determine the
actual obtainable Si to Al ratio in a series of reaction kinetics to produce geopolymers,
and consequently act for the fly ash-based geopolymer structure. Fascinatingly, a recent
investigation by Ma et al., 2013 [239] uncovered that the addition of Na2 SiO3 to a solution
of alkali could augment such a Si to Al ratio, resulting in a low porosity and a finer pore
network in a geopolymer matrix.
The setting time for fly-ash geopolymer is generally taken into account for the worka-
bility of the final products of fly ash-based geopolymer. Usually, the ultimate setting can
be achieved in 1 to 2 h at room temperature, while the higher CaO and calcium additive
Class C fly ash content, as CaCl2 , reduces fly ash-based geopolymer paste setting time [240].
During the course of geopolymerization, Al3+ and Si4+ ions react with Ca2+ , either into the
fly ash or from the outside calcium additives, to produce gel of calcium-silicate-hydrate,
gel of calcium-aluminate-hydrate or gel of calcium-aluminium-silicate-hydrate (CASH) [C
1/4 CaO, S 1/4 SiO2 , A 1/4 Al2 O4 , H 1/4 H2 O] in the presence of water [241]. Ca2+ ions lend a
hand to accelerate CASH gel and CSH gel, and the nuclei development and agglomeration
of Ca2+ ions lend a hand in accelerating CASH gel and CSH gel nuclear development and
agglomeration [242]. The swift development of amorphous of CASH gel and CSH gel re-
sults in less setting time, creating ultimate products and diminishing the porosity, whereas
a quick setting time has a negative effect on the development of more geopolymeric gel.
The higher concentration of NaOH could lengthen the time for setting by restricting the
leaking of Ca and permitting the usual process of geopolymerization to manage the setting
time of geopolymeric paste [243].
Nevertheless, the fly ash dissolution at room temperature is incomplete, and the lower
fly ash reactivity increases the time that is needed to set up a geopolymer based on fly
ash. Curing is, thus, essential, i.e., that geopolymer paste must be kept within a practical
range of humidity and temperature, and the prolonged duration of the cure promotes the
growth of a more crosslinked bond and denser microstructure. It has been recorded that
the reactivity of fly ash becomes high while the temperature for curing is from 30 ◦ C to
50 ◦ C [244].
To enhance the performances of geopolymer and the reactivity of fly ash, slag, fibre,
chitosan, red mud and rice husk–bark ash (RHBA) can be supplemented with fly ash to
synthesize geopolymer. Captivatingly, the addition of blast furnace slag (BFS) [245] can
improve fly ash reactivity while geopolymerizing. Idawati et al. [246] studied the fly ash
plus slag-based geopolymer with dissimilar ratios of fly ash to slag and revealed that the
geopolymerization of geopolymer based on slag was dominated by CASH gel, whereas
fly ash-based geopolymer was dominated by gel of sodium-alumino-silicate (NASH).
Kumar et al. [247] replaced fly ash with 5–50% slag to produce geopolymer at 27 ◦ C and
noted that the reaction was obtained through the dissolution and precipitations of the gel
of CSH. Likewise, Yang et al. [248] discovered that the initial setting period for fly ash
plus GBFS-based geopolymer was boosted and the level of polymerization of geopolymer
declined due to the higher calcium content of GBFS. The rice husk–bark ash (RHBA)
contains around seventy-five percent SiO2 , enhances the pozzolanic content of the matrix of
J. Compos. Sci. 2022, 6, 219 20 of 59

geopolymers and increases the quantity of geopolymer –Si-O-Si- bonds in the geopolymer
gel (NASH). Red mud is a highly alkaline material consisting essentially of Fe, Al and Si, as
well as minor CaO and TiO2 oxides and hydroxides. Its addition can control the Si: Al ratio
and lower alkaline activator consumption [249]. Fly ash-based geopolymer can solidify the
heavy metals trace and is capable of immobilizing them.

4.2. Fly Ash Based Geopolymer: Properties

The properties of geopolymers may differ not merely in accordance with the origin,
morphology and size of a particle of fly ash, but also with the metal, alkali and amorphous
contents. The properties of geopolymers also depend on various parameters such as
sodium hydroxide NaOH concentration, an alkaline solution to FA ratio, sodium silicate to
sodium hydroxide ratio, alkaline liquid to fly ash ratio, curing duration, curing temperature,
superplasticiser dose, added water content and rest period. Fly ash-based geopolymers
are very useful materials for green constructions in the form of paste, mortar, binder and
concrete. Hence, they should essentially exhibit the acceptable mechanical attributes—
especially of strength, as well as durability—to establish them as promising sustainable
building materials of the future [250].

4.2.1. Compressive Strength

The value of the compressive strength of fly ash-based geopolymers depends upon
Si/Al ratios, alkali activator solutions, the content of calcium, a choice from a variety of
additives and curing conditions such as temperature, as well as period.
The concentration, as well as the alkaline activator solution, affects the release of Si4+
and Al3+ ions from fly ash during geopolymerization reaction kinetics. It is established
that alkaline activator solution with a higher concentration is usually advantageous for
achieving elevated compressive strength; however, there exists an optimum limit [251].
Gorhan and Kürklü [252] have manufactured fly ash-based geopolymer by using dissimilar
concentrations such as three, six and nine mol/L of NaOH. The best possible compressive
strength figuring of 22 MPa was attained on activation of the geopolymer paste-based on
fly ash with the concentration of 6 mol/L of sodium hydroxide, and subsequently cured
at a temperature of 85 ◦ C for 24 h. The solution of sodium silicate (Na2 SiO3 ) is generally
employed with NaOH to boost the compressive strength of resultant geopolymer based
on fly ash [253]. This is because of the greater viscosity of sodium silicate, which can
help to form geopolymeric gels and achieve a compact, eventual micro-structure of a fly
ash-based geopolymer.
Additionally, the course of separate activation also affects the compressive strength
of geopolymer based on fly ash. For illustration, Rattanasak and Chindaprasirt [254] first
attempted to add NaOH activator liquid to fly ash to release the Si4+ and Al3+ ions for
10 min, which was followed by employing Na2 SiO3 activation to favour the formation of
a homogeneous geopolymer paste for another minute. This type of separate activation
has contributed to the higher strength of fly ash geopolymer. While fly ash was mixed
separately and activation was made with 10 mol/L concentrated NaOH plus sodium
silicate with a molar ratio of 1.0, followed by a curing temperature of 65 ◦ C for 48 h, the
resultant compressive strength value of geopolymer based on fly ash was found to range
from 60 to 70 MPa.
The ratios of Si: Al are confirmed by precursor materials, and the alkaline solution
that was employed was Na2 SiO3 . Higher ratios of Si/Al enhance the quantity of –Si-
O-Si- bonds, giving them the elevated compressive strength of an entirely consolidated
structural matrix of geopolymer, because the –Si-O-Si- bonds are stronger than that of
–Al-O-Al- and –Si-O-Al- bonds. For instance, Yang et al. [255] produced high magnesium-
nickel slag and fly ash geopolymer by activation through a solution of Na2 SiO3 . They
revealed that the key phase in fly ash plus high magnesium-nickel slag (HMNS)-based
geopolymer was a sort of sodium magnesium aluminosilicate gel. The addition of high
magnesium-nickel slag (HMNS) boosted the content of silica. Furthermore, the particles
J. Compos. Sci. 2022, 6, 219 21 of 59

of HMNS played the role of micro-aggregates and mitigated the entire volume of pores
that were present in the geopolymeric pastes. On employing 20% of HMNS in the said
manufacturing process, the geopolymer exhibited an improved compressive strength of
more than 60 MPa. However, the elevated quantity of slag (like slag/binder was greater
than 70%) escalated the compressive strength of geopolymer based on fly ash plus HMNS.
Regrettably, it caused a quick setting and cracked on account of the autogenous shrinkage
of the slag [256]. Moreover, Wang et al. [257] produced fly ash plus slag-based geopolymer
by using unlike ratios of fly ash/slag such as 0, 20, 40, and 60 wt.% and similarly dissimilar
NaOH activator solutions with 0.5, 1 and 1.5%, and subsequently cured them for one,
three, seven and twenty-eight days. The increase in the quantity of slag enhanced the
value of the resulting geopolymer’s compressive strength, and the best possible value
of compressive strength that was obtained in this case was 93.06 MPa. Deb et al. [258]
utilized a fusion of Class F type fly ash addition of slag to obtain a blended geopolymer
of slag plus Class F type fly ash in a ratio of 0, 10 and 20% by activating with Na2 SiO3
plus NaOH activator solutions, correspondingly. The value of the compressive strength of
the resultant product was enhanced with a boost of the ratio of slag/Class F fly ash. The
geopolymer concrete is manufactured by fly ash of 80% and 20% slag, and having used 40%
NaOH plus Na2 SiO3 activator solutions and cured subsequently at a temperature of 20 ◦ C,
achieved the optimal compressive strength value of 51 MPa. Xu et al. [259] employed slag
and fly ash to produce geopolymer through activation by activator that was made from
Hanford secondary waste, with the concentration of 5 mol per 1L sodium hydroxide liquid
with solid binders. In this case, the best possible value of compressive strength that was
obtained was 52.5 MPa when the ratio of fly ash to GBFS by mass was kept as 5/3. The
addition of rice husk–bark ash enhanced the silica content of the geopolymer composite
and escalated the quantity of bonds (–Si-O-Si-) in the geopolymer, and the value of the
compressive strength [259]. Nazari et al. [260] supplemented rice husk–bark ash added
with fly ash to manufacture geopolymeric paste with oven curing at 80 ◦ C for 28 days.
The study achieved geopolymer with a compressive strength value of 60 MPa. Likewise,
Songpiriyakij et al. [261] synthesized geopolymer based on fly ash by employing the fusion
of fly ash with rice husk–bark ash with NaOH as the activator solution, subsequently
curing it at 27 ◦ C for 24 h, and then again at 60 ◦ C for up to 24 h. Here, the optimum
ratio of SiO2 /Al2 O3 to achieve the best possible value of compressive strength of 73 MPa
was recorded as 15.9. Zhang et al. [262] manufactured fly ash plus red mud blended
geopolymer at a curing temperature of 23 ◦ C. The values that were obtained for the highest
compressive strengths were found to vary from 11.3 to 21.3 MPa, while the Si to Al ratio was
2. Calcium hindered the gelation of alumina and silica in the course of geopolymerization
and modified the microstructures of geopolymer based on fly ash, hence, altering the
compressive strength value [263]. The coexistence of NASH gels and CSH gel generally
enhances the compressive strength of ultimate yields. One of the reasons for this is that the
CSH amorphous gel mitigates the porosity factor [209]. In addition, temperature curing
and duration also influence fly ash-based geopolymer compressive strength. Prolonged
periods of curing that range from 6 to 28 days display the enhanced value of fly ash-
based geopolymer compressive strength. The elevated temperature curing enhances the
compressive strength through eliminating water from the early formed geopolymer and
achieves the collapse of the capillary pores through a denser structure [264]. Geopolymer
can be cured at a lower, i.e., even room, temperature, but the development of compressive
strength takes place gradually and slowly, which forever necessitates a long and drawn
out curing period [265]. Nasvi and Gamage [266] uncovered that the crack commencement
and sealing of the thresholds of geopolymer based on fly ash cured at higher temperatures,
varying from 60 ◦ C to 80 ◦ C, in comparison with those that were cured at an ambient
temperature of 23 ◦ C and 40 ◦ C. Nonetheless, the lengthened elevated temperature curing
shatters the geopolymer granular structure, causing dehydration, as well as excessive
shrinkage, and at last mitigating the value of its compressive strength [70].
J. Compos. Sci. 2022, 6, 219 22 of 59

The conventional heating technique such as “Steam curing” depends upon the heat
conductivity from the exterior to the interior surface fly ash-based geopolymer paste
through steam. This heating is inconsistent and necessitates a prolonged period of heating
to obtain the desired temperature. On the other hand, microwave heating works based on
internal energy dissipation, which is accompanied by the excitation of molecular dipoles
in electro-magnetic areas, and it conveys swiftly with more consistent heat [267]. Chin-
daprasirt et al. [268] synthesized the paste of geopolymer based on fly ash with 10 mol
per 1 L concentrated Na2 SiO3 with NaOH solutions, and subsequently cured it in the
90W radiation of a microwave for five minutes. After that, supplementary heating oc-
curred at a 65 ◦ C curing temperature for a curing period of 6 h, resulting in a similar
compressive strength to that which was obtained with a 65 ◦ C curing temperature for
24 h of fly ash-based geopolymer. The radiation from the microwave accelerated the fly
ash dissolution in an alkaline liquid and developed a denser microstructure. Given that,
the microwave radiation reduced the requisite curing period and further improved the
geopolymerization kinetics.
Altogether, boosting the Si/Al ratio largely augments the value of fly ash-based
geopolymer’s compressive strength. The improvements in the Si to Al ratio can be seen
in addition to the outer slag, red mud and rice husk–bark ash, but the intrinsic causes are
difficult and complex. The progress in the synthesis signalled that one of the prominent
reasons could be attributed to the escalated quantity of -Si-O-Si- bonds to a certain extent,
rather than -Al-O-Al- and -Si-O-Al- bonds. To sum up, the application of K2 SiO3 or Na2 SiO3
along with sodium hydroxide as activators for fly ash activation can augment the Si to
Al ratios and, in this way, pilot a structure which is more compact and which displays
elevated compressive strength. Not only this, the existence of calcium within fly ash or
employed as an additive is advantageous for synthesizing the amorphous gel of CASH,
as well as CSH, and mitigates the available porosity and attains the higher compressive
strength of geopolymer. Curing demonstrated a remarkable impact by modification of
the product density and porosity on the value of the compressive strength of the fly-ash
based geopolymer.

4.2.2. Flexural and Splitting Tensile Strength

No doubt, geopolymers based on fly ash perform extremely well under compression
strength examinations. Their performance is controlled by the start of cracks in mass; how-
ever, this is under tensile loads. Lee et al. [269] accounted for the investigational upshots
of the tensile performance of geopolymeric concrete. With an increase in the sand to fly
ash ratio, a gradual drop in tensile strength was monitored. Zhuang et al. [270] recorded
a comparison between ACI standard design strength and the results of experiments that
examined geopolymer concrete tensile performance. They observed that the splitting
tensile strength of geopolymer concrete was likely to be similar to the design values that
were provided by the ACI standard. Zhang et al. [271] noted that the geopolymer concrete
performed more than the OPC-based concrete in the context of tensile strength. Adak
et al. [272] unearthed that the supplement of 5 to 6 percent of nano silica enhanced the
geopolymer concrete‘s tensile strength with standard curing. Al-Majidi et al. [273] un-
covered the findings through experiments on geopolymer concrete that employed fly ash
plus GGBFS. The outcomes demonstrated that the application of slag in the geopolymer
concrete had an optimistic impact on the direct tensile performance. The impact of slag
on the tensile attributes of geopolymer concrete, whereby an enhancement of up to 30%
can be monitored, leads to the augmentation of its tensile strength. Moreover, the review
of past research revealed that the tensile performance of geopolymer concrete is more
magnificent than OPC concrete, possessing identical compressive strength [274,275]. Nath
and Sarker [276] provided an idea for a geopolymer concrete and OPC concrete mix, manu-
factured through various proportions, as well as additive materials of GGBFS, OPC and
calcium hydroxide, for investigating fly ash-based geopolymer concrete’s flexural strength
at an ambient curing temperature. The flexural strength of geopolymer concrete based on
J. Compos. Sci. 2022, 6, 219 23 of 59

fly ash is affected considerably by the kind of additive that is employed, accompanied by
fly ash. In comparison with calcium hydroxide and GGBFS additives, the addition of OPC
with fly ash enhances the flexural strength of geopolymer concrete.

4.3. Durability Properties

The significant parameters for the durability of fly ash-based geopolymers such as
resistance to sulphate, chloride, thermal, acid, efflorescence and freeze–thaw, must be
taken into consideration to establish it as a potential construction material. The durability
property is strictly associated to the microstructure, as well as the migratory ions conduct
from geopolymer based on fly ash, which, consecutively, could be regulated by the alkali
activator, the supplement of composite materials of calcium, as well as by silica fume, along
with curing through its synthesis.

4.3.1. Resistance against Chloride

Resistance against chloride is one of the key aspects for the durability of fly ash-
based geopolymer composites. The penetration of chloride encourages the corrosion of the
entrenched steel bars in reinforced geopolymer concrete. The chloride ions infiltrate into the
geopolymers through capillary pores absorption, ions diffusion and hydrostatic pressure.
The comparatively higher concentration of sodium hydroxide facilitated the leaking of
additional Si4+ and Al3+ ions from fly ash precursor and produced a superior level of
poly-condensation, resulting in a dwindling of fly ash-based geopolymer porosity. The
chloride penetration depends upon the porosity of the material. For instance, Chindaprasirt
and Chalee [277] synthesized a geopolymer based on fly ash utilizing Na2 SiO3 plus sodium
hydroxide mix activator solutions. In this case, dissimilar concentrations of NaOH were
used such as 8, 10, 12,14, 16 and 18 mol/L, but the molar ratio of SiO2 /Al2 O3 was kept as
a constant. The rate of chloride penetration reduced with the boost in the concentration
of NaOH, which was employed in the course of geopolymerization on account of the
refinement of the pore structures, due to the reaction of polycondensation. Ismail et al. [278]
studied the chloride permeability of an infusion of Class F type fly ash plus slag-based
geopolymer by the chloride accelerated technique and the ponding technique. AgNO3
was useful to disclose the depths of chloride penetration. The upshot displayed that a
slight development of silver chloride (AgCl) was found for the geopolymer based on slag.
They reported that the slag favoured the development of a denser gel of CASH, offering to
enhance the durability and mechanical strength when exposed to chloride, while fly ash
encouraged the production of additional porous NASH gels, reducing the chloride ions’
resistance transportation.
Even though a greater porosity was monitored in the case of the geopolymer in
comparison with the OPC- system samples, still, the geopolymer exhibited greater chloride
resistance. Yang et al. [279] manufactured a fly ash addition with a slag-based geopolymer,
with a ratio of slag to fly ash of 0, 0.25, as well as 0.50, along with the exposure of the
precursor materials to a 3% NaCl solution for 72 h. The CASH gel in the fly ash plus slag-
based geopolymer led to a lower diffusion of chloride than the NASH gel. Moreover, the
fusion of slag with fly ash-based geopolymers led to the enhancement of the pore structure.

4.3.2. Resistance against Sulphate

The migration of sodium-ion (Na+ ) into the sulphate solution from the fly-ash-based
geopolymer results in vertical cracks. Not only this, the solution of sulphate generally
causes the breakdown of the bond –Si-O-Si- in geopolymeric gel with the leaking of silicon.
Bakharev [280] produced geopolymer based on fly ash, utilizing solutions of KOH, NaOH or
Na2 SiO3 as activators, and studied the durability subsequent to exposing them to sulphate
media, which consisted of 5% solutions of MgSO4 alone, Na2 SO4 alone and MgSO4 plus
Na2 SO4 combined for five months. Subsequent to immersion, the geopolymer based on
fly ash specimens were found to be slightly altered. The production of the geopolymer
that was activated by NaOH displayed the highest resistance to sulphate on account of an
J. Compos. Sci. 2022, 6, 219 24 of 59

additional steady cross-linked structure. A mixture of silty clays plus fly ash was used by
Sukmak et al. [281] to synthesise a geopolymer and to examine its resistance by five percent
Na2 SO4 plus MgSO4 in solutions by weight. The decline in the compressive strength
that was observed for the clay plus fly ash-based geopolymer subsequent to exposure for
240 days was in 10.8% solution of Na2 SO4 and 21.6% solution of MgSO4 . The ettringite,
brucite and gypsum were noticed after being subjected to sulphate conditions. Due to the
reaction to the development of ettringite and sulphates, the CSH phase disappeared. The
magnesium sulphate degraded the GPC significantly in the calcium-rich geopolymer that
was produced in the end products. By replacing the calcium in the structure, it breaks the
CSH link and creates the Mg-SH. The magnesium-formed structure increased the volume,
causing fracture development in the GPC. At the same time, sodium sulphate does not
significantly degrade the GPC. The mechanical properties of GPC-mixed specimens are
reduced by magnesium sulphate [282]. The high-calcium BA geopolymer mortar has
exceptional resistance to sodium sulphate [283].

4.3.3. Acid Resistance

The acidic conditions can rigorously reduce the life-cycle period of composites. Acid
attack is found to be accompanied by the depolymerization of an alumino-silicate structure,
as well as the release of silicic acid in the geopolymer based on fly ash. While submerged in
a solution of a strong acid, K+ and Na+ of fly ash-based geopolymer might be replaced by
H3 O+ or H+ , the breakdown of bonds –Si-O-Al-, as well as –Si-O-Si-, along with a release
of silicic acid.
Diverse solutions of alkali such as NaOH, Na2 SiO3 and KOH were employed by
Bakharev [284] to produce a fly ash-based geopolymer, following their immersion into
5% solutions of CH3 COOH and H2 SO4 for five months. The fly ash-geopolymers were
been manufactured by activating them with 8% NaOH solution. They displayed a steadier
structure and higher resistance against both solutions of CH3 COOH and H2 SO4 acid, in
addition to the fly ash form geopolymer that was produced by activation through KOH
(which demonstrated an enhancement in the average pore diameter and the active sites in
the geopolymeric gels lying on the surface, leading to inferior durability).
In addition, there is an emphasis on the impact of silica and calcium on the acid
resistance of the geopolymer based on fly ash. In acid solutions for nitric acid HNO3
and sulfuric acid H2 SO4 , Lloyd et al. [285] studied corrosion rates in a Class C fly ash
plus slag-based geopolymer. The calcium content of Class C fly ash or slag was found
mitigate the mass transport rates by developing tortuous pores and fine networks in the
geopolymer. Not only this, because of the enhancement in the content of alkali in the form
of Na2 O, the layer that underwent corrosion became more robust, and further vulnerable
to the formation of cracks. The high content of alkali is advantageous for the release of
more aluminium and calcium, as well as for producing geopolymeric gels. When it was
removed upon exposure to acids, the structure of the geopolymer was more susceptible
under acid exposure conditions. Chindaprasirt et al. [277] supplemented silica fume in the
proportion of 1.5, 3.75, as well as 5.0% with fly ash to synthesize geopolymeric mortars.
A resistance to acid by the said mortars was examined in three volumetric percentages of
H2 SO4 acid. The best possible addition of 3.75% silica fume improved the strength of fly
ash-form geopolymer and exhibited the optimum resistance to acid because of the boost in
CSH gels, resulting in a denser structure.
With higher temperature curing, resistance to acid by a fly ash-form geopolymer is
advantageous. Nguyen et al. [286]maintained a curing temperature of 80 ◦ C for curing
period of 10 hours for the fly ash-based geopolymer at and after that the immersion in
a solution of 1, 2 and 4 mol/L of concentrated HCl. They noticed that the fly ash-form
geopolymer maintained a value for compressive strength of roughly 20 MPa, greater than
OPC in the 1, 2 and 4 mol/L HCl solution. Furthermore, Chindaprasirt et al. [287] cured
fly ash-form geopolymer with a 90W microwave for five minutes and observed that the
microwave radiation escalated the process of geopolymerization and provided improved
J. Compos. Sci. 2022, 6, 219 25 of 59

densification that was analogous to the traditional curing. The fly ash-form geopolymer
that was cured with a microwave had a dip in the 3 volume % of H2 SO4 and recorded that
it merely had a little strength loss when subjected to the acid exposure.

4.3.4. Resistance against High Temperatures

Although the geopolymer based on fly ash is subjected to higher temperatures, the
amount of water that evaporates from its structure results in shrinkage [288]. Some of
them demonstrate an enhancement in strength, subsequent to their exposure to higher
temperatures, proving themselves fit to use for constructions as concrete, thermal barriers,
fire-resistant structures, refractory and thermal insulators, etc.
It has been made known that heat can travel more swiftly in geopolymer concrete than
its counterpart from the OPC system during fire exposure, resulting in a lower temperature
gradient within geopolymer concrete [289]. The OPC concrete exhibited average residual
strengths of 90, 52 and 11 to 16%, subsequent to its exposure to fire at 400, 650 and 800 to
1000 ◦ C, respectively, while in the context of geopolymer concretes, the average residual
strengths were 93, 82, and 21 to 29%, i.e., higher than OPC concrete, following the same
kind of treatments. Furthermore, the OPC concrete underwent rigorous spalling and
widespread surface cracking, subsequent to the exposure to temperatures of 800 to 1000 ◦ C,
whereas there was an absence of spalling and merely negligible surface cracking in the case
of geopolymer concrete. Guerrieri and Sanjayan [290] exposed the fly ash plus slag-form
geopolymer, maintaining the ratio of fly ash to slag as 100, 65/35, 50/50, 35/65 at 800 ◦ C.
Their outcomes evidenced that the geopolymer samples with very low early strengths
of less than 7.6 MPa displayed an enhancement in the residual compressive strength of
up to 90%, following exposure at 800 ◦ C, whereas the samples with an early strength of
28 MPa—along with samples with an initial strength of 83 MPa—lost roughly 70 and 90%
in residual strength, following 800 ◦ C thermal exposure, correspondingly. These dissimilar
residual strengths of fly ash plus slag-formed geopolymer, subsequent to its exposure at
a temperature of 800 ◦ C, were the result of sintering of the non-reacted fly ash–slag and
further hydration. Geopolymer has high early strength and is less able to permit thermal
incompatibilities among the internal and external parts of the sample on account of uneven
temperatures during the heating period. Rickard et al. [291] studied the thermal attributes
at a temperature of more than 500 ◦ C for Class F fly ash-formed geopolymer. The peak
shrinkage was about 3%, which was found at 900 ◦ C thermal exposure temperatures. The
Fe2 O3 that was present with fly ash at 15% by weight directly influenced the thermal
characteristics of the geopolymer, by impacting the thermal expansion, modifying the
composition and altering the morphology, following the course of heating.
The density and pore structure of the geopolymer based on fly ash encourages escape
from the moisture and facilitates damage protection during heating. Kong et al. [292]
synthesized and exposed a fly ash-based geopolymer to heating at a temperature of 800 ◦ C
and found that a little quantity of moisture fled from the fly ash matrix, as well as the pores
creating furnished routes to escape moisture in the matrix, thus, reducing the possibility of
damage to the matrix at very high temperatures. Bakharev [293] compared the influences of
the course of thermal temperature at 800 to 1200 ◦ C on the geopolymer that was composed
of Class F type fly ash, activated by sodium hydroxide, as well as potassium hydroxide,
correspondingly. The geopolymer that was activated by sodium hydroxide activator solu-
tion showed a quick strength drop, in addition to a higher shrinkage at temperature 800 ◦ C
because of the theatrical enhancement of the average pore size, whereas another geopoly-
mer that was produced with activation by potassium hydroxide displayed a noteworthy
escalation in the value of compressive strength on heating course (whereby the strength
deterioration was only initiated at 1000 ◦ C). The supplement of low-concentrated foaming
agent led to a lower density through the cellular structure. Rickard and van Riessen [294]
also developed the foamed Class F type fly ash geopolymer, maintaining a ratio of Si to
Al of 2.5, and exposed it to a simulated fire for 60 to 90 min, resulting in its considerable
loss of strength. Foaming notably diminished the strength of Class F type fly ash-formed
J. Compos. Sci. 2022, 6, 219 26 of 59

geopolymer, whereas the thermal insulating characteristic was also enhanced, since their
thermal conductivities are mitigated by more or less half.
The use of Ca(OH)2 in the production of geopolymers based on fly ash led to the
development of the CSH gel and the different mineral developments and changes at high
temperatures. Fly ash-based geopolymer was produced, and the effect of calcium on the
thermal resistance was examined by Dombrowski et al. [295]. While the geopolymer was
subjected to temperatures that were greater than 600 ◦ C, the formation of amorphous
alumino-silicates and mineral sodalite took place, and this was converted into nepheline,
afterwards exhibiting a denser structure. The nepheline transformed into mineral albite
with its additional temperature increase. The fly ash-based geopolymer with a production
of eight percent Ca(OH)2 showed optimum strength and the lowest shrinkage with a
maximum nepheline content of 800 ◦ C and of feldspar at 1000 ◦ C. Geopolymer, when
subjected to fire, demonstrated not only the propensity to shrinkage, but also to crack. In
accordance with the standard that was fixed by the International Standards Organization,
Sarker et al. [296] tested the fire resistance by the fly ash of the geopolymer and OPC system
through exposure of the specimens to heating through fire at 400, 650, 800 and even at
1000 ◦ C. However, when the exposure to heat through fire was made of fly ash-formed
geopolymer at 1000 ◦ C, it showed only slight cracks on the surface and a mass loss of 4.8%,
whereas that of the OPC-system had a mass loss of 90%, proving fly ash geopolymer as an
excellent fire and thermal resistant.

4.3.5. Freeze–Thaw Resistance

In regions with severe environmental conditions, the freeze–thaw attack generally
accounts for the expansion of cement, as well as concrete, in-house cracking, and mass
loss [297]. It can be considered as a severe attack on composites next to chloride attack.
Remarkably, geopolymer based on fly ash has not exhibited any sign of deterioration, even
with 150 freezing cycles.
Temuujin et al. [298] synthesized a geopolymer using Class F type fly ash, activated by
a NaOH + Na2 SiO3 activator solution, and afterwards cured it with a curing temperature
of 70 ◦ C for 22 h. The supplement of Na2 SiO3 solution did not enhanced the durability cri-
terion of the freeze–thaw of geopolymer based on fly ash. The amorphous Ca-compounds,
such as lime and anhydrite in fly ash, and the existence of crystalline negatively impacted
the resistance to freeze and thaw. The solution of Na2 SiO3 reacted with compounds of
calcium viz., CaO, amorphous calcium alumino-silicate and CaSO4 that were present in
the fly ash, as well as developed a CASH gel or Ca(OH)2 . The development of Ca(OH)2
weakened the internal structure and increased the water penetration, as well as demon-
strated a negative effect on freeze–thaw resistance. Air entrainment has been evidenced as
an efficient technique to raise the OPC system’s resistance to freeze–thaw.
Sun and Wu [299] made a comparison of both the geopolymer based on fly ash and the
OPC system with or without air entrainment for three hundred freeze–thaw cycles. OPC
without air entrainment suffered deterioration most gravely, displaying a loss in strength
of roughly 20% following 300 cycles, while 5% strength loss was seen for the OPC with air
entrainment. In the case of the geopolymer based on fly ash, without air entrainment, this
was found with an ultimate loss of 8.4%, with 300 cycles. Fly ash-based geopolymer with
the air entrainment exhibited a loss in strength of 6.8%. Undoubtedly, the air entrainment
did not show much of an optimistic impact on the fly ash geopolymer.
The influence of air entrainment on the scaling rate of fly ash-based geopolymer was
investigated by Brooks et al. [300]. Air-entrained geopolymer based on fly ash demonstrated
minor scaling after 40 cycles of freeze–thaw, whereas the geopolymer based on fly ash sans
air-entrainment was found without scaling. The compressive strength of fly ash-formed
geopolymer declined considerably through air entrainment from 10 to 30%, compared
to the sans air-entrained fly ash-based geopolymer, as well as the homogeneous, steady
pore structure, which is supposed to boost durability in the context of resistance to freeze–
J. Compos. Sci. 2022, 6, 219 27 of 59

thaw. This was not found to be absent in the case of fly ash-based geopolymer that was
not air-entrained.

4.3.6. Resistance against Efflorescence

Particularly, a geopolymer with higher alkali, as well as lower calcium contents tends
to be porous with an open micro-structure. The water solution is captured or linked with
the network in the pores, while the geopolymer 3D structure is finally developed [53]. In-
side the pore structure, the surplus sodium oxide is movable. In addition, this is susceptible
to producing crystal in a white colour, i.e., efflorescence, while contact with carbon dioxide
that is present in the atmosphere causes the degradation of the geopolymer [301]. The efflo-
rescent nature of fly ash-formed geopolymers is highly reliant on the kind of alkali activator
solution, the calcium that is present and the curing temperature. The application of KOH
in place of NaOH as an activator solution reduces the efflorescence of the geopolymer [302].
The higher concentration of alkali in the pore solution and the low connection of Na+ in the
geopolymeric structure are the root causes of moving Na+ in pore solution and lead to a
severe geopolymer efflorescence [303].
On the other hand, K+ represents a stronger bond to the alumino-silicate gel framework
and crystals of K2 CO3 are generally visually less evident than their sodium counterparts.
Zhang et al. [304] activated fly ash with sodium hydroxide to produce geopolymer. In
addition, they maintained a curing temperature of 23 ◦ C and 80 ◦ C. They revealed that
geopolymer displayed greatly inferior efflorescence at an elevated temperature, compared
to those that were manufactured at the lower temperature. The curing was beneficial to
crystallize and restructure NASH gels, as well as to reduce the rate of efflorescence. The
presence of calcium helps to develop CSH gel in geopolymer based on fly ash and a smaller
pore size with lower penetration, which puts stops the diffusion of alkali [305]. On the
contrary, in the case of the foamed geopolymer based on fly ash, the foaming resulted in
the large pore size and high porosity of the geopolymer based on fly ash, which led to the
quick leaking of alkali and, hence, resulted in speedy efflorescence [304].

4.4. Fly Ash-Based Geopolymer for Concrete

The emerging concerns regarding the environment and restricted natural resources
have motivated scientists, researchers, engineers and people related to construction and in-
frastructure industries to seek alternative construction materials [306]. Fly ash is one of the
profuse industrial by-product waste materials, employed as either precursor or supplemen-
tary cementitious material in manufacturing diverse geopolymers for the concrete industry.
Geopolymer concrete based on fly ash differs from OPC production regarding the higher
carbon dioxide emissions that are linked to it [307]. In several respects or under specific
conditions, fly ash-based cement has sometimes demonstrated a superior performance to
OPC. In comparison with OPC concrete, fly ash-based geopolymer concrete has a dense
microstructure with a lower diffusion of chloride and low porosity.
Reddy et al. [308] utilized Class F type fly ash as a precursor with Na2 SiO3 plus
NaOH as alkaline activator solutions to produce geopolymer cement. They revealed that
the referred geopolymer concrete demonstrated outstanding chloride attack resistance
with lesser cracks owing to corrosion, while it was subjected to an induced current and
simulated seawater. Alkali-silica reaction is a familiar phenomenon among the OH− in
the pores that are present inside the concrete matrix and the reactive aggregates of the
concrete. Alkali-silica reaction is accountable for the loss in strength, the distribution of
the concrete structure and, significantly, for cracking. It is well-known that fly ash-based
geopolymer concrete is considered to be susceptible to a lesser amount of ASR than OPC
concrete. Kupwade-Patil and Allouche [309] manufactured a geopolymer concrete based
on fly ash with reinforcement by steel bars using aggregates of quartz, siliceous limestone
and sandstone. Afterwards, they compared the cyclic wet and dry chloride medium for
chloride ion diffusion for more than 12 months, along with OPC concrete for comparative
study. Surprisingly, the outcomes suggested that OPC concrete specimens went beyond
J. Compos. Sci. 2022, 6, 219 28 of 59

the allowable limit by the ASTM standard for expansion, whereas geopolymer concrete
samples were found to be within the permissible range.
Additionally, the leaking and visual cracking were monitored in OPC concrete, while
geopolymer concrete-based fly ash demonstrated no such footprint of cracks. Normally,
aggregates encircle as high as 85% of the total material that is present in concrete. In
the case of fly ash-based geopolymer concrete, the interactions between the alumino-
silicate framework, alkali cations, aggregates and additives are key factors which affect
the mechanical performances on the whole. The powerful interfacial interactions among
the geopolymer matrix and the aggregates in a greater region provide the higher splitting
tensile strength amid steel reinforcements and geopolymers [310]. Moreover, the size of the
aggregates impacts on the performances of the fly ash-formed geopolymer concrete.
The influence of the aggregate size on the compression strength of fly-ash-based
geopolymer concrete with aggregates of crushed old basalt, slag and river sand at elevated
temperature was investigated by Kong and Sanjayan [311]. They reported that the thermal
incompatibility among the aggregates and the matrix of the geopolymer resulted in a
loss in strength for geopolymer concrete samples at very high temperatures. The larger
aggregates of more than 10 mm in size demonstrated high-quality performances in the
context of strength at both ambient and higher temperatures, whereas aggregates that were
less than 10mm in size favoured not only the spalling, but also wide-ranging cracking
at the higher temperature. The coarse recycled aggregate was employed to manufacture
geopolymer concrete based on fly ash with up to the standard attributes. Sata et al. [312]
utilized crushed bricks comprised of clay and structural beams of concrete subsequent to
crushing as recycled coarse aggregates to produce geopolymer concrete based on fly ash.
The referred recycled aggregate containing fly ash-formed geopolymer concrete displayed
inferior compressive strength values ranging from 2.9 to 10.3 MPa than the one possessing
natural aggregates.
Moreover, the ratio of the total void was 21.7 to 26.9% of the geopolymer concrete made
up of recycled aggregate, which was just analogous to those containing natural aggregate at
24.2 to 27.4%, and the water permeability that was recorded was 0.71–1.47 cm/s versus 1.18–
1.71 cm/s. Nuaklong et al. [313] employed high calcium fly ash with recycled aggregates
that were obtained from old concrete, possessing the compressive strength of 30–40 MPa
to synthesize the fly ash-based geopolymer, and examined the strength criterion. In this
case, they monitored the range of values of compressive strengths from 30.6 to 38.4 MPa,
less than those of fly ash-formed geopolymer concrete possessing crushed limestone as
an aggregate. The diverse superplasticizers such as polycarboxylates and naphthalene
(N) as the water reducer admixture were applied by Nematollahi and Sanjayan [314] to
enhance the workability of the geopolymer concrete. The polycarboxylates superplasticizer
of 3.3 wt.% caused a noteworthy decrease of 54% in strength, regarding concrete with no
use of superplasticizer.
On the contrary, N superplasticizer with a 1.19% weight caused a 22% decline in
strength. At a higher temperature, the use of superplasticizers is not useful to geopolymer
concrete at elevated temperatures. The lower permeability of the geopolymer based on fly
ash can effectively stop CO2 leakage.
Nasvi et al. [315] investigated the apparent permeability of the CO2 of geopolymer
cement based on fly ash. Furthermore, Nasvi et al. [316] synthesized geopolymer cement
by employing fly ash with NaOH plus Na2 SiO3 activator solutions and examined the
permeability of CO2 under three conditions, such as (i) temperatures of 23 to 70 ◦ C; (ii) con-
fining pressures of 12 to 20 MPa, (iii) CO2 injection pressures of 6 to 17 MPa. The findings
exhibited that the apparent permeability of CO2 for geopolymer escalated with a boost in
curing temperature. These outcomes indicated that geopolymer cement based on fly ash
possesses an excellent potential for its use in the storage of carbon. Table 2 represents the
existing literature based on the properties of geopolymer concrete.
J. Compos. Sci. 2022, 6, 219 29 of 59

Table 2. Existing literature properties of geopolymer concrete.

Sr. No Paper Test Conducted Observations

Geopolymer composites based on fly ash exhibited
Hardjito [317],
high early strength compressive strength, compared
Llyod [318],
to cement concrete. Higher temperature and higher
Panias et al. [319], Compressive strength
sodium hydroxide concentration give the highest
Sofi et al. [320]
compressive strength. There is no major reduction in
Rangan [321],
compressive strength with concrete age.
The flexural strength determines the tensile
properties of concrete under internal or external
loading. The flexural strength of geopolymer
Sofi et al. [320] Flexural strength concrete is more privileged than that of cement
concrete, which exhibits a decreasing rate of crack
propagation due to corrosion of embedded steel bars
Strength in the concrete.
1.
studies The split tensile strength of geopolymer concrete
decreased as the proportion of rubber tyre waste
Sofi et al. [320] Split tensile strength increased. However, the strength is higher than that
of cement concrete due to good bonding between the
geopolymer paste and aggregates.
The modulus of elasticity of geopolymer concrete is
dependent on the modulus of elasticity of the
Sofi et al. [320] aggregate, as well as the microstructure and modulus
Fernande et al. [322] of elasticity of the geopolymer paste. Geopolymer
Modulus of elasticity
Neville [323] concrete exhibits good
Hardjito et al. [324] bonding between the geopolymer paste and
aggregates. However, geopolymer concrete has a
higher modulus of elasticity than cement concrete.
The coefficient of water permeability is low in
geopolymer concrete as compared to OPC concrete.
Cheema et al. [325] Permeability As the alkaline ratio increases,
the water permeability of geopolymer
concrete decreases.
As the alkaline liquid ratio increased from 0.75 to
Adam et al. [326],
1.25, the sorptivity of geopolymer concrete decreased.
Thokchom et al. [327] Sorptivity
An increase in Na2 O content in geopolymer concrete
Mishra et al. [328]
decreased the sorptivity.
Song [329] The water absorption of geopolymer concrete is
Water absorption
Sathia et al. [330] lower than in cement concrete.
Geopolymer concrete exhibits excellent performance
Durability against sulphates. Significant changes in mass and
2. compressive strength have been observed in
studies
geopolymer concrete, as compared to
Bakharev [331] cement concrete,
Wallah et al. [332] Sulphate resistance as a result of alkaline liquid enhancing the stability of
Thokchom et al. [327] the geopolymeric
structure. Increased alkaline content in the
geopolymer mixture
can improve the performance of geopolymer concrete
against sulphates.
The degradation of mass and compressive strength of
Bharkdev [333] specimens after immersion in acid solution is less
Acid resistance
Song et al. [334] than observed in cement
concrete specimens under an acidic environment.
J. Compos. Sci. 2022, 6, 219 30 of 59

Table 2. Cont.

Sr. No Paper Test Conducted Observations

The corrosion of steel reinforcement embedded
in geopolymer
Monita et al. [335] Corrosion
concrete is similar to that of steel embedded in
cement concrete.
Durability Adam et al. [326] The carbonation performance of geopolymer concrete
2. Carbonation
studies Roy [336] is excellent compared to that of cement concrete.
Chloride ion The chloride-ion penetration of fly ash geopolymer
Monita et al. [335]
penetration was higher than for OPC concrete.
Wallah and Geopolymer concrete has very little drying shrinkage
Shrinkage
Rangan [337] compared to that of OPC concrete.
Residual strength of Sodium silicate is more resistant to degradation
Rashad and alkali-activated fly ash caused by exposure to elevated temperatures than
Zeedan [338] paste at a Portland cement specimens. The compressive
different temperature strength and thermal shock resistance decreased.
Geopolymer strength increased by approximately
Residual thermal
Kong and 53% after exposure to elevated temperatures.
damage of
Sanjayan [339] Aggregate expanded with temperature. At 800 ◦ C,
geopolymer composites
expansion reached approximately 1.5–2.5%.
Compressive strength Aggregates larger than 10 mm show higher strength
Luhar et al. [340]
of geopolymer paste at both ambient and elevated temperatures.
The compressive strength of geopolymer mortar
Compressive strength
Zhu pan et al. [341] decreases in some cases and increases in others after
of geopolymer mortar
exposure to high temperatures.

3. Compressive strength,
Palm oil fuel ash and fly ash used as source materials.
density and TGA of
Ranjbar et al. [342] Geopolymer mortar accelerated micropore formation
fuel ash-based
at elevated temperatures.
geopolymer mortar
The compressive strength of fly ash-based
Compressive strength
geopolymer concrete is increased beyond 800 ◦ C but
Kong et al. [343] of fly ash
Elevated the strength of the metakaolin based geopolymer
and metakaolin
temperature concrete decreases at the same temperature.
effect Compressive strength
At 550 ◦ C, the strength of geopolymer paste
and transient creep of
Zhu pan et al. [344] increased, whereas the OPC paste exhibited
geopolymer and
little change.
OPC composites
Mass loss, compressive In comparison to OPC concrete at high temperatures,
Hussain et al. [345] strength of blended ash geopolymer concrete provides better
geopolymer concrete compressive strength.
Study includes the thermo-mechanical properties of
class F
Thermo-Mechanical
Fenghong Fan [346] fly ash based geopolymer materials prepared using
Properties
KOH and Na2 SiO3 alkaline activators
with different curing and cooling methods.
Compressive strength The unexposed geopolymers have excellent
4. of lightweight mechanical and microstructural properties. The
Omar et al. [347]
geopolymer paste, deterioration of the properties of geopolymers begins
mortar, and concrete at 800 ◦ C.
Compressive strength, As source material, ceramic waste is used. A
TGA, SEM and FT-IR compressive resistance of 28 days of 71.1 MPa before
Sun et al. [348]
analysis of and 75.6 MPa after thermal treatment at 1000 ◦ C was
geopolymer paste presented with the synthesized geopolymer paste.
J. Compos. Sci. 2022, 6, 219 31 of 59

4.5. Fly Ash-Based Geopolymer for Mortar

The potential applications of geopolymers based on fly ash as mortar necessitate the
study of its significant properties, in order to establish it as a successful building material.

4.5.1. Properties
Workability
The degree of workability of fresh geopolymer mortar is an imperative attribute, which
determines the characteristics of hardened geopolymer mortar. Water is usually used to
control the fluidity of fresh mortar without decreasing the visible strength [349]. Flow is
often used to calculate the workability of the mortar, which can be measured with the flow
test. Flow is normally utilized to assess the functioning ability of fresh mortars, that is
given away in the percent of the early base diameter. The devices for testing comprise a
mould for flow, a trowel, tamper, measuring tape and flow table. During the flow test, the
new characteristics of workability can be achieved, as well as the mortar constancy and the
filling ability.
Jumrat et al. [350] disclosed that geopolymer mortar’s flow value reduced with the
increase in Na2 SiO3 /NaOH ratio and fly ash to alkaline solution ratio on account of the
higher viscosity of a solution of Na2 SiO3 . Further, additional water might be supplemented
to acquire the geopolymer mortar with a functioning workable characteristic. The enhance-
ment of Na2 SiO3 constituent resulted in the rapid development and superior viscosity
ability of the binder, which was increased with the augment in the level of Na2 SiO3 and
NaOH [351].
The investigations obtained the fluidity at 30s and 30 min, due to the measurement in-
dex of the workability property of mortar. Further, the monitored geopolymer mortar fluid-
ity accelerated when the NaOH concentration reduced [352]. Moreover, Patankar et al. [353]
had the same opinion concerning geopolymer mortar having dissimilar ratios of activator
solution to fly ash.
Bhowmick and Ghosh [354] revealed that the fly ash to sand ratio escalated the
flow value percentage of geopolymer mortar, in addition to the ability of flow with the
cohesiveness of the geopolymer mortar, which boosts with the escalating the ratio of
SiO2 /Na2 O. The outcomes of their study also made known that the uniformity of the
mortar and flowability are affected by the size of the particle and grading of the aggregate.
Malkawi et al. [355] conducted a flow test and accounted that the flowability of the
geopolymer mortar that was synthesized by using fly ash was strongly influenced by the
concentration of sodium hydroxide, and the workability was monitored as lessening with
the acceleration of NaOH concentration.
Lee [356] manufactured the geopolymer mortars that were produced by slag and fly
ash, in addition to employing styrene–butadiene latex and measuring the flow accordance
with a flow test, demonstrating that the coarse bottom ash and SB latex dose had more
or less no impact on the value of the flow, whereas the supplement of alkali activators
enhanced the value of the flow.
Sathonsaowaphak [357] studied the workability performance of geopolymer mortars
that were produced by using the bottom ash waste from lignite source. The bottom ash can
be used to replace the finer aggregate in the geopolymer mortar; nevertheless, the bottom
ash substitution reaches lower flow levels than those where the standard sand is used [358].
The effects of the alkaline solution and calcium to silicate ratio on the flow of the
geopolymer mortar were calculated by Huseien et al. [359]. Their results showed that the
use as an alkaline-activator solution of sodium silicate could reduce the geopolymer mortar
flow without sodium hydroxide, due to the higher Na2 SiO3 viscosity.

Compressive Strength
The geopolymer mortars based on fly ash were manufactured using 70% of GGBFS
and 30% of POFA by Islam et al. [360], who demonstrated the best possible compressive
strength of roughly 66 MPa. In high-calcium fly ash-based geopolymers, a significantly
J. Compos. Sci. 2022, 6, 219 32 of 59

higher concentration of NaOH may gain less compressive strength than low-calcium fly-ash
geopolymer mortar [361].
The upshots of Temuujin et al. [362] pointed out the bonding among geopolymer
binders with aggregates. Nevertheless, Zejak [363] uncovered that the compressive strength
property of geopolymer mortar that was prepared with fly ash was enhanced by the addi-
tion of limestone sand. However, the existence of the sand particles with well-combined
grains amends the gel phase of the geopolymer structure.
The influence of the ratio of SiO2 /Na2 O and the ratio of water to fly ash on the
compressive strength performance of geopolymer mortar. The impact of an escalating
SiO2 /Na2 O ratio on the compressive strength property of the geopolymer mortar is not
identical with the alkaline liquid ratio [364].
The authors Kotwal et al. [365] illustrated the impact of sand to fly ash ratio on
compressive strength. The compressive strength augments with the addition in the ratio
of Na2 SiO3 to fly ash. While the ratio of NaOH to fly ash increases from 0.05 to 0.125,
the compressive strength property of the geopolymer mortar also enhances at first, but
subsequently declines. Moreover, the ratio of binder/sand influences the compressive
strength performance of geopolymer mortars.
Patankar et al. [353] reported that the compressive strength measurement of geopoly-
mer mortars with a curing age of three days was found to be improved with an augment
in curing temperature, whereas the strength improved slightly after the curing by oven
heating for more than three days.
Gorhan and Kurklu [366] found an accelerating propensity concerning the compressive
strength performance of geopolymer mortar that was cured at 85 ◦ C, while the concentration
of sodium hydroxide and time for curing increased. The optimal 6 M concentration of
NaOH and 85 ◦ C temperature for curing generated the brilliant compressive strength of
the referred geopolymer mortar.
The findings of Bashar [367] suggested that the fly ash geopolymer mortar that was
synthesized with 100% quarry dust with manufactured sand did not show a visible reduc-
tion in strength in comparison with the geopolymer mortar that was produced with 100%
conventional mining sand.
Helmy [368] investigated the intermittent curing technique for geopolymer mortars at
a curing temperature of 70 ◦ C for four stages, whereby each stage was of 6 h/day, resting
afterwards for 18 h. The monitoring indicates that the intermittent curing of geopolymer
mortar can enhance compressive strength.
The outcomes of Li et al. [369] for geopolymer mortars synthesized using Class C
type fly ash at 70 ◦ C with a curing period for 20 h obtained the best possible compressive
strength. Nevertheless, Adam and Horianto [370] accounted that fly ash-based geopolymer
mortar attained optimum compressive strength, obtained with a 120 ◦ C curing temperature
for up to 20 h.
A comparative study was made by Narayanan and Shanmugasundaram [371] for
diverse curing techniques of geopolymer mortars such as oven curing, heat chamber
ambient temperature, and autoclave by. They reported that the optimum compressive
strength of the geopolymer mortar was observed at an 80 ◦ C curing temperature for 6 h.
Increased compression strength with the increment in the fly ash substitution rate with
GGBFS was observed for geopolymer mortar [372]. The geopolymer mortar based on fly
ash, which employed a different percentage of the colloidal nano-silica supplement [373].
They reported that a 6% fly ash substitution rate was the maximum dose of nano silica
that was necessary to achieve agreeable compressive strength at an ambient temperature
curing condition.

Tensile Strength
Furthermore, the fly ash geopolymer mortar is commonly recognized to have excep-
tional performance under compressive loading. Chuah et al. [374] compared the average
geopolymers’ tensile strength with the design strength of the ACI standard and reported
J. Compos. Sci. 2022, 6, 219 33 of 59

that the tensile splitting force of geopolymers could satisfy the design requirements of the
ACI code, irrespective of sand type.
Guades [375] assessed the tensile attributes of geopolymer mortars via carrying out
the experiments. The tensile strength property of geopolymer mortars accelerates gradually
with the augment in the sand to fly ash ratio as 7 to 28 days of curing.
Adak [373] upshots revealed that the 6% nano-silica mixture improved the geopolymer
mortar tensile strength at ambient temperature curing, and the escalation in the molar
concentration of the activator solution increased the tensile strength of the mortar. The
kinds of alkaline activator solutions and curing temperature have a significant effect on
geopolymer mortar tensile strength. The geopolymer mortar that is cured at 27 ◦ C is
stronger than the mortar that is cured at 60 to 90 ◦ C. The sodium hydroxide liquid solution
that is employed as the activator results in an enhanced tensile characteristic compared to
the sodium alumino-silicate hydrate solution [359].

Flexural Strength
By and large, the cement mortar with higher compressive strength shows a prominent
flexural strength performance. Nevertheless, the geopolymer mortar demonstrates higher
flexural and lower compressive strength on account of the exceptional bonding of geopoly-
mer paste to the aggregates and the extraordinary fragility of the geopolymer [376]. The
kinds of alkali activator solution and temperature for curing considerably influence the
flexural strength performance of geopolymer mortar.
Atis et al. [377] studied the discrepancies of the flexural strength behaviour of geopoly-
mer mortars with a variety of contents of Na, which were cured for a period of 24, 48 as well
as 72 h at 45 to 115 ◦ C. The findings showed that the geopolymer mortar, which combines
fourteen percent sodium when cured for 24 h below 115 ◦ C, had the best possible flexural
strength, while the geopolymer mortar with four percent of Na had the least flexural
strength, which had been cured at 105 ◦ C for 24 h. While the ratio of bottom ash to fly ash
is enhanced from 0 to 3, the flexural strength of the geopolymer mortar improves first, but
subsequently tends to mitigate, failing to reach the optimum value at a ratio of the bottom
ash to fly ash [358]. The blending of nano-silica in geopolymer mortars has a significant
influence on the flexural strength of the mortar. The geopolymer mortar with 6% of nano
silica displays elevated flexural strength than the mortar sans nanoparticles. In addition
the flexural strength accelerates gradually with the addition of a concentration of molar or
alkaline activator solution, irrespective of a supplement of nano silica [272].
Huseien et al. [359] uncovered that geopolymer mortars that were cured at 27 ◦ C
had elevated flexural strength, compared to the mortars that were cured at 60 and 90 ◦ C.
Moreover, the solution for sodium alumino-silicate hydrate resulted in less flexural bending
strength than the sodium hydroxide solution.

Acid Resistance
The structural integrity of the geopolymer mortar relies upon alumina-silicate and not
calcium silicate hydrate bonds. Several researchers have conducted experiments on the
acid resistance of geopolymer mortars. Satya et al. [378] summed up that the synthesized
geopolymer mortars that were incorporated with fly ash and POFA displayed brilliant
resistance to acidic water on account of the development a few novel zeolite-type phases.
Moreover, fly ash-based geopolymer mortar showed a very high resistance to acidic
peat water, compared to the geopolymer mortar that was incorporated with POFA [379].
Further, the findings of Sreevidya et al. [380] monitored the resistance of geopolymer mortar
against muriatic and nitric acids and compared a compressive strength value before and
after immersion in acid solutions. Nevertheless, the augment of the content of OPC in the
geopolymer mortar led to a higher degree of weight loss of the samples, following their
immersion in a 10% solution of sulphuric acid [381].
Thokchom [382] assessed the resistance to acid by geopolymer mortars containing
Na2 O of about 5–8%, following the immersion in nitric, as well as sulphuric acids, for
J. Compos. Sci. 2022, 6, 219 34 of 59

an exposure period of 24 weeks. The author suggested that geopolymer mortar with 8%
of Na2 O demonstrated a minor loss of compressive strength. In addition, the loss in the
compressive strength of the samples that were immersed in sulphuric acid was superior to
the samples that were immersed in nitric acid.

Water Absorption
The water absorption of the geopolymer mortar depends on the pores, especially the
apparent porosity value and the pores’ size. Adak et al. [272] concluded that geopolymer
mortar with 6% of nano silica particles with dissimilar concentrations of molar displayed
an inferior absorption of water after the curing of samples for 28 days, compared to the
geopolymer mortars with the absence of nano silica particles.
Kurklu [383] synthesized the geopolymer mortars employing fly ash and blast furnace
slag (BFS) and assessed the impact of slag dose on the water absorption of the mortars
through a heat curing period of 5–168 h. The water absorption values of the mortars
containing dissimilar doses of fly ash ranged inconsistently with the increase in BFS
quantity, and the least absorption of water was seen in the sample with 100% BFS after
24 h of curing, whereas the optimum absorption of water became visible in the sample
incorporating 25% BFS, following curing for 5 h.
Abdollahnejad [381] gauged the water absorption capillarity coefficient of diverse
kinds of geopolymer mortars. The authors reported that the single part of the geopolymer
mortar enclosing 8% calcined content demonstrated high capillary water absorption on
account of a huge quantity of capillary pores.
It was reported by Helmy [252] that the increase in treatment time resulted in the
water absorption mitigation of geopolymer mortars, while the specimens were thermally
cured at 85 ◦ C, and that NaOH concentrations influenced water absorption.
The water absorption of geopolymer mortar that was synthesized in volcanic ash was
examined by Djobo et al. [384]. The water absorption of the sample that was cured below
80 ◦ C was higher than the specimen that was cured below 27 ◦ C, and the maximum value
for water absorption was seen before 28 days, while the water absorption was constant,
regardless of the curing temperature.

Micro-Structures of Fly Ash-Based Geopolymer Mortar

For geopolymer mortars that were synthesized using class C Fly Ash when examined
for micro-structures by Li et al. [352], their SEM micrographs displayed relatively denser
reaction product development in the mortars. The amalgamation of nano silica for making
the geopolymer mortars is competent enough to modify its morphology. The geopolymer
mortar enclosing six percent particles of nano silica is found to comprise a higher amount
of crystalline compound transformed from an amorphous material, compared to the one
which does not contain nano-particles [373]. The microstructures of the geopolymer mortars
with or without exposure at higher temperatures through SEM micrographs were studied
by Abdulkareem et al. [385]. They revealed that the appearance of the microstructure
of geopolymer mortars altered to some extent when they were exposed to an elevated
temperature of 400 ◦ C.
Nevertheless, it was unearthed that the structural water evaporation caused some
smaller micro-cracks in the geopolymeric gel, leading to the deterioration of the strength of
the geopolymer mortar when subjected to a temperature of 600 ◦ C. The referred deteriora-
tion in the micro-structure turned out to be more severe on the elevation of the temperature
to 800 ◦ C. The geopolymer mortars that were produced through employing dissimilar acti-
vators, along with the incorporation of POFA and fly ash, were studied micro-structurally
by Huseien et al. [359]. They found that the FESEM images of geopolymer mortar that was
synthesized through employing sodium silicate displayed a fragile matrix, as well as a
lower density. They also saw the presence of more non-reacted or partly reacted particles
of POFA and fly ash in the composite [359].
J. Compos. Sci. 2022, 6, 219 35 of 59

4.6. Fly Ash Based Geopolymer Paste

The properties of fly ash-based geopolymers have been examined in the past by many
researchers, mainly concerning their workability, flowability, setting time, water absorption,
compressive strength and drying shrinkage.

4.6.1. Properties
Workability
The workability property of geopolymer paste was studied by Kumar and Rama-
murthy [386], who established that for constant ratios of NaOH and Na-Si to NaOH, as
well as an alkaline liquid to fly ash, there is a noteworthy impact on the workability of
geopolymer paste and mortar. The mix becomes more workable when the liquid alkaline
is used in the mix. While there is an elevated ratio of La/ash such as 0.75 for geopolymer
mortar and 0.45 for geopolymeric paste, an enhancement in NaOH contents in terms of
molarity results in steep mitigation in the workability of the mixture. This is because of a
boost in the solution viscosity with NaOH molarity. However, the mixture was found to be
very stiff when the La to ash ratio was maintained as 0.65 for geopolymer mortar and 0.4
for geopolymer paste, regardless of the ratios of Na-Si to NaOH and NaOH molarity.

Flowability
The average slump flow of geopolymeric mixes was determined by Ling et al. [387],
who accounted that none of the investigated geopolymer pastes demonstrated notable
bleeding during the mini-slump test. The activator concentration affected the flowability of
geopolymeric paste more extensively than the module. When comparing them with cement
pastes, pastes with a concentration of twenty-five percent significantly reduced the slump
flux, while pastes with a concentration of twenty percent significantly increased the slump
flux. According to Zuda et al. [388], the augmented silica was probably associated with
the high module activator solution, which promoted the precipitation of larger molecular
species and led to a stronger gel of improved density. Additionally, a solution with a high
module activator presented an elevated quantity of Na2 SiO3 . Moreover, Chindaprasirt [350]
accounted for analogous findings and explained that these owed to an elevated concentra-
tion of activator, which would have led to the enhanced viscosity property of the mix. A
high module also reduced the slump flow. The mitigation was more rigorous for pastes
with a higher concentration of activator. The elevated viscosity of Na2 SiO3 might also
have influenced the flowability of the paste [355]. As per Lee et al. [269], the measurement
upshots for the flow and images of the geopolymeric paste in the context of the Si/Al
ratio were as follows: The flow measurements were 187.5 mm, 177.5 mm and 167.5 mm on
maintaining the Si to Al ratios as 1.5, 3.5, and 4.0, correspondingly, suggesting that the flow
reduced the increase in the ratio of Si/Al. When the value of the ratio of Si/Al was fixed as
3.5 and 4.0, the flow possibly diminished on account of the higher viscosity of the activator
of Na2 SiO3 ·H2 O, compared to the case whereby the value of the Si to Al ratio was 1.5. For
this reason, while Na2 SiO3 ·H2 O is used as the activator to synthesize geopolymers, it is
highly important to observe it for any deterioration concerning the fluidity.

4.6.2. Setting Time

Saha and Rajasekaran [389] observed from their experimental investigations that the
setting time for both the early and final stages of geopolymer paste that was prepared
with fly ash were found to be considerably lower with the augment of the GGBFS in the
mixtures. It was found that a blending of GGBFS in mixtures increases the initial setting
time from 420 to 480 min, to 25 to 130 min, and the final setting time from 1425 to 1600 min,
to 90 to 355 min. The initial and final setting times of geopolymer paste were observed
to change from 73 to 94% and by 77 to 92%, respectively, on the addition of slag from 10
to 50% in the mixtures, in comparison to the setting time of geopolymer paste mixtures
with no slag. The discrepancies of geopolymer paste occurred with a variety of GGBFS
within the initial setting time and final setting time. The geopolymer paste is found to
J. Compos. Sci. 2022, 6, 219 36 of 59

rely characteristically upon the production of NASH gel. Since the quantity of calcium
oxide is significantly greater in the slag, geopolymer paste mixtures that are developed
incorporating slag may also develop CSH gel in association with NASH gel in the initial
period. Consequently, geopolymer paste that is incorporated with a higher amount of
GGBFS takes considerably less time for both the initial and final settings, according to the
findings of setting time by Hanjitsuwan et al. [243]. The initial and final set-up times were
both enhanced by NaOH concentration acceleration. The final times were recorded for
various samples, including 130, 160, 205, 245, as well as 260 min. The leakage of alumina
and silica was also found to be low when the NaOH concentration remained low [254]. The
leakage of Ca2+ ions into the solution was not disrupted and, therefore, the solution was
full of calcium. The referred quantity of calcium was adequate for precipitation and reacted
to develop CSH gel and CAH gel that result in the paste setting. Consequently, the setting
time became shorter [390,391]. As a result, the geopolymer paste setting time is connected
to the quantity of the accessible calcium [240]. When the concentration of NaOH was high,
the leaking of alumina and silica was superior to a great extent. The leaking of Ca ions was
delayed, and the quantity of Ca in the solution was restricted.

4.6.3. Compressive Strength

The discrepancy in the context of the compressive strength property of aerated geopoly-
mer paste formed with fly ash was studied by Kumar and Ramamurthy [386]. Kumar and
Ramamurthy [386] illustrated that (i) for a provided alumina dose, the density and the
compressive strength improved with the NaOH molarity value. This may be assigned to
the higher fly ash dissolution and increased NaOH concentration with advanced geopoly-
merization, and that a liquid alkaline/ashes ratio of 0.4 provides a comparatively higher
strength-to-density ratio. (ii) On the other hand, an increase of 2 in a ratio of Na-Si to NaOH
extends a number of lower densities such as 1250 to 700 kg/m3 , matching compressive
strength mitigation, which is altered in pH by modification in the silicate [224].
Ling et al. [387] confirmed the value for the compressive strength of geopolymeric
paste. Ling et al. [387] suggested that geopolymeric pastes possess superior strength to
ordinary Portland cement pastes at every age, except the mixtures containing a molar ratio
of 1.5 SiO2 /Na2 O at twenty percent concentration for 28 days. On the 7th day, 90% of
geopolymer pastes had a 28th-day compressive strength, whereas the strength of cement
pastes was more or less established for approximately 60% of their strength after 28 days.
Following seven days, the compressive strength property of geopolymer pastes improved
at a snail’s pace, but that of PC pastes was augmented quickly. The molar mixtures of
1.0 for SiO2 /Na2 O had the best possible concentration compressive strength at the 25%
concentration, followed by those of the 1.0 molars at the 20% concentration. Keeping the
constant water/binder ratio of 0.33, the fly ash-based geopolymer paste that was synthe-
sized using an activator with a ratio of molar 1.0 SiO2 /Na2 O and twenty-five percent
concentration demonstrated the compressive strength value of 76.0 MPa after 28 days,
whereas the cement-paste exhibited the value of compressive strength as 59.4 MPa. The
impacts of geopolymerization that were encouraged by an increased alkaline concentration
could also be determined by the effects on the fluctuating porosity of the ultimate geopoly-
mer products [392]. The referred tendencies correspond with the outcomes of not only
Fernandez and Palomo [393], but also Rattanasak and Chindaprasirt [254]. The value of the
compressive strength of the geopolymeric pastes with a range of substitutions of fly ash
with water glass powder were studied by Liu et al. [394]. The upshots designated that the
levels of substitution for both fluorescent lamp glass (FP), as well as ground container glass
(CP), had imperative influences on the compressive strength properties of geopolymeric
pastes. The best possible presentations for FP, as well as CP substitutions, are achieved
from the samples with 10 FP and 20 CP content, with the compressive strength values as
41.1 MPa and 47.6 MPa, correspondingly, whereas the reference paste exhibited the com-
pressive strength value of 45.7 MPa. The value of compressive strength has the propensity
to reduce as the echelon of substitution by FP is boosted. Due to its higher silicone content,
J. Compos. Sci. 2022, 6, 219 37 of 59

the decreasing value of the compressive strength can be assigned to FP substitution and can
change the ratio of silicon/aluminium. The higher ratios of silicon/aluminium encouraged
the development of lower cross-linked alumino-silicate materials with mitigated strengths,
which was intimated by Rattanasak et al. and Fletcher et al. [395,396]. The characteristics of
geopolymers are drastically modified with comparatively lower alterations in the contents
of aluminium and silicon during geopolymerization of alumino-silicates, as revealed by De
Silva et al., [397]. Davidovits [63], as well as Chindaprasirt et al. [390], who found that for a
good-quality strength geopolymer, the optimum ratio of silicon/aluminium was among
3.5 to 4.0. Nevertheless, the geopolymer samples employing 10% to 30% FP displayed
the values of compressive strength of 87% to 90%, compared to the reference paste, due
to the FP-particles being and finer. The finer particles of FP performed as micro-fillers
and induced matrix densification to the geopolymeric paste. Moreover, the compressive
strengths performance of geopolymer pastes incorporating CP dropped, analogous to those
possessing FP, on account of the enhanced ratios of silicon/aluminium. Nevertheless, the
compressive strengths measurement of the pastes blended with CP, i.e., CaO as 12.80%,
were greater than those that were manufactured with FP, i.e., with 7.43% CaO content, at the
identical substitution echelons. The high CaO levels for the geopolymer pastes were consid-
ered as a generating factor in the formation of denser structures and enhanced strengths in
combination with other rates of geopolymerization, following Saha and Rajasekaran, [389]
and Temuujin et al. [398]. The twenty percent CP geopolymer paste represents the best
compressive strength value of 47.6 MPa, a little higher than the reference paste. This is
possibly attributed to the blending of an appropriate quantity of finer particles of CP with a
higher content of CaO. In relation to the ratio of amorphous Si/Al in fly ash, Lee et al. [269]
analyzed the results of compressive strength measures in the geopolymer paste. When the
compressive strength of the samples was cured at 70 ◦ C for one day, the attained values
were 15.0, 23.0, and 9.5 MPa for 1.5, 3.5, and 4.0 as the ratio of Si/Al, correspondingly. After
more than one day of age, the values for compressive strength were augmented when
cured at 20 ◦ C. The compressive strength values of the samples were 43 MPa following
the 28 days and showed the most compressive strength possible for the sample with an
Si to Al ratio of 3.5 and with NaOH plus Na2 SiO3 ·H2 O used as the alkali activator. In
the meantime, the value of compressive strength for the samples that were cured at a
temperature of 70 ◦ C between one and 28 days at 3 days of age was about 1.29–1.45 times
greater than for the samples that were healed 20 ◦ C between the age of two and 28 days.
Moreover, for the samples with a ratio of Si/Al as 1.5, the value of compressive strength
due to curing at a higher temperature until the age of 28 days was found as 48.1 MPa,
which was more than the compressive strength value of the sample that had a ratio of
Si/Al as 3.5. The compressive strength of the geopolymer paste that was preserved as
cube specimens and at ambient curing temperature by Saha and Rajasekaran [389] was
recorded to have an escalating drift, whereas the concentration of the solution of NaOH
and the GGBFS quantity percentage in the mixtures were both found to be enhanced. An
enhancement in the compressive strength was monitored more while the slag was present
in an elevated amount. The compressive strength of the geopolymer paste is assigned to
develop a 3D network of silicon aluminium structures through the manufacture of a gel of
sodium aluminium silicate hydration (NASH). The elevated concentration of the solution
of NaOH helps to produce an adequate gel of sodium-aluminate-silicate-hydrate (NASH)
and leads to polycondensation. Consequently, the stable 3D network of silico-aluminates is
developed to offer greater strength to the geopolymer based on fly ash. Moreover, the de-
velopment of CSH gel besides structures of silico-aluminates in the paste mixtures provide
a notably improved strength. The compressive strength of geopolymer paste is improved
after 7, 28 and 56 days with a various percentage of slag. The best possible compressive
strength value of geopolymer paste on the 7th, 28th and 56th days were monitored as
66.4, 78 and 78.2 MPa, correspondingly, for the mixture with a solution of 16 M NaOH
and 50% quantity by weight of GGBFS. of the compressive strength value for geopolymer
paste mixtures following 28 days is found to be greatly reduced. The mixture that was
J. Compos. Sci. 2022, 6, 219 38 of 59

manufactured with the solution of 16 molarity concentration of NaOH and 50% by weight
of slag demonstrated optimum compressive strength, and exhibited a 14.8% increase in
compressive strength after 7 days, and 0.26% growth after 28 days. This is according to the
findings of the compressive strength by Hanjitsuwan et al. [243]. The recorded value of
compressive strength accelerated with an augment in NaOH concentration such as 43.3,
46.7, 50.0, 54.1, as well as 56.0 MPa of pastes, in that order. The dissolution of Si4+ and
Al3+ ions from fly ash increased, while the concentration of NaOH was higher and the
development of sodium-alumino-silicate was augmented, leading to an increase in the
compressive strength [251,254,399].

4.6.4. Water Absorption

Kumar and Ramamurthy [386] studied the geopolymer paste and mortar water ab-
sorption property. Generally, the absorption of water reduces with an increase in the density
of the geopolymer composites (paste and mortar). For an analogous density, an acceleration
in the temperature for curing resulted in inferior water absorption. When the ratio of
Na-Si/NaOH was elevated, although the mitigation in density could be obtained, the
resultant absorption of water was much higher. For an equivalent density, where the curing
temperature was 90 ◦ C for a ratio of Na-Si/NaOH as 1, the disparity in the absorption of
water among ratios of La/ash as 0.4 and 0.45 was trivial; therefore, the selection of the
mixture should be that which contributes superior strength for a required density.

4.6.5. Drying Shrinkage

Ling et al. [387] investigated the drying shrinkage attribute of geopolymers. The
drying shrinkage tests of all mixtures were made up of Portland cement (PC) and fly
ash-based geopolymer (FG) for a drying period of 56 days. However, the main free drying
shrinkage also occurred in the initial 14 days, and the trend in the free drying shrinkage test
results was not the loss of paste mass. FG pastes with a high activator solution concentration
usually had more drying shrinkage. The pastes with 25% activator concentration suffered
high shrinkage, whereas the pastes with a lesser concentration of activator solution of 20%
demonstrated less free drying shrinkage than their respective PC pastes.

4.6.6. Microstructures of Fly Ash-Based Geopolymers Composites

The chemistry and microstructure of geopolymer composites based on fly ash are
controlled through the particle size distribution analysis and mineralogical composition
of the primary fly ash, the type of activator and a few other variables. The microstructure
of geopolymer concrete that is formed with fly ash regarding reaction, and the type of
activator that is employed have been studied by many renowned scientists [400,401]. In
the SEM images of the fly ash, the referred figure shows that the dissimilar, spherical size,
shaped series of glass particles vary in length from 10 to 20 µm, and a few of these spherical
particles might hold other particles of a lesser size in internals.
Akin to Weir et al.’s models [402], which clarify the microstructure of OPC concrete,
as well as its hydration reaction, the reaction that occurs while fly ash is geopolymerized
is characterized by Fernández-Jiménez and Palomo [393]. In the commencement, the
attack against the chemical initiates at a particular place on the surface of the particle and
subsequently forms to manufacture a larger hole; Dissimilar smaller particles either vacate
or else are partially filled with other small ashes, toward a bi-directional alkali attack, in
accordance with Brouwers and Van [403]. Afterwards, the reaction form is developed in
both the exterior and interior of the sphere-shell until the ash particle is entirely or more
or less completely utilized. A few significant outcomes regarding the microstructure of
geopolymer concrete that is formed with fly ash have been characterized. Nevertheless, the
similarity among investigations has been frequently restricted on account of disparities in
experimental points of view.
J. Compos. Sci. 2022, 6, 219 39 of 59

X-ray Diffraction (XRD)

Abdulkareem et al. [385] accounted for a wide hump from 20 to 35 that was indicative
of the presence of amorphous geopolymeric yields. On the basis of a precedent investiga-
tion, the presence of mullite, as well as quartz, reflected the composition of characteristic
fly ash. Fly ash consists of Ca and Fe. Hence, it described the crystalline phases in the
geopolymeric paste. A few peaks were made known in nano silica blended geopolymer
concrete that designated the development of the novel phases of Albite NaAlSi3 O8 ; silica
SiO2 ; anhydrous aluminium silicate Al2 Si2 O5 (OH)4 ; mullite 3Al2 O3 ·2SiO2 ; calcium silicon
oxide Ca3 SiO5 ; and calcium hydroxide Ca(OH)2 crystalline type compound. After the addi-
tion of the alkaline solution, the crystalline phases were exposed, followed by a comparison
of the amorphous hump. Zeolite was produced after dissolution, while all of the fly ashes
had mullite (2Al2 O3 ·SiO2 ); quartz (SiO4 ); and hematite (Fe2 O3 ). The XRD analyses for fly
ash-based geopolymers with a ground glass container (CP) for 7 days were explained by
Tho-In et al. [394]. The geopolymeric fly ash paste has a broad hump with 25–35 phases and
is in the lower calcite phase, which corresponds to the geopolymerization level [404]. Fly
ash–CP pastes have the same XRD drifts as 100FA paste. The calcite and quartz spikes were
nevertheless monitored, with the higher CaO and SiO2 presence increasing the percentage
of ground CP [405]. At a high percentage of CP substitution, tridymite and cristobalite
peaks were noticed.

Fourier Transform Infrared Spectroscopy (FTIR)

Adak et al. [406] endeavoured to determine the geopolymeric structure by means of
an FTIR analysis. The distinct intensity band in the vicinity of 460 cm−1 was identified
for the Si-O-Si vibration bending. Due to the AlO4 vibration, the band between 750 cm−1
and 800 cm−1 was monitored. The asymmetrical span of Si-O-T is further enhanced by
T = Al, Si; the most powerful band was described and recorded in the area of 950 cm−1
to 1050 cm−1 [407]. The position, i.e., 1420 cm−1 of Si-O-Si in 12GC0H was moved to the
exact position, i.e., 1485 cm−1 , in 12GC6. Moreover, an important band was situated at
just about 3450 cm−1 for OH stretching bonding. Tho-In et al. [394] carried out the FTIR
analysis on geopolymer with fly ash with container glass pastes and a ground fluorescent
lamp (FP). The absorption bands at more or less 3450 cm−1 and the band, which is weak
at 1650 cm−1 , are accompanied by O-H and H-O-H bond vibrations in the molecules of
the water. The preceding investigations accounted that the bands were recorded and
uncovered [394]. Tho-In et al. [394] stated that the water molecules were incorporated
into pores or absorbed on a surface during geopolymerization [393,408,409]. The band
at approximately 1450 cm−1 was the indication of the expansion of O-C-O in carbonate
groups because of the reaction to atmospheric CO2 of alkali metal hydroxides. Every sample
shows an irregular Si-O-X stretch at 1050 cm−1 , in which the X represents an aluminium
or tetrahedral silicon. The Si-O-X bond assisted the course of geopolymerization with the
phases of amorphous alumino-silicates that were developed. Researchers also explained
that the sharp absorption band connects to many tetrahedral aluminium particles in the
geopolymeric gel [410]. Additionally, the stretching of Si-O-Si and O-Si-O bonds is alike to
that of the Si-O-Al group and is located at 450 cm−1 [411]. Moreover, the corresponding
wide bands accounted for both fly ash that was incorporated with GP and FP, as well as
100 FA specimens. On the other hand, samples of 100 FA evidenced the elevated rate of
geopolymerization kinetics because of the absorption band at 1050 cm−1 , which was greater
than the FP and GP samples.

Thermogravimetric Analysis
In order to measure the mass loss in terms of temperature between 25 ◦ C and 800 ◦ C,
a thermal analysis was performed by Abdulkareem et al. [385]. The water loss due to the
evaporation of both the geopolymer chemically bound water and free water was confirmed
by a fast reduction in mass prior to 150 ◦ C [385]. A sharp loss in weight was exemplified
by more or less 55 to 60% of the free water in the geopolymeric matrix, which evaporated
J. Compos. Sci. 2022, 6, 219 40 of 59

ahead of 100 ◦ C in specimens. Nevertheless, it is monitored that the loss rate in weight is
steady from 150 ◦ C to 780 ◦ C, because of the disappearance of the hydroxyl groups-OH
and chemically bonded water. No added loss in mass was noticed with the augment of at
800 ◦ C temperature. The average mass following the heating at 800 ◦ C was found to be
79.8%, which was depicted. According to Abdulkareem et al. [385], the loss in weight that
was found at 250 ◦ C in place of 150 ◦ C was also assigned to the evaporation of hydroxyl
group-OH [238]. The modification in weight is somewhat stable after 300 ◦ C. Kong and
Sanjayan [311] analyzed the behaviour of fly ash-based geopolymer paste that was subjected
to a very high temperature. Kong and Sanjayan [311] hypothesised that the slower rate of
shrinkage that was witnessed from 300 ◦ C and beyond was accompanied by a lower rate of
weight loss. The average mass that was evidenced following heating at 800 ◦ C was found
to be 89. Duan et al. [412] investigated the thermal analysis of geopolymeric paste with
iron ore tailing (IOT). The calcium hydroxide content diminished when the IOT quantity
that was assigned to the smaller loss in mass augmented, in comparison with the specimen
of reference. It is comprehended that the supplement of iron ore tailing (IOT) aided the
CSH gel development by employing Ca(OH)2 . Nonetheless, Ca(OH)2 decomposition was
demonstrated to correspond to the endothermic peak, even after making a thirty percent
IOT supplement in the mixture. Following Abdulkareem et al. [385], each specimen had an
insignificant mass loss rate at high temperatures following 800 ◦ C. In order to investigate
the thermal stability for geopolymers, Okoye et al. [413] conducted a thermal analysis.
The weight loss for the fly ash geopolymer specimens that were incorporated in kaolin
occurred at approximately 100 ◦ C. When the temperature increased, while the fly ash-based
geopolymer-incorporated kaolin showed a complex curve type, a relatively sharp dip in
weight was monitored. The examination of both specimens made it obvious that the ideal
temperature for curing might range from 80 ◦ C to 100 ◦ C. Cai et al. [414] explained that
the earliest method of quality deterioration was dehydration. The authors toughened fly
ash-based geopolymer by using polyvinyl alcohol (PVA) fibre and powder geopolymer
composites. In the temperature range of 0–150 ◦ C, all the samples lost 7–9% of their quality.
This process was connected to the evaporation of free water on the sample’s surface or in
the pores. Then, at around 650 ◦ C, all the samples lost their weight entirely, including the
loss of bound water and the disintegration of polyvinyl alcohol, accounting for around 8%
of the overall mass.

Mercury Intrusion Porosimetry (MIP)

Das et al. [412] studied the pore structure dimension of geopolymer fly ash ranging
from 0.0036 to 10 lm through MIP to endorse the X-ray tomography (XRT) investigations.
The cumulative porosity for the geopolymer that was formed with fly ash was more or less
32%. Nevertheless, the bulk of the pores in the geopolymeric matrix were of 0.0036–1 lm
dimension. Kaze et al. [415] The assessment of mercury intrusion porosimetry (MIP) and
the porosity of hardened geopolymer binders revealed that using a silica modulus of 1.5
and MH as the precursor provided the best performance in terms of porosity, cumulate pore
area, and pore size distribution. The reduction in the pore characteristics of geopolymers
that were created with a silica modulus of 1.5 can be attributed to the creation of additional
aluminosilicate products when compared to bulk density values that were obtained with
a silica modulus of 1.3. Higher porosity is predicted to be harmful to the mechanical
characteristics of the geopolymer binders; therefore, these results are compatible with the
mechanical performance results. Ramli et al. [416] investigated the pore structure of alkali-
activated kaolin at various sintering temperatures in this work. The results of the research
revealed the presence of open and closed pores in alkali-activated kaolin geopolymer
ceramic samples. The distributions of the key components within the geopolymer ceramic
edifice were discovered using Si and Al maps, allowing the kaolin geopolymer to be
identified. The results further verified that raising the sintering temperature to 1100 ◦ C
resulted in big holes with an average size of 80 µm3 and a layered porosity distribution in
the alkali-activated kaolin geopolymer ceramic samples.
J. Compos. Sci. 2022, 6, 219 41 of 59

5. Advantages of Fly Ash-Based Geopolymer Concrete

Fly ash-based geopolymeric composites attract researchers universally, since their
manufacturing generates 90% less CO2 than that of the OPC system. This simply means
that nine times more fly ash-based geopolymeric cement for building and infrastructure ap-
plications can be obtained for the sake of an equal quantity of CO2 emissions [80,417]. This
proves that geopolymer technology is capable of reducing CO2 emissions in the environ-
ment [79,418], ameliorating the course of global climate modifications. Consequently, the
development of geopolymer technology helps to relieve concern for the dilemma of global
warming and can help for systematic fly ash waste disposal, which would otherwise fill
land spaces and create health hazards, and contaminate the environment, soils, surface and
subsurface waters. This innovative kind of sustainable, user- and eco-benign construction
composite has proved to be a promising building material for the future. The composites
possess numerous benefits such as:
• The abundant waste of fly ash will find its systematic disposal;
• Necessitates 60% less energy than OPC and only needs a low, or room temperature, as
well as low atmospheric pressure, to be produced;
• Emits nine times less carbon dioxide as compared to OPC [419,420];
• Even short curing periods at room temperature can achieve analogous strength to
OPC composites [419,420];
• The formation of fly ash-based geopolymers is trouble-free, since they can be obtained
directly through mixing alumina silicates and alkaline activator solutions [421,422];
• Suffers 80% less shrinkage than OPC [419,420];
• Does not drop functionality even at 1000–1200 ◦ C, proving its low thermal conductivity
and excellent resistance to fire [100,419,420];
• It is effectively employed for residential buildings, pedestrian driveways, etc., due to
its light weight;
• Exhibits brilliant durability and strength, sustainability, immobilization of toxic waste,
relief from global warming by lowering emissions of GHG, and the organized solu-
tion of the disposal of diverse wastes by consuming them for their manufacturing;
otherwise, they would fill land spaces and pollute the environment, soils, surface and
subsurface water;
• Conservation of limited natural resources such as limestones, coals, etc., otherwise
they would be exhausted by using them as either raw material or be burned up for
obtaining an elevated temperature for calcination to produce OPC;
• Fly ash-based cement can be used underground as a sealant to store CO2 ;
• Demonstrate excellent mechanical properties; remarkable resistance to chemicals, acid,
sulphate, fire and thermal; fast curing speed; and high interfacial binding force, etc.;
• CFA-based adsorbents are efficient and eco-benevolent in comparison with commer-
cial adsorbents, and they are utilized to clean up real wastewaters containing dyes,
petroleum compounds, heavy metals, agricultural nutrients, radionuclides, etc;
• The radiological characteristic of fly ash is an important parameter. Research on uses of
radioactive fly ash for mine acid water or the fixation of radioactive elements could be
of interest in terms of applicability, as mine locations are usually far from residences.
According to the World Bank, global metropolitan areas generate around 3.5 million
tons of MSW every day, with this figure expected to rise to 6.1 million tons by 2025 [423].
In 2017, the quantity of MSW that was generated per capita in the EU, Australia, and the
United States was 482, 558, and 742 kg, respectively [424]. The planet is anticipated to
create 3.4 billion tons of municipal solid garbage per year by 2050 [425]. Waste management
has evolved into a set of issues across the world. MSWI FA-based geopolymer maintained
remarkable durability in acidic or alkaline environments. The use of MSWI FA as a
precursor in geopolymers can significantly minimize or even eliminate environmental
problems. It also allows MSWI FA resource usage, while avoiding the constraint of limited
landfill disposal space.
J. Compos. Sci. 2022, 6, 219 42 of 59

6. Conclusions and Discussion

This comprehensive review on a geopolymer based on fly ash leads to the conclusion
that the development of novel and ultramodern geopolymer technology, together with
relevant advanced research in the past couple of decades, has revolutionized the geopoly-
meric constructions and infrastructure industries. Consequently, a modern era of green
building materials through the feasible replacement of ordinary Portland cement (OPC)
with geopolymer cement (GPC) has commenced. Moreover, this innovative, user and
an eco-benevolent inorganic class of geopolymeric materials has a low carbon footprint
and can be synthesized with a straightforward process at a low temperature, and with
lower energy at atmospheric pressure, in comparison with present OPC production. This
is why higher energy or elevated temperature reactions are no longer necessary, as found
in the case of the OPC system. The unique attribute of ninefold lower carbon dioxide
emissions also provides relief to the gigantic dilemma of global warming. Not has only this,
the quandary of the degradation of natural confined resources such as limestones, coals,
etc., will be addressed and, thus, geopolymer technology will save natural resources that
are necessary to consume as raw materials for producing OPC construction composites.
At this juncture, the coal fly ash—an industrial waste—can be employed as a source of
alumino-silicate to manufacture fly ash-based geopolymers productively. It is not only
highly accessible and low-priced, but also found with a pozzolanic nature. The size, spheri-
cal shape and fineness of fly ash particles are the key parameters found to noticeably impact
the properties of eventual geopolymers based on fly ash. The finer size of fly ash particles
helps to develop the strength of the geopolymer, and the coarser size particles possess
definite constructive performances. Remarkably, when both finer and coarser particles
are employed collectively in the proper ratio, the strength and durability attributes of an
ultimate geopolymer composite based on fly ash are improved. Additionally, extremely
amorphous fly ashes are more efficient in picking up the pace of the pozzolanic reaction.
Fly ash with a low calcium content reacts slowly because of the existence of more crystalline
phases, which are considered as chemically inert. Green geopolymer based on fly ash; paste,
mortar and concrete envelop a wide range of possible future materials for construction.
Moreover, the organized disposal of copious wastes of fly ash by utilizing “the Best from
the Wastes” strategy makes it cost-effective too. Not only this, the application of fly ash
for manufacturing fly ash-based geopolymers and as supplementary cementitious mate-
rial will reduce the pollution of the environment, soils, surface and sub-surface waters,
owing to their heaps filling land spaces. The excellent attributes of fly ash in particular
and fly ash-based geopolymers such as sealant for storing CO2 in the underground; the
immobilization of heavy metals containing compounds; fast curing rate, greater force of
interfacial binding; low emissions of gaseous pollutants such as CO2 , SO2 , H2 SO4 , H2 S,
NO, Hg, BTX, etc., have altogether proved outstandingly beneficial. More recently, the use
of the categorization tools viz., X-ray diffractometer, scanning electron microscopy, Fourier
transform infrared analyzer, thermo-gravimetric analyzer, etc., has returned favourable
results regarding the physical and chemical characteristics of fly ash-based geopolymers,
enabling them to be employed more competently. The penetration rate of chloride reduced
with the increase in the concentration of NaOH activator liquid that was employed during
the geopolymerization, owing to the enhancement of the pore structure. This is attributed
to the reaction of polycondensation. Fly ash supports the production of more porous
NASH gels, which decrease chloride resistance. Even though geopolymer was more porous
compared to the OPC system, the geopolymer still showed improved chloride resistance.
Noteworthily, the synthesis of the geopolymer, whereby NaOH was used as an activator,
displayed the highest resistance to sulphate because of its more steady cross-linked struc-
ture. Moreover, the influence of silica fume and calcium on the resistance to acid by fly
ash-based geopolymer is quite significant. Furthermore, curing at an elevated temperature
is noted to be advantageous in the case of the geopolymer’s resistance to acid. While the
geopolymer based on the fly ash is exposed to very high temperatures, it undergoes a
shrinkage in the amount of water that is evaporated from its structure. There were no signs
J. Compos. Sci. 2022, 6, 219 43 of 59

of spalling, and only insignificant surface cracking was found in the case of geopolymer
concrete that was formed by fly ash. Extraordinarily, fly ash-formed geopolymer did not
indicate deterioration, even following 150 freeze–thaw cycles. The efflorescent nature of
fly ash-based geopolymers is very much dependent on the type of alkali activator liquid
solution, the content of calcium and the curing temperature. Fascinatingly, fly ash-based
geopolymer concrete is noticeably vulnerable to a smaller quantity of ASR than its OPC
counterpart. Overall, the chief factors that are found to affect the mechanical performances
of geopolymer concrete based on fly ash are: the interactions between the alumino-silicate
framework; alkali cations; aggregates, additives, etc. The size of the aggregates also influ-
ences the performances of the geopolymer concrete that is formed with fly ash. The thermal
incompatibility among the aggregates and the matrix of the geopolymer resulted in a loss
in strength for geopolymer concrete at very high temperatures. The bigger aggregates size
of more than 10 mm showed superior performances concerning the strength at ambient
temperature, as well as elevated temperatures, while those with a size that was smaller
than 10 mm supported both the spalling and extensive cracking at an elevated temper-
ature. Likewise, the inferior permeability of geopolymer based on fly ash proved to be
competent enough to proficiently seal the leakage of CO2 . The geopolymer cement based
on fly ash has huge potential for its application in the storage of carbon. The chemistry
and microstructure of geopolymer composites based on fly ash are controlled through the
particle size distribution analysis, a mineralogical component of the primary fly ash, the
type of activator and a few other variables. The SEM images of fly ash-based geopolymer
composites, along with EDS, exhibit the composition of numerous hydrated products. The
case of low calcium fly ash-,based concrete after 28 days shows non-reacted fly ash and
non-hydrated spots, while the cases with higher calcium are less sensitive to unsatisfactory
curing and react more swiftly to contribute enhanced early age strength. Fly ash-based
geopolymers are excellent-quality binders and, hence, could be employed as cement to
bind with aggregates with a view to manufacture the fly ash-based geopolymer concrete.
Geopolymer concrete based on fly ash has a denser microstructure with an inferior chloride
ion diffusion, as well as low porosity, as compared to OPC concrete. The fly ash/sand ratio
accelerates the flow-value of the geopolymer mortar. The flowability and uniformity of the
geopolymer mortar enhances with augmenting the ratio of SiO2 to Na2 O ratio. The unifor-
mity and flowability of the mortar are found to be affected by the particle size and grading
of the aggregate. The ratio of binder/sand impacts the compressive strength property of
geopolymer mortars. The geopolymer mortar based on fly ash is normally considered to
have exceptional performance under the loading action of a compressive type. The kinds
of alkali activator solutions and curing temperature are worth mentioning due to their
impact on the tensile strength of geopolymer mortars. The kinds of alkali activator solution
and curing temperature considerably affect the flexural strength property of geopolymer
mortar. An inclusion of nano silica showed a momentous effect on the flexural strength of
the geopolymer mortars. In the context of the good-quality compressive strength property
of geopolymer paste formed by fly ash, the optimum ratio of silicon/aluminium was found
to range from 3.5 to 4.0. In the case of water absorption in the context of the geopolymer
paste and mortar of an analogous density, acceleration with regard to the curing temper-
ature was observed as inferior. When the ratio of Na-Si/NaOH was elevated, the result
of the water absorption was much higher; however, the reduction in density could be
observed. The lower shrinkage and the higher tensile strength that were demonstrated by
geopolymer composites based on fly ash provides technical advantages over the traditional
counterpart of the OPC system—in particular, in structural components that are subject
to exterior restraint, proving them a workable alternative solution to their counterpart of
a conventional system, and contributing to systematic fly ash waste management. The
compressive strength property of geopolymers based on fly ash is found to be influenced by
Si/Al ratios, the type of alkali activators, the content of calcium, selection of additives, the
process of separate activation, the co-existence gels of NASH and CSH, as well as the curing
temperature and age. The elevated ratios of Si to Al increase the magnitude of the –Si-O-Si-
J. Compos. Sci. 2022, 6, 219 44 of 59

bond, obtaining an improved compressive strength of an entirely condensed structural

geopolymer matrix. This is because the –Si-O-Si- bonds are authentically stronger than the
–Al-O-Al- and –Si-O-Al- bonds. A slow but sure plunge in the tensile strength property
of geopolymer based on fly ash is evidenced through augmenting the ratio of sand/fly
ash. While the splitting tensile strength of geopolymer concrete that is formed with fly
ash is similar to the design values that are provided by the ACI standard, on the other
hand, the flexural strength performance of geopolymer concrete based on fly ash is found
to be influenced by the kind of additive that is utilized with fly ash. Additives of calcium
hydroxide and GGBFS are compatible with the OPC supplement by fly ash to increase the
flexural strength of geopolymer concrete-based fly ash. The potential applications of a typi-
cal type of structure of geopolymer based on fly ash, i.e., silicon tetrahedral and aluminium
tetrahedral, form ring chain type structures such as closed cage cavity, which favours its
application as a building material. Geopolymer composites that are formed with fly ash
come in various forms viz., fly ash-based geopolymer paste, mortar, binder and concrete,
all of which offer a facile approach for fly ash utilization and have attracted researchers, and
construction and infrastructure industries universally. This is because their manufacturing
generates 90% less CO2 than that of the OPC system, helping to relieve concern for the
dilemma of global warming, and offering a method of systematic fly ash waste disposal
management—otherwise, it would fill land spaces, create health hazards, and contaminate
the environment, soils, surface and sub surface waters. Other advantages of geopolymer
composites are as follows: they are an innovative kind of sustainable material, user- and
eco-benign construction composites; necessitate 60% less energy than OPC and only need
low (as low as room) temperature and atmospheric pressure for a simple and trouble free
synthesis process; the accelerated polymerization places a supplement in the amorphous
content, which augments the strength performance of GPC that is prepared with fly ash;
even short curing periods at room temperature can achieve equivalent strength to OPC
composites; they suffer an 80% lower shrinkage than the OPC system; they are not found
to drop in functionality, even at 1000–1200 ◦ C, proving their low thermal conductivity and
excellent resistance to fire and championing them as exceptional heat-insulating materials;
they can be efficiently utilized for residential buildings, pedestrian driveways, etc., on
account of their light weight; they exhibit brilliant durability, strength and sustainability be-
cause of their inorganic origin and generally content of massive minerals of zeolitic nature
viz., sodalite, analcime, etc.; they can immobilize toxic waste; they have an extremely low
level of creep and permeability; inferior shrinkage, no water curing requisite; conservation
of natural restricted resources such as limestones, coals, etc.; fly ash-based geopolymer
binder can be utilized as a sealant to store carbon dioxide in the underground; they have
outstanding mechanical properties such as high early strength due to the quicker speed
of curing and higher interfacial binding force with the rapid development of gel and fast
dehydration in comparison with OPC system, contributing sustainable composites; they
show extraordinary resistance to chemicals, acid, sulphate and chemicals on account of
possessing the Si-O and Al-O bonding; swift curing; higher interfacial binding force, etc.;
their adsorbents are competent and enough in comparison with commercial adsorbents and
utilized to clean up real waste-waters enclosing dyes, heavy metals, petroleum compounds,
radionuclides, agricultural nutrients, etc.; radioactive fly ash either for mine acid water
or fixation of radioactive elements and thus, proving competent enough to immobilize
even peril wastes of radioactive type into geopolymer matrix; they have an exceptional
resistance to freeze–thaw conditions, providing evidence of being a structurally steady and
intact material even under severe conditions, owing to a special 3D network structure of
aluminosilicate and a network framework of [–Si-O-Al-O]n bonding that is equivalent to
zeolites (as this structure does not depend on lower strength bonds, as found with the OPC
system); their hardening mechanism is swifter and at lower temperatures; they are found to
be strongly bonded to aggregate; they have a lower cost and extensive sources of fly ash rich
in silica plus alumina; and their pozzolanic nature, etc. Nevertheless, advanced research
and examinations of fly ash-based geopolymeric materials concerning their properties are
J. Compos. Sci. 2022, 6, 219 45 of 59

still needed to establish them as proper substitutes of OPC-based counterpart composites.

The production of geopolymers based on fly ash with advanced inputs on a huge industrial
scale, as well as their latest applications, are worth exploring and desirable. Nevertheless,
while prepared through employing profusely accessible economical precursors, activators
and supplementary cementitious materials under the acceptable and necessitated quality
control of diverse attributes—chiefly strength, durability and low carbon footmarks of fly
ash-based geopolymers—are a significant potential component of the future toolbox of
sustainable and affordable construction materials. The all-embracing applications of fly
ash-based geopolymers, especially in the context of construction and infrastructure indus-
tries, have proved to be acceptable. Furthermore, these excellent attributes and advantages
of fly ash-based geopolymeric composites have not merely attracted researchers but also
established them as the “promising construction materials of very near future to “go green”!
However, establishing and promoting the feasibility of geopolymer based on fly ash as a
most promising, durable, sustainable, affordable, green, user and eco-friendly building
composite necessitates full awareness and promotion of these innovative materials, in order
to offer full confidence to construction and infrastructure-related persons and engineers.
Eventually, it can be said that fly ash-based geopolymer technology has enough potential
competencies to establish it as a fully durable, sustainable, cost-effective and promising
one. It has proved to be a great strategy of “convert the waste for the best”, which is a need
of the hour for the novel concept of “Go Green and Live Green”!

Author Contributions: Conceptualization, S.L. and I.L.; methodology, S.L.; validation, S.L. and I.L.;
formal analysis, I.L.; investigation, S.L. and I.L.; resources, I.L.; writing—original draft preparation,
S.L. and I.L.; writing—review and editing, I.L.; visualization, I.L. and S.L. All authors have read and
agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Imbabi, M.S.; Carrigan, C.; McKenna, S. Trends and developments in green cement and concrete technology. Int. J. Sustain. Built
Environ. 2012, 1, 194–216. [CrossRef]
2. Zaidi, F.H.A.; Ahmad, R.; Abdullah, M.M.A.B.; Wan Ibrahim, W.A.N.; Aziz, I.H.; Junaidi, S. Assessment of Geopolymer Concrete
for Underwater Concreting Properties. Arch. Metall. Mater. 2022, 2, 677–684.
3. Arokiasamy, P.; Abdullah, M.M.A.B.; Abd Rahim, S.Z.; Sandu, A.V.; Jamil, N.H.; Nabiałek, M. Synthesis methods of hydroxyap-
atite from natural sources: A review. Ceram. Int. 2022, 48, 14959–14979. [CrossRef]
4. Petrillo, A.; Farina, I.; Travaglioni, M.; Salzano, C.; Puca, S.; Ramondo, A.; Olivares, R.; Cossentino, L.; Cioffi, R. Opportunities
and future challenges of geopolymer mortars for sustainable development. In Handbook of Sustainable Concrete and Industrial Waste
Management; Woodhead Publishing: Sawston, UK, 2022; pp. 661–686. [CrossRef]
5. Luhar, I.; Luhar, S.; Abdullah, M.M.A.B.; Razak, R.A.; Vizureanu, P.; Sandu, A.V.; Matasaru, P.-D. A State-of-the-Art Review
on Innovative Geopolymer Composites Designed for Water and Wastewater Treatment. Materials 2021, 14, 7456. [CrossRef]
[PubMed]
6. Antunes, M.; Santos, R.L.; Pereira, J.; Rocha, P.; Horta, R.B.; Colaço, R. Alternative Clinker Technologies for Reducing Carbon
Emissions in Cement Industry: A Critical Review. Materials 2021, 15, 209. [CrossRef] [PubMed]
7. Luhar, S.; Luhar, I. Additive Manufacturing in the Geopolymer Construction Technology: A Review. Open Constr. Build. Technol. J.
2020, 14, 150–161. [CrossRef]
8. Andrew, R.M. Global CO2 emissions from cement production, 1928–2018. Earth Syst. Sci. Data 2019, 11, 1675–1710. [CrossRef]
9. McCaffrey, R. Climate Change and the Cement Industry. Glob. Cem. Lime Mag. 2022, 15, 19.
10. Nanthagopalan, P.; Santhanam, M. Fresh and hardened properties of self- compacting concrete produced with Manufactured
sand. Cem. Concr. Compos. 2011, 33, 353–358. [CrossRef]
11. Pacheco-Torgal, F.; Shasavandi, A.; Jalali, S. Eco-Efficient Concrete Using Industrial Wastes: A Review. Mater. Sci. Forum 2012,
730–732, 581–586. [CrossRef]
J. Compos. Sci. 2022, 6, 219 46 of 59

12. Luhar, S.; Luhar, I.; Shaikh, F.U.A. A Review on the Performance Evaluation of Autonomous Self-Healing Bacterial Concrete:
Mechanisms, Strength, Durability, and Microstructural Properties. J. Compos. Sci. 2022, 6, 23. [CrossRef]
13. Luhar, I.; Luhar, S.; Savva, P.; Theodosiou, A.; Petrou, M.F.; Nicolaides, D. Light Transmitting Concrete: A Review. Buildings 2021,
11, 480. [CrossRef]
14. Luhar, S.; Luhar, I.; Abdullah, M.M.A.B.; Hussin, K. Challenges and prospective trends of various industrial and solid wastes
incorporated with sustainable green concrete. In Advances in Organic Farming; Woodhead Publishing: Sawston, UK, 2021;
pp. 223–240. [CrossRef]
15. Dananjayan, R.R.T.; Kandasamy, P.; Andimuthu, R. Direct mineral carbonation of coal fly ash for CO2 sequestration. J. Clean.
Prod. 2016, 112, 4173–4182. [CrossRef]
16. Ukwattage, N.L.; Ranjith, P.G.; Yellishetty, M.; Bui, H.H.; Xu, T. A laboratory-scale study of the aqueous mineral carbonation of
coal fly ash for CO2 sequestration. J. Clean. Prod. 2015, 103, 665–674. [CrossRef]
17. Bai, Y.; Guo, W.; Wang, X.; Pan, H.; Zhao, Q.; Wang, D. Utilization of municipal solid waste incineration fly ash with red
mud-carbide slag for eco-friendly geopolymer preparation. J. Clean. Prod. 2022, 340, 130820. [CrossRef]
18. Nurruddin, M.F.; Sani, H.; Mohammed, B.S.; Shaaban, I. Methods of curing geopolymer concrete: A review. Int. J. Adv. Appl. Sci.
2018, 5, 31–36. [CrossRef]
19. Luhar, S.; Luhar, I. Rubberized Geopolymer Concrete: Application of Taguchi Method for Various Factors. Int. J. Recent Technol.
Eng. 2020, 8, 1167–1174. [CrossRef]
20. Luhar, S.; Luhar, I. Application of artificial neural network for predicting compressive strength of geopolymer concrete. Indian
Concr. J. 2019, 93, 38–43.
21. Luhar, S.; Luhar, I. Application of Seawater and Sea Sand to Develop Geopolymer Composites. Int. J. Recent Technol. Eng. 2020,
8, 5625–5633. [CrossRef]
22. Huseien, G.F.; Mirza, J.; Ismail, M.; Ghoshal, S.; Hussein, A.A. Geopolymer mortars as sustainable repair material: A comprehen-
sive review. Renew. Sustain. Energy Rev. 2017, 80, 54–74. [CrossRef]
23. Liew, Y.-M.; Heah, C.-Y.; Mohd Mustafa, A.B.; Kamarudin, H. Structure and properties of clay-based geopolymer cements: A
review. Prog. Mater. Sci. 2016, 83, 595–629. [CrossRef]
24. Ambaye, T.G.; Vaccari, M.; Bonilla-Petriciolet, A.; Prasad, S.; van Hullebusch, E.D.; Rtimi, S. Emerging technologies for biofuel
production: A critical review on recent progress, challenges and perspectives. J. Environ. Manag. 2021, 290, 112627. [CrossRef]
25. Hasanbeigi, A.; Price, L.; Lin, E. Emerging energy-efficiency and CO2 emission-reduction technologies for cement and concrete
production: A technical review. Renew. Sustain. Energy Rev. 2012, 16, 6220–6238. [CrossRef]
26. Luhar, S.; Khandelwal, U. A study on durability of dredged marine sand concrete. Int. J. Eng. Res. Rev. 2015, 3, 56–76.
27. Roy, D.M.; Jiang, W.; Silsbee, M.R. Chloride diffusion in ordinary, blended, and alkali-activated cement pastes and its relation to
other properties. Cem. Concr. Res. 2000, 30, 1879–1884. [CrossRef]
28. Bakharev, T.; Sanjayan, J.; Cheng, Y.-B. Sulfate attack on alkali-activated slag concrete. Cem. Concr. Res. 2002, 32, 211–216.
[CrossRef]
29. Puertas, F.; Gutierrez, R.D.; Fernández-Jiménez, A.; Delvasto, S.; Maldonado, J. Alkaline cement mortars. Chemical resistance to
sulfate and seawater attack. Mater. Constr. 2002, 52, 55–71. [CrossRef]
30. Fernandez-Jimenez, A.; García-Lodeiro, I.; Palomo, A. Durability of alkali-activated fly ash cementitious materials. J. Mater. Sci.
2006, 42, 3055–3065. [CrossRef]
31. Luhar, S.; Luhar, I.; Gupta, R. Durability performance evaluation of green geopolymer concrete. Eur. J. Environ. Civ. Eng. 2020,
26, 4297–4345. [CrossRef]
32. Shi, C.; Stegemann, J.A. Acid corrosion resistance of different cementing materials. Cem. Concr. Res. 2000, 30, 803–808. [CrossRef]
33. Pu, X.; Yang, C.; Liu, F. Studies on resistance of alkali activated slag concrete to acid attack. In Proceedings of the 2nd International
Conference on Alkaline Cements and Concretes; VIPOL Stock Company: Kiev, Ukraine, 1999; pp. 717–721.
34. Luhar, S. Performance Evaluation of Rubberized Geopolymer Concrete and Fly Ash based Geopolymer Mortar. Ph.D. Thesis,
MNIT, Jaipur, India, 2018.
35. Puertas, F.; Amat, T.; Fernández-Jiménez, A.; Vázquez, T. Mechanical and durable behaviour of alkaline cement mortars reinforced
with polypropylene fibres. Cem. Concr. Res. 2003, 33, 2031–2036. [CrossRef]
36. Luhar, S.; Luhar, I.; Nicolaides, D.; Gupta, R. Durability Performance Evaluation of Rubberized Geopolymer Concrete. Sustainabil-
ity 2021, 13, 5969. [CrossRef]
37. Shi, C. Corrosion resistance of alkali-activated slag cement. Adv. Cem. Res. 2003, 15, 77–81. [CrossRef]
38. Jimenez, A.M.F.; Palomo, J.; Puertas, F. Alkali-activated slag mortars: Mechanical strength behaviour. Cem. Concr. Res. 1999,
29, 1313–1321. [CrossRef]
39. Krizan, D.; Zivanovic, B. Effects of dosage and modulus of waterglass on early hydration of alkali–slag cements. Cem. Concr. Res.
2002, 32, 1181–1188. [CrossRef]
40. Luhar, S.; Luhar, I. Effect of different variables on fly ash based geopolymer concrete. Indian Concr. J. 2020, 94, 62–68.
41. Escalante-García, J.I.; Fuentes, A.F.; Gorokhovsky, A.; Fraire-Luna, P.E.; Mendoza-Suarez, G. Hydration Products and Reactivity
of Blast-Furnace Slag Activated by Various Alkalis. J. Am. Ceram. Soc. 2003, 86, 2148–2153. [CrossRef]
42. Fernández-Jiménez, A.; Puertas, F.; Sobrados, I.; Sanz, J. Structure of calcium silicate hydrates formed in alkaline-activated slag:
Influence of the type of alkaline activator. J. Am. Ceram. Soc. 2003, 86, 1389–1394. [CrossRef]
J. Compos. Sci. 2022, 6, 219 47 of 59

43. Puertas, F.; Fernández-Jiménez, A.; Blanco-Varela, M. Pore solution in alkali-activated slag cement pastes. Relation to the
composition and structure of calcium silicate hydrate. Cem. Concr. Res. 2004, 34, 139–148. [CrossRef]
44. Luhar, S.; LUHAR, I. Durability performance of Green Concrete Incorporating Various Wastes: A Review. J. Mater. Eng. Struct.
2019, 6, 469–484.
45. Zhang, Z.; Provis, J.L.; Reid, A.; Wang, H. Geopolymer foam concrete: An emerging material for sustainable construction. Constr.
Build. Mater. 2014, 56, 113–127. [CrossRef]
46. Pérez-Villarejo, L.; Bonet-Martínez, E.; Eliche-Quesada, D.; Sánchez-Soto, P.; Rincón-López, J.; Galiano, E.C. Biomass fly ash and
aluminium industry slags-based geopolymers. Mater. Lett. 2018, 229, 6–12. [CrossRef]
47. Luhar, S.; Luhar, I.; Shaikh, F. Review on Performance Evaluation of Autonomous Healing of Geopolymer Composites. Infrastruc-
tures 2021, 6, 94. [CrossRef]
48. Zhang, Z.; Zhu, H.; Zhou, C.; Wang, H. Geopolymer from kaolin in China: An overview. Appl. Clay Sci. 2015, 119, 31–41.
[CrossRef]
49. Singh, N.; Kumar, M.; Rai, S. Geopolymer cement and concrete: Properties. Mater. Today Proc. 2020, 29, 743–748. [CrossRef]
50. Luhar, I.; Luhar, S. Rubberized Geopolymer Composites: Value-Added Applications. J. Compos. Sci. 2021, 5, 312. [CrossRef]
51. Albitar, M.; Ali, M.M.; Visintin, P. Experimental study on fly ash and lead smelter slag-based geopolymer concrete columns.
Constr. Build. Mater. 2017, 141, 104–112. [CrossRef]
52. Hajimohammadi, A.; Ngo, T.; Kashani, A. Glass waste versus sand as aggregates: The characteristics of the evolving geopolymer
binders. J. Clean. Prod. 2018, 193, 593–603. [CrossRef]
53. Davidovits, J. Geopolymer Chemistry and Applications; Geopolymer Institute: Saint-Quentin, France, 2008.
54. Guo, B.; Liu, B.; Yang, J.; Zhang, S. The mechanisms of heavy metal immobilization by cementitious material treatments and
thermal treatments: A review. J. Environ. Manag. 2017, 193, 410–422. [CrossRef]
55. Yakubu, Y.; Zhou, J.; Ping, D.; Shu, Z.; Chen, Y. Effects of pH dynamics on solidification/stabilization of municipal solid waste
incineration fly ash. J. Environ. Manag. 2017, 207, 243–248. [CrossRef]
56. Sarker, P.; Haque, R.; Ramgolam, K.V. Fracture behaviour of heat cured fly ash based geopolymer concrete. Mater. Des. 2013,
44, 580–586. [CrossRef]
57. Rabiaa, E.; Mohamed, R.A.S.; Sofi, W.H.; Tawfik, T.A. Developing Geopolymer Concrete Properties by Using Nanomaterials and
Steel Fibers. Adv. Mater. Sci. Eng. 2020, 2020, 5186091. [CrossRef]
58. Verma, M.; Dev, N.; Rahman, I.; Nigam, M.; Ahmed, M.; Mallick, J. Geopolymer Concrete: A Material for Sustainable Development
in Indian Construction Industries. Crystals 2022, 12, 514. [CrossRef]
59. Luhar, S.; Rajamane, N.P.; Corbu, O.; Luhar, I. Impact of incorporation of volcanic ash on geopolymerization of eco-friendly
geopolymer composites: A review. In Proceedings of the IOP Conference Series: Materials Science and Engineering, Iasi, Romania,
16–17 May 2019; IOP Publishing: Bristol, UK, 2019; Volume 572, p. 012001. [CrossRef]
60. Siddika, A.; Hajimohammadi, A.; Mamun, M.A.A.; Alyousef, R.; Ferdous, W. Waste Glass in Cement and Geopolymer Concretes:
A Review on Durability and Challenges. Polymers 2021, 13, 2071. [CrossRef] [PubMed]
61. Manikandan, P.; Vasugi, V. A Critical Review of Waste Glass Powder as an Aluminosilicate Source Material for Sustainable
Geopolymer Concrete Production. Silicon 2021, 13, 3649–3663. [CrossRef]
62. Sulthan, F. Literature Review On Geopolymer Mortar Using Agricultural Waste As Precursor. Int. J. Sci. Technol. Res. 2019,
8, 232–236.
63. Turner, L.K.; Collins, F.G. Carbon dioxide equivalent (CO2 -e) emissions: A comparison between geopolymer and OPC cement
concrete. Constr. Build. Mater. 2013, 43, 125–130. [CrossRef]
64. Verdolotti, L.; Iannace, S.; Lavorgna, M.; Lamanna, R. Geopolymerization reaction to consolidate incoherent pozzolanic soil. J.
Mater. Sci. 2007, 43, 865–873. [CrossRef]
65. Luhar, S.; Cheng, T.W. Impact of Integration of Industrial Wastes on Microstructural Properties of Geopolymer Composites—A
Review. Int. J. Mech. Prod. Eng. 2020, 8, 1–6.
66. Luhar, S.; Chaudhary, S.; Luhar, I. Development of rubberized geopolymer concrete: Strength and durability studies. Constr.
Build. Mater. 2019, 204, 740–753. [CrossRef]
67. Khan, M.A.; Memon, S.A.; Farooq, F.; Javed, M.F.; Aslam, F.; Alyousef, R. Compressive Strength of Fly-Ash-Based Geopolymer
Concrete by Gene Expression Programming and Random Forest. Adv. Civ. Eng. 2021, 2021, 6618407. [CrossRef]
68. Hardjito, D. Studies of Fly Ash-based Geopolymer Concrete. Ph.D. Dissertation, Curtin University, Bentley, WA, Australia, 2005.
69. Zhang, Z.; Provis, J.L.; Reid, A.; Wang, H. Mechanical, thermal insulation, thermal resistance and acoustic absorption properties
of geopolymer foam concrete. Cem. Concr. Compos. 2015, 62, 97–105. [CrossRef]
70. Palomo, A.; Blanco-Varela, M.; Granizo, M.; Puertas, F.; Vazquez, T.; Grutzeck, M. Chemical stability of cementitious materials
based on metakaolin. Cem. Concr. Res. 1999, 29, 997–1004. [CrossRef]
71. Choudhary, V.; Luhar, S. Fly Ash Utilization: A Review. Int. J. Civ. Eng. Technol. 2017, 8, 301–312.
72. Luhar, S.; Dave, U. Investigations on mechanical properties of fly ash and slag based geopolymer concrete. Ind. Concr. J. 2016,
2, 34–41.
73. Barbosa, V.F.; MacKenzie, K.J.; Thaumaturgo, C. Synthesis and characterisation of materials based on inorganic polymers of
alumina and silica: Sodium polysialate polymers. Int. J. Inorg. Mater. 2000, 2, 309–317. [CrossRef]
74. Xu, H.; Deventer, J.S. The geopolymerisation of alumino-silicate minerals. Int. J. Miner. Process. 2000, 59, 247–266. [CrossRef]
J. Compos. Sci. 2022, 6, 219 48 of 59

75. Jaarsveld, V.; Deventer, V.; Lorenzen, L. The potential use of geopolymeric materials to immobilise toxic metals: Part I. Theory
and applications. Miner. Eng. 1997, 10, 659–669. [CrossRef]
76. Falah, M.; Ohenoja, K.; Obenaus-Emler, R.; Kinnunen, P.; Illikainen, M. Improvement of mechanical strength of alkali-activated
materials using micro low-alumina mine tailings. Constr. Build. Mater. 2020, 248, 118659. [CrossRef]
77. Davidovits, J.; Orlinski, J. Proceedings Geopolymer; Geopolymer Institute: Saint-Quentin, France, 1988.
78. Mierzwiński, D.; Walter, J. Autoclaving of alkali-activated materials. In Proceedings of the IOP Conference Series: Materials
Science and Engineering, Montevideo, Uruguay, 28–29 November 2019; IOP Publishing: Bristol, UK, 2019; Volume 706, p. 012012.
79. Davidovits, J. Global Warming effect on cement and aggregate industries. Worlds Resour. Rev. 1994, 6, 263–278.
80. Davidovits, J. Environmentally Driven Geopolymer Cement Applications. In Proceedings of the Geopolymer Conference,
Melbourne, Australia, 28–29 October 2002.
81. Provis, J.L.; Lukey, A.G.C.; van Deventer, J.S.J. Do Geopolymers Actually Contain Nanocrystalline Zeolites? A Reexamination of
Existing Results. Chem. Mater. 2005, 17, 3075–3085. [CrossRef]
82. Davidovits, J. Geopolymers: Inorganic polymeric new materials. J. Therm. Anal. Calorim. 1991, 37, 1633–1656. [CrossRef]
83. Davidovits, J. Soft Mineralurgy and Geopolymers. In Proceedings of the the Geopolymer 88, First European Conference on Soft
Mineralurgy, Compiegne, France, 1–3 June 1988.
84. Davidovits, J. Geopolymer Chemistry and Properties. In Proceedings of the the Geopolymer 88, First European Conference on
Soft Mineralurgy, Compiegne, France, 1–3 June 1988.
85. Jaarsveld, V.; Deventer, V.; Lukey, G.C. The effect of composition and temperature on the properties of fly ash- and kaolinite-based
geopolymers. Chem. Eng. J. 2002, 89, 63–73. [CrossRef]
86. Lan, T.; Meng, Y.; Ju, T.; Chen, Z.; Du, Y.; Deng, Y.; Song, M.; Han, S.; Jiang, J. Synthesis and application of geopolymers
from municipal waste incineration fly ash (MSWI FA) as raw ingredient—A review. Resour. Conserv. Recycl. 2022, 182, 106308.
[CrossRef]
87. Weng, L.; Sagoe-Crentsil, K. Dissolution processes, hydrolysis and condensation reactions during geopolymer synthesis: Part
I—Low Si/Al ratio systems. J. Mater. Sci. 2007, 42, 2997–3006. [CrossRef]
88. Mackenzie, K.J.D. What are these things called geopolymers? A physico-chemical perspective. Ceram. Trans. 2003, 153, 175–186.
89. EUR 7716; Davidovits, J. The Need to Create a New Technical Language for the Transfer of Basic Scientific Information. Transfer and
Exploitation of Scientific and Technical Information; Commission of the European Communities: Luxembourg, 1982.
90. Davidovits, J. Properties of geopolymer cements. In Proceedings of the First International Conference on Alkaline Cements and
Concretes; Kiev State Technical University, Scientific Research Institute on Binders and Materials: Kiev, Ukraine, 1994; Volume 1,
pp. 131–149.
91. Chanh, N.V.; Trung, D.B.; Tuan, D.V. Recent Research Geopolymer Concrete. In Proceedings of the 3rd ACF International
Conferance, Ho Chi Minh City, Vietnam, 11–13 November 2008.
92. Luhar, S.; Nicolaides, D.; Luhar, I. Fire Resistance Behaviour of Geopolymer Concrete: An Overview. Buildings 2021, 11, 82.
[CrossRef]
93. He, R.; Dai, N.; Wang, Z. Thermal and Mechanical Properties of Geopolymers Exposed to High Temperature: A Literature Review.
Adv. Civ. Eng. 2020, 2, 7532703. [CrossRef]
94. Rangan, B.V.; Hardjito, D.; Wallah, S.E.; Sumajouw, D.M.J. Studies on Fly Ash Based Geopolymer Concrete. In Green Chemistry
and Sustainable Development Solutions, 1st ed.; Geopolymer: Saint-Quentin, France, 2005.
95. Thaarrini, J.; Dhivya, S. Comparative study on the production cost of geopolymer and conventional concretes. Int. J. Civ. Eng. Res.
2016, 7, 117–124.
96. Bhavin, B.; Pitroda, J.; Bhavsar, J.J. Geopolymer concrete and its feasibility in India. In Proceedings of the National Conference
CRDCE13, Vasad, India, 20–21 December 2013; pp. 20–21.
97. Timmons, S.F. Cementitious composition. U.S. Patent 7,442,248, 28 October 2008.
98. Gourley, J.T. Geopolymers; Opportunities for Environmentally Friendly Construction Materials. In Proceedings of the Materials
2003 Conference: Adaptive Materials for a Modern Society, Sydney, Australia, 1–3 October 2003.
99. Gourley, J.T.; Johnson, G.B. Developments in Geopolymer Precast Concrete. In Proceedings of the International Workshop on
Geopolymers and Geopolymer Concrete, Perth, Australia, 28–29 September 2005.
100. Ganesan, N.; Indira, P.V.; Santhakumar, A. Prediction of ultimate strength of reinforced geopolymer concrete wall panels in
one-way action. Constr. Build. Mater. 2013, 48, 91–97. [CrossRef]
101. Dawczyńnski, S.; Krzywon, R.; Orski, M.G.; Dubińnska, W.; Samoszuk, M. Geopolymer concrete—Applications in civil engineer-
ing. In Proceedings of the XXXI Salon Tecnologico de la Construccion—EXCO 2017, Valencia, Spain, 20–24 February 2017.
102. Ober, J.A. Mineral Commodity Summaries; US Geological Survey: Reston, VA, USA, 2018.
103. Ma, C.-K.; Awang, A.Z.; Omar, W. Structural and material performance of geopolymer concrete: A review. Constr. Build. Mater.
2018, 186, 90–102. [CrossRef]
104. Pilehvar, S.; Cao, V.D.; Szczotok, A.M.; Valentini, L.; Salvioni, D.; Magistri, M.; Pamies, R.; Kjøniksen, A.-L. Mechanical properties
and microscale changes of geopolymer concrete and Portland cement concrete containing micro-encapsulated phase change
materials. Cem. Concr. Res. 2017, 100, 341–349. [CrossRef]
105. Zuhua, Z.; Xiao, Y.; Huajun, Z.; Yue, C. Role of water in the synthesis of calcined kaolin-based geopolymer. Appl. Clay Sci. 2009,
43, 218–223. [CrossRef]
J. Compos. Sci. 2022, 6, 219 49 of 59

106. Cao, V.D.; Pilehvar, S.; Salas-Bringas, C.; Szczotok, A.M.; Valentini, L.; Carmona, M.; Rodriguez, J.F.; Kjøniksen, A.-L. Influence of
microcapsule size and shell polarity on thermal and mechanical properties of thermoregulating geopolymer concrete for passive
building applications. Energy Convers. Manag. 2018, 164, 198–209. [CrossRef]
107. Cao, V.D.; Pilehvar, S.; Salas-Bringas, C.; Szczotok, A.M.; Bui, T.Q.; Carmona, M.; Rodriguez, J.F.; Kjøniksen, A.-L. Thermal
performance and numerical simulation of geopolymer concrete containing different types of thermoregulating materials for
passive building applications. Energy Build. 2018, 173, 678–688. [CrossRef]
108. Zeyad, A.M.; Johari, M.A.M.; Abutaleb, A.; Tayeh, B.A. The effect of steam curing regimes on the chloride resistance and pore
size of high–strength green concrete. Constr. Build. Mater. 2021, 280, 122409. [CrossRef]
109. Zeyad, A.M.; Johari, M.A.M.; Alharbi, Y.R.; Abadel, A.A.; Amran, Y.M.; Tayeh, B.A.; Abutaleb, A. Influence of steam curing
regimes on the properties of ultrafine POFA-based high-strength green concrete. J. Build. Eng. 2021, 38, 102204. [CrossRef]
110. Humphreys, K.; Mahasenan, M. Toward a Sustainable Cement Industry. Substudy 8, Climate Change 2; World Business Council for
Sustainable Development: Geneva, Switzerland, 2002.
111. Panda, B.; Unluer, C.; Tan, M.J. Investigation of the rheology and strength of geopolymer mixtures for extrusion-based 3D
printing. Cem. Concr. Compos. 2018, 94, 307–314. [CrossRef]
112. Bernal, S.A.; Provis, J.; Rose, V.; De Gutierrez, R.M. Evolution of binder structure in sodium silicate-activated slag-metakaolin
blends. Cem. Concr. Compos. 2011, 33, 46–54. [CrossRef]
113. Wang, C.; Xu, G.; Gu, X.; Gao, Y.; Zhao, P. High value-added applications of coal fly ash in the form of porous materials: A review.
Ceram. Int. 2021, 47, 22302–22315. [CrossRef]
114. Zhang, X.; Bai, C.; Qiao, Y.; Wang, X.; Jia, D.; Li, H.; Colombo, P. Porous geopolymer composites: A review. Compos. Part A Appl.
Sci. Manuf. 2021, 150, 106629. [CrossRef]
115. Jeremiah, J.J.; Abbey, S.J.; Booth, C.A.; Kashyap, A. Geopolymers as Alternative Sustainable Binders for Stabilisation of Clays—A
Review. Geotechnics 2021, 1, 439–459. [CrossRef]
116. Paz-Gómez, D.C.; Vilarinho, I.S.; Pérez-Moreno, S.M.; Carvalheiras, J.; Guerrero, J.L.; Novais, R.M.; Seabra, M.P.; Ríos, G.; Bolívar,
J.P.; Labrincha, J.A. Immobilization of Hazardous Wastes on One-Part Blast Furnace Slag-Based Geopolymers. Sustainability 2021,
13, 13455. [CrossRef]
117. Amran, M.; Al-Fakih, A.; Chu, S.H.; Fediuk, R.; Haruna, S.; Azevedo, A.; Vatin, N. Long-term durability properties of geopolymer
concrete: An in-depth review. Case Stud. Constr. Mater. 2021, 15, e00661. [CrossRef]
118. Cong, P.; Cheng, Y. Advances in geopolymer materials: A comprehensive review. J. Traffic Transp. Eng. 2021, 8, 283–314. [CrossRef]
119. Ganesh, A.C.; Muthukannan, M. Development of high performance sustainable optimized fiber reinforced geopolymer concrete
and prediction of compressive strength. J. Clean. Prod. 2021, 282, 124543. [CrossRef]
120. Han, Q.; Zhang, P.; Wu, J.; Jing, Y.; Zhang, D.; Zhang, T. Comprehensive review of the properties of fly ash-based geopolymer
with additive of nano-SiO2 . Nanotechnol. Rev. 2022, 11, 1478–1498. [CrossRef]
121. Hardjito, W.; Sumajouw, R. Fly ash-based geopolymer concrete. Aust. J. Struct. Eng. 2015, 73, 77–86. [CrossRef]
122. Heah, C.; Kamarudin, H.; Al Bakri, A.M.; Binhussain, M.; Luqman, M.; Nizar, I.K.; Ruzaidi, C.; Liew, Y. Effect of Curing Profile on
Kaolin-based Geopolymers. Phys. Procedia 2011, 22, 305–311. [CrossRef]
123. Rovnaník, P. Effect of curing temperature on the development of hard structure of metakaolin-based geopolymer. Constr. Build.
Mater. 2010, 24, 1176–1183. [CrossRef]
124. Ranjbar, N.; Kuenzel, C.; Spangenberg, J.; Mehrali, M. Hardening evolution of geopolymers from setting to equilibrium: A review.
Cem. Concr. Compos. 2020, 114, 103729. [CrossRef]
125. Farooq, F.; Jin, X.; Javed, M.F.; Akbar, A.; Shah, M.I.; Aslam, F.; Alyousef, R. Geopolymer concrete as sustainable material: A state
of the art review. Constr. Build. Mater. 2021, 306, 124762. [CrossRef]
126. Shehata, N.; Mohamed, O.; Sayed, E.T.; Abdelkareem, M.A.; Olabi, A. Geopolymer concrete as green building materials: Recent
applications, sustainable development and circular economy potentials. Sci. Total Environ. 2022, 836, 155577. [CrossRef] [PubMed]
127. Cui, Y.; Wang, D. Effects of Water on Pore Structure and Thermal Conductivity of Fly Ash-Based Foam Geopolymers. Adv. Mater.
Sci. Eng. 2019, 2019, 3202794. [CrossRef]
128. 128. Promoda Kumar Behera. Influence of High Temperatures on Properties of Geopolymers Filled by Inorganic Fibrous Particles.
Masters’s Thesis, Technical University of Liberec, Liberec, Czechia, 2019.
129. Aleem, M.A.; Arumairaj, P.D. Geopolymer concrete–A review. Int. J. Eng. Sci. Emerg. Technol. 2012, 1, 118–122. [CrossRef]
130. Ahmaruzzaman, M. A review on the utilization of fly ash. Prog. Energy Combust. Sci. 2010, 36, 327–363. [CrossRef]
131. Gorai, B.; Jana, R.K.; Premchand. Characteristics and utilization of copper slag a review. Resour. Conserv. Recycl. 2006, 39, 299–313.
[CrossRef]
132. International Energy Outlook; U.S. Energy Information Administration: Washington, DC, USA, 2018.
133. Klima, K.; Schollbach, K.; Brouwers, H.; Yu, Q. Thermal and fire resistance of Class F fly ash based geopolymers—A review.
Constr. Build. Mater. 2022, 323, 126529. [CrossRef]
134. Querol, X.; Juan, R.; Lopez-Soler, A.; Fernandez-Turiel, J.; Ruiz, C.R. Mobility of trace elements from coal and combustion wastes.
Fuel 1996, 75, 821–838. [CrossRef]
135. Jegadeesan, G.; Al-Abed, S.R.; Pinto, P. Influence of trace metal distribution on its leachability from coal fly ash. Fuel 2008,
87, 1887–1893. [CrossRef]
J. Compos. Sci. 2022, 6, 219 50 of 59

136. Huggins, F.; Rezaee, M.; Honaker, R.; Hower, J. On the removal of hexavalent chromium from a Class F fly ash. Waste Manag.
2016, 51, 105–110. [CrossRef] [PubMed]
137. Yao, Z.T.; Ji, X.S.; Sarker, P.K.; Tang, J.H.; Ge, L.Q.; Xia, M.S.; Xi, Y.Q. A comprehensive review on the applications of coal fly ash.
Earth-Sci. Rev. 2015, 141, 105–121. [CrossRef]
138. Bhattacharjee, U.; Kandpal, T.C. Potential of fly ash utilisation in India. Energy 2002, 27, 151–166. [CrossRef]
139. European Coal Combustion Products Association. Production and Utilisation of CCPs in 2016 in Europe (EU 15); European Coal
Combustion Products Association: Essen, Germany, 2016.
140. American Coal Ash Association. Coal Combustion Products Production & Use Reports; American Coal Ash Association: Denver, CO,
USA, 2020.
141. Moreno, N.; Querol, X.; Ayora, C.; Pereira, C.F.; Janssen-Jurkovicová, M. Utilization of Zeolites Synthesized from Coal Fly Ash for
the Purification of Acid Mine Waters. Environ. Sci. Technol. 2001, 35, 3526–3534. [CrossRef] [PubMed]
142. Mukherjee, A.B.; Zevenhoven, R.; Bhattacharya, P.; Sajwan, K.S.; Kikuchi, R. Mercury flow via coal and coal utilization by-
products: A global perspective. Resour. Conserv. Recycl. 2008, 52, 571–591. [CrossRef]
143. Sibanda, V.; Ndlovu, S.; Dombo, G.; Shemi, A.; Rampou, M. Towards the Utilization of Fly Ash as a Feedstock for Smelter Grade
Alumina Production: A Review of the Developments. J. Sustain. Met. 2016, 2, 167–184. [CrossRef]
144. Yao, Z.; Xia, M.; Sarker, P.; Chen, T. A review of the alumina recovery from coal fly ash, with a focus in China. Fuel 2014, 120, 74–85.
[CrossRef]
145. Belviso, C. State-of-the-art applications of fly ash from coal and biomass: A focus on zeolite synthesis processes and issues. Prog.
Energy Combust. Sci. 2018, 65, 109–135. [CrossRef]
146. Belviso, C.; Cavalcante, F.; Fiore, S. Synthesis of zeolite from Italian coal fly ash: Differences in crystallization temperature using
seawater instead of distilled water. Waste Manag. 2010, 30, 839–847. [CrossRef]
147. Belviso, C.; Cavalcante, F.; Ragone, P.; Fiore, S. Immobilization of Ni by synthesising zeolite at low temperatures in a polluted soil.
Chemosphere 2010, 78, 1172–1176. [CrossRef]
148. Belviso, C.; Cavalcante, F.; Lettino, A.; Fiore, S. Effects of ultrasonic treatment on zeolite synthesized from coal fly ash. Ultrason.
Sonochemistry 2011, 18, 661–668. [CrossRef] [PubMed]
149. Belviso, C.; Cavalcante, F.; Ragone, P.; Fiore, S. Immobilization of Zn and Pb in Polluted Soil by In Situ Crystallization Zeolites
from Fly Ash. Water Air Soil Pollut. 2012, 223, 5357–5364. [CrossRef]
150. Wang, P.; Hu, Y.; Cheng, H. Municipal solid waste (MSW) incineration fly ash as an important source of heavy metal pollution in
China. Environ. Pollut. 2019, 252, 461–475. [CrossRef] [PubMed]
151. Havlica, J.; Brandstetr, J.; Odler, I. Possibilities of Utilizing Solid Residues from Pressured Fluidized Bed Coal Combustion (PSBC)
for the Production of Blended Cements. Cem. Concr. Res. 1998, 28, 299–307. [CrossRef]
152. Li, X.-G.; Chen, Q.-B.; Ma, B.-G.; Huang, J.; Jian, S.-W.; Wu, B. Utilization of modified CFBC desulfurization ash as an admixture
in blended cements: Physico-mechanical and hydration characteristics. Fuel 2012, 102, 674–680. [CrossRef]
153. Brandštetr, J.; Havlica, J. Phase composition of solid residues of fluidized bed coal combustion, quality tests, and application
possibilities. Chem. Pap. 1996, 50, 188–194.
154. Kaewmanee, K.; Krammart, P.; Sumranwanich, T.; Choktaweekarn, P.; Tangtermsirikul, S. Effect of free lime content on properties
of cement–fly ash mixtures. Constr. Build. Mater. 2013, 38, 829–836. [CrossRef]
155. Dvořák, R.; Chlápek, P.; Jecha, D.; Puchýř, R.; Stehlík, P. New approach to common removal of dioxins and NOx as a contribution
to environmental protection. J. Clean. Prod. 2010, 18, 881–888. [CrossRef]
156. Brendel, G.F.; Bonetti, J.E.; Rathbone, R.F.; Frey, R.N.F., Jr. Investigation of Ammonia Adsorption on Fly Ash Due to the Installation of
Selective Catalytic Reduction Systems; U.S. Department of Energy, Office of Scientific and Technical Informatio: Pittsburgh, PA,
USA, 2000.
157. Mazur, M.; Janda, T.; Zukowski, W. Chemical and ThermalMethods for Removing Ammonia from Fly Ashes. Tech. Trans. 2017,
6, 31–50.
158. Michalik, A.; Babińska, J.; Chyliński, F.; Piekarczuk, A. Ammonia in Fly Ashes from Flue Gas Denitrification Process and its
Impact on the Properties of Cement Composites. Buildings 2019, 9, 225. [CrossRef]
159. Procházka, L.; Boháčová, J.; Vojvodíková, B. Influence of Fly Ash Denitrification on Properties of Hybrid Alkali-Activated
Composites. Crystals 2022, 12, 633. [CrossRef]
160. Jimenez, A.M.F.; Garcia-Lodeiro, I.; Maltseva, O.; Palomo, A. Mechanical-Chemical Activation of Coal Fly Ashes: An Effective
Way for Recycling and Make Cementitious Materials. Front. Mater. 2019, 6, 51. [CrossRef]
161. Pavithra, P.; Reddy, M.S.; Dinakar, P.; Rao, B.H.; Satpathy, B.; Mohanty, A. A mix design procedure for geopolymer concrete with
fly ash. J. Clean. Prod. 2016, 133, 117–125. [CrossRef]
162. Kurtoglu, A.E.; Alzeebaree, R.; Aljumaili, O.; Nis, A.; Gulsan, M.E.; Humur, G.; Cevik, A. Mechanical and durability properties of
fly ash and slag based geopolymer concrete. Adv. Concr. Constr. 2018, 6, 345.
163. Okoye, F.; Durgaprasad, J.; Singh, N. Effect of silica fume on the mechanical properties of fly ash based-geopolymer concrete.
Ceram. Int. 2016, 42, 3000–3006. [CrossRef]
164. Xie, T.; Ozbakkaloglu, T. Behavior of low-calcium fly and bottom ash-based geopolymer concrete cured at ambient temperature.
Ceram. Int. 2015, 41, 5945–5958. [CrossRef]
J. Compos. Sci. 2022, 6, 219 51 of 59

165. Assi, L.; Ghahari, S.; Deaver, E.; Leaphart, D.; Ziehl, P. Improvement of the early and final compressive strength of fly ash-based
geopolymer concrete at ambient conditions. Constr. Build. Mater. 2016, 123, 806–813. [CrossRef]
166. Hager, I.; Sitarz, M.; Mróz, K. Fly-ash-based geopolymer mortar for high-temperature application–Effect of slag addition. J. Clean.
Prod. 2021, 316, 128168. [CrossRef]
167. Embong, R.; Kusbiantoro, A.; Shafiq, N.; Nuruddin, M.F. Strength and microstructural properties of fly ash based geopolymer
concrete containing high-calcium and water-absorptive aggregate. J. Clean. Prod. 2016, 112, 816–822. [CrossRef]
168. Sreevidya, V.; Anuradha, R.; Dinakar, D.; Venkatasubramani, R. Acid resistance of flyash based geopolymer mortar under ambient
curing and heat curing. Int. J. Eng. Sci. Technol. 2012, 4, 681–684.
169. Duan, P.; Yan, C.; Luo, W.; Zhou, W. Effects of adding nano-TiO2 on compressive strength, drying shrinkage, carbonation and
microstructure of fluidized bed fly ash based geopolymer paste. Constr. Build. Mater. 2016, 106, 115–125. [CrossRef]
170. Rajak, M.; Rai, B. Effect of Micro Polypropylene Fibre on the Performance of Fly Ash-Based Geopolymer Concrete. J. Appl. Eng.
Sci. 2019, 9, 97–108. [CrossRef]
171. Liu, M.Y.J.; Alengaram, U.J.; Santhanam, M.; Jumaat, M.Z.; Mo, K.H. Microstructural investigations of palm oil fuel ash and fly
ash based binders in lightweight aggregate foamed geopolymer concrete. Constr. Build. Mater. 2016, 120, 112–122. [CrossRef]
172. Park, Y.; Abolmaali, A.; Kim, Y.H.; Ghahremannejad, M. Compressive strength of fly ash-based geopolymer concrete with crumb
rubber partially replacing sand. Constr. Build. Mater. 2016, 118, 43–51. [CrossRef]
173. Khan, M.; Castel, A.; Akbarnezhad, A.; Foster, S.; Smith, M. Utilisation of steel furnace slag coarse aggregate in a low calcium fly
ash geopolymer concrete. Cem. Concr. Res. 2016, 89, 220–229. [CrossRef]
174. Assaedi, H.; Shaikh, F.U.A.; Low, I.M. Influence of mixing methods of nano silica on the microstructural and mechanical properties
of flax fabric reinforced geopolymer composites. Constr. Build. Mater. 2016, 123, 541–552. [CrossRef]
175. Gunasekara, C.; Law, D.; Setunge, S. Long term permeation properties of different fly ash geopolymer concretes. Constr. Build.
Mater. 2016, 124, 352–362. [CrossRef]
176. Leong, H.Y.; Ong, D.E.L.; Sanjayan, J.; Nazari, A. Suitability of Sarawak and Gladstone fly ash to produce geopolymers: A
physical, chemical, mechanical, mineralogical and microstructural analysis. Ceram. Int. 2016, 42, 9613–9620. [CrossRef]
177. Huiskes, D.M.A.; Keulen, A.; Yu, Q.L.; Brouwers, H.J.H. Design and performance evaluation of ultra-lightweight geopolymer
concrete. Mater. Des. 2016, 89, 516–526. [CrossRef]
178. Zeng, S.; Wang, J. Characterization of mechanical and electric properties of geopolymers synthesized using four locally available
fly ashes. Constr. Build. Mater. 2016, 121, 386–399. [CrossRef]
179. Tho-In, T.; Sata, V.; Boonserm, K.; Chindaprasirt, P. Compressive strength and microstructure analysis of geopolymer paste using
waste glass powder and fly ash. J. Clean. Prod. 2018, 172, 2892–2898. [CrossRef]
180. Das, S.; Yang, P.; Singh, S.S.; Mertens, J.C.; Xiao, X.; Chawla, N.; Neithalath, N. Effective properties of a fly ash geopolymer:
Synergistic application of X-ray synchrotron tomography, nanoindentation, and homogenization models. Cem. Concr. Res. 2015,
78, 252–262. [CrossRef]
181. Pilehvar, S.; Cao, V.D.; Szczotok, A.M.; Carmona, M.; Valentini, L.; Lanzón, M.; Pamies, R.; Kjøniksen, A.-L. Physical and
mechanical properties of fly ash and slag geopolymer concrete containing different types of micro-encapsulated phase change
materials. Constr. Build. Mater. 2018, 173, 28–39. [CrossRef]
182. Blissett, R.S.; Rowson, N.A. A review of the multi-component utilisation of coal fly ash. Fuel 2012, 97, 1–23. [CrossRef]
183. Bhatt, A.; Priyadarshini, S.; Mohanakrishnan, A.A.; Abri, A.; Sattler, M.; Techapaphawit, S. Physical, chemical, and geotechnical
properties of coal fly ash: A global review. Case Stud. Constr. Mater. 2019, 11, e00263, Erratum in Case Stud. Constr. Mater. 2021,
14, e00486. [CrossRef]
184. Korniejenko, K.; Halyag, N.P.; Mucsi, G. Fly ash as a raw material for geopolymerisation-chemical composition and physical
properties. IOP Conf. Ser. Mater. Sci. Eng. 2019, 706, 012002. [CrossRef]
185. Chindaprasirt, P.; Phoo-Ngernkham, T.; Hanjitsuwan, S.; Horpibulsuk, S.; Poowancum, A.; Injorhor, B. Effect of calcium-rich
compounds on setting time and strength development of alkali-activated fly ash cured at ambient temperature. Case Stud. Constr.
Mater. 2018, 9, e00198. [CrossRef]
186. Yadav, V.K.; Fulekar, M.H. Advances in Methods for Recovery of Ferrous, Alumina, and Silica Nanoparticles from Fly Ash Waste.
Ceramics 2020, 3, 384–420. [CrossRef]
187. Nyale, S.M.; Eze, C.P.; Akinyeye, R.O.; Gitari, W.M.; Akinyemi, S.A.; Fatoba, O.O.; Petrik, L.F. The leaching behaviour and
geochemical fractionation of trace elements in hydraulically disposed weathered coal fly ash. J. Environ. Sci. Health Part A 2013,
49, 233–242. [CrossRef]
188. Tiwari, M.; Sahu, S.K.; Bhangare, R.C.; Ajmal, P.Y.; Pandit, G.G. Elemental characterization of coal, fly ash, and bottom ash using
an energy dispersive X-ray fluorescence technique. Appl. Radiat. Isot. 2014, 90, 53–57. [CrossRef]
189. Neupane, G.; Donahoe, R.J. Leachability of elements in alkaline and acidic coal fly ash samples during batch and column leaching
tests. Fuel 2013, 104, 758–770. [CrossRef]
190. Shibayama, A.; Kim, Y.; Harjanto, S.; Sugai, Y.; Okada, K.; Fujita, T. Remediation of contaminated soil by fly ash containing
dioxins from incineration by using flotation. Mater. Trans. 2005, 46, 990–995. [CrossRef]
191. Nomura, Y.; Fujiwara, K.; Terada, A.; Nakai, S.; Hosomi, M. Prevention of lead leaching from fly ashes by mechanochemical
treatment. Waste Manag. 2010, 30, 1290–1295. [CrossRef] [PubMed]
192. Slanička, Š. The influence of fly ash fineness on the strength of concrete. Cem. Concr. Res. 1991, 21, 285–296. [CrossRef]
J. Compos. Sci. 2022, 6, 219 52 of 59

193. Erdoğdu, K.; Türker, P. Effects of fly ash particle size on strength of portland cement fly ash mortars. Cem. Concr. Res. 1998,
28, 1217–1222. [CrossRef]
194. Chindaprasirt, P.; Chotithanorm, C.; Cao, H.; Sirivivatnanon, V. Influence of fly ash fineness on the chloride penetration of
concrete. Constr. Build. Mater. 2007, 21, 356–361. [CrossRef]
195. Chindaprasirt, P.; Jaturapitakkul, C.; Sinsiri, T. Effect of fly ash fineness on microstructure of blended cement paste. Constr. Build.
Mater. 2007, 21, 1534–1541. [CrossRef]
196. Chindaprasirt, P.; Homwuttiwong, S.; Sirivivatnanon, V. Influence of fly ash fineness on strength, drying shrinkage and sulfate
resistance of blended cement mortar. Cem. Concr. Res. 2004, 34, 1087–1092. [CrossRef]
197. Jones, M.; McCarthy, A.; Booth, A.; Jones, R. Characteristics of the ultrafine component of fly ash. Fuel 2006, 85, 2250–2259.
[CrossRef]
198. Yazici, S.; Arel, H.S. Effects of fly ash fineness on the mechanical properties of concrete. Sadhana 2012, 37, 389–403. [CrossRef]
199. Vassilev, S.V.; Vassileva, C.G. A new approach for the classification of coal fly ashes based on their origin, composition, properties,
and behaviour. Fuel 2007, 86, 1490–1512. [CrossRef]
200. ASTM-C618-8a; Standard Specification for Coal Fly Ash and Raw or Calcined Natural Pozzolan for Use in Concrete; ASTM International:
West Conshohocken, PA, USA, 2009.
201. Bankowski, P.; Zou, L.; Hodges, R. Reduction of metal leaching in brown coal fly ash using geopolymers. J. Hazard. Mater. 2004,
114, 59–67. [CrossRef] [PubMed]
202. Antiohos, S.; Tsimas, S. A novel way to upgrade the coarse part of a high calcium fly ash for reuse into cement systems. Waste
Manag. 2007, 27, 675–683. [CrossRef]
203. Medhat, H.; Michail, D. The effect of fly ash composition on the expansion of concrete due to alkali silica reaction. Cem. Concr.
Res. 2000, 30, 1063–1072.
204. Wedding, P.; Dunstan, E. A Possible Method for Identifying Fly Ashes That Will Improve the Sulfate Resistance of Concretes.
Cem. Concr. Aggregates 1980, 2, 20–30. [CrossRef]
205. Smith, R. Is the available alkali test a good durability predictor for fly ash concrete incorporating reactive aggregate. In Proceedings
of the MRS Symposium, Pittsburg, PA, USA, 30 November–5 December 1988; pp. 249–256.
206. Odler, I. Special Inorganic Cements; CRC Press: London, UK, 2009.
207. Diamond, S. Effects of two Danish fly ashes on alkali contents of pore solutions of cement-fly ash pastes. Cem. Concr. Res. 1981,
11, 383–394. [CrossRef]
208. Joshi, R.C.; Lohtia, R.P. Fly Ash in Concrete Production, Properties and Uses; Gordon and Breach Science Publishers: Amsterdam, The
Netherlands, 1997.
209. Temuujin, J.; Van Riessen, A. Effect of fly ash preliminary calcination on the properties of geopolymer. J. Hazard. Mater. 2009,
164, 634–639. [CrossRef] [PubMed]
210. McCarthy, G.; Solem, J.; Manz, O.; Hassett, D. Use of a Database of Chemical, Mineralogical, and Physical Properties of North American
Fly Ash to Study the Nature of Fly Ash and Its Utilization as a Mineral Admixture in Concrete; Materials Research Society: Boston, MA,
USA, 1989; p. 178.
211. Durdzinski, P.T.; Snellings, R.; Dunant, C.F.; Haha, M.B.; Scrivener, K.L. Fly ash as an assemblage of model Ca-Mg-
Naealuminosilicate glasses. Cem. Concr. Res. 2015, 78, 263–272. [CrossRef]
212. Sakai, E.; Miyahara, S.; Ohsawa, S.; Lee, S.-H.; Daimon, M. Hydration of fly ash cement. Cem. Concr. Res. 2005, 35, 1135–1140.
[CrossRef]
213. Tkaczewska, E. Effect of size fraction and glass structure of siliceous fly ashes on fly ash cement hydration. J. Ind. Eng. Chem.
2014, 20, 315–321. [CrossRef]
214. Malhotra, V. Durability of concrete incorporating high-volume of low-calcium (ASTM Class F) fly ash. Cem. Concr. Compos. 1990,
12, 271–277. [CrossRef]
215. Sobolev, K.; Vivian, I.F.; Saha, R.; Wasi, N.M.W.; Saltibus, N.E. The effect of fly ash on the rheological properties of bituminous
materials. Fuel 2014, 116, 471–477. [CrossRef]
216. Rubel, A.; Andrews, R.; Gonzalez, R.; Groppo, J.; Robl, T. Adsorption of Hg and NOX on coal by-products. Fuel 2005, 84, 911–916.
[CrossRef]
217. Pereira, C.F.; Luna, Y.; Querol, X.; Antenucci, D.; Vale, J. Waste stabilization/solidification of an electric arc furnace dust using fly
ash-based geopolymers. Fuel 2009, 88, 1185–1193. [CrossRef]
218. Ukwattage, N.; Ranjith, P.; Bouazza, M. The use of coal combustion fly ash as a soil amendment in agricultural lands (with
comments on its potential to improve food security and sequester carbon). Fuel 2013, 109, 400–408. [CrossRef]
219. Teixeira, E.R.; Mateus, R.; Camões, A.; Bragança, L.; Branco, F.G. Comparative environmental life-cycle analysis of concretes
using biomass and coal fly ashes as partial cement replacement material. J. Clean. Prod. 2016, 112, 2221–2230. [CrossRef]
220. Chang, H.-L.; Shih, W.-H. Synthesis of Zeolites A and X from Fly Ashes and Their Ion-Exchange Behavior with Cobalt Ions. Ind.
Eng. Chem. Res. 2000, 39, 4185–4191. [CrossRef]
221. Luhar, S.; Cheng, T.W.; Nicolaides, D.; Luhar, I.; Panias, D.; Sakkas, K. Valorisation of glass wastes for the development of
geopolymer composites–Durability, thermal and microstructural properties: A review. Constr. Build. Mater. 2019, 222, 673–687.
[CrossRef]
J. Compos. Sci. 2022, 6, 219 53 of 59

222. Asokan, P.; Saxena, M.; Asolekar, S.R. Coal combustion residuesdenvironmental implications and recycling potentials. Resour.
Conserv. Recycl. 2005, 43, 239–262. [CrossRef]
223. Heidrich, C.; Feuerborn, H.-J.; Weir, A. Coal combustion products: A global perspective. In Proceedings of the 2013 World of Coal
Ash (WOCA) Conference, Lexington, KY, USA, 22–25 April 2013.
224. Kovler, K. Radiological constraints of using building materials and industrial by-products in construction. Constr. Build. Mater.
2009, 23, 246–253. [CrossRef]
225. Luhar, S.; Cheng, T.W.; Nicolaides, D.; Luhar, I.; Panias, D.; Sakkas, K. Valorisation of glass waste for development of Geopolymer
composites–Mechanical properties and rheological characteristics: A review. Constr. Build. Mater. 2019, 220, 547–564. [CrossRef]
226. McLellan, B.C.; Williams, R.P.; Lay, J.; van Riessen, A.; Corder, G.D. Costs and carbon emissions for geopolymer pastes in
comparison to ordinary portland cement. J. Clean. Prod. 2011, 19, 1080–1090. [CrossRef]
227. Jen, G.; Skalamprinos, S.; Whittaker, M.; Galan, I.; Imbabi, M.S.; Glasser, F.P. The impact of intrinsic anhydrite in an experimental
calcium sulfoaluminate cement from a novel, carbon-minimized produc-tion process. Mater. Struct. 2017, 50, 144. [CrossRef]
228. Şahmaran, M.; Li, V.C. Durability properties of micro-cracked ECC containing high volumes fly ash. Cem. Concr. Res. 2009,
39, 1033–1043. [CrossRef]
229. Nath, S.K.; Mukherjee, S.; Maitra, S.; Kumar, S. Kinetics study of geopolymerization of fly ash using isothermal conduction
calorimetry. J. Therm. Anal. 2016, 127, 1953–1961. [CrossRef]
230. Steins, P.; Poulesquen, A.; Diat, O.; Frizon, F. Structural Evolution during Geopolymerization from an Early Age to Consolidated
Material. Langmuir 2012, 28, 8502–8510. [CrossRef] [PubMed]
231. Dimas, D.; Giannopoulou, I.; Panias, D. Polymerization in sodium silicate solutions: A fundamental process in geopolymerization
technology. J. Mater. Sci. 2009, 44, 3719–3730. [CrossRef]
232. Davidovits, J. 30 years of successes and failures in geopolymer applications, market trends and potential breakthroughs. In
Proceedings of the Geopolymer 2002 Conference, Melbourne, Australia, 28–29 October 2002.
233. He, J.; Zhang, J.; Yu, Y.; Zhang, G. The strength and microstructure of two geopolymers derived from metakaolin and red mudefly
ash admixture: A comparative study. Constr. Build. Mater. 2012, 30, 80–91. [CrossRef]
234. Duxson, P.; Provis, J.L.; Lukey, G.C.; Mallicoat, S.W.; Kriven, W.M.; van Deventer, J.S.J. Understanding the relationship between
geopolymer composition, microstructure and mechanical properties. Colloids Surf. A Physicochem. Eng. Asp. 2005, 269, 47–58.
[CrossRef]
235. Kriven, W.M.; Bell, J.L.; Gordon, M. Microstructure and Microchemistry of Fully-Reacted Geopolymers and Geopolymer Matrix
Composites. Ceram. Trans. 2006, 153, 227–250.
236. Xu, H.; van Deventer, J.S.J. The geopolymerisation of natural alumino-silicates. In Proceedings of the 2nd International Conference
on Geopolymer, Saint-Quentin, France, 30 June–2 July 1999; pp. 43–63.
237. Lizcano, M.; Kim, H.S.; Basu, S.; Radovic, M. Mechanical properties of sodium and potassium activated metakaolin-based
geopolymers. J. Mater. Sci. 2011, 47, 2607–2616. [CrossRef]
238. Duxson, P.; Lukey, G.C.; Separovic, F.; van Deventer, J.S.J. Effect of Alkali Cations on Aluminum Incorporation in Geopolymeric
Gels. Ind. Eng. Chem. Res. 2005, 44, 832–839. [CrossRef]
239. Ma, Y.; Hu, J.; Ye, G. The pore structure and permeability of alkali activated fly ash. Fuel 2013, 104, 771–780. [CrossRef]
240. Rattanasak, U.; Pankhet, K.; Chindaprasirt, P. Effect of chemical admixtures on properties of high-calcium fly ash geopolymer. Int.
J. Miner. Met. Mater. 2011, 18, 364–369. [CrossRef]
241. Diaz, E.; Allouche, E.; Eklund, S. Factors affecting the suitability of fly ash as source material for geopolymers. Fuel 2010,
89, 992–996. [CrossRef]
242. Geetha, S.; Ramamurthy, K. Properties of geopolymerised low-calcium bottom ash aggregate cured at ambient temperature. Cem.
Concr. Compos. 2013, 43, 20–30. [CrossRef]
243. Hanjitsuwan, S.; Hunpratub, S.; Thongbai, P.; Maensiri, S.; Sata, V.; Chindaprasirt, P. Effects of NaOH concentrations on physical
and electrical properties of high calcium fly ash geopolymer paste. Cem. Concr. Compos. 2014, 45, 9–14. [CrossRef]
244. Hardjito, D.; Wallah, S.; Sumajouw, D.; Rangan, B. On the development of fly ash-based geopolymer concrete. ACI Mater. J. 2004,
101, 467–472.
245. Li, Z.; Liu, S. Influence of Slag as Additive on Compressive Strength of Fly Ash-Based Geopolymer. J. Mater. Civ. Eng. 2007,
19, 470–474. [CrossRef]
246. Idawati, I.; Bernal, S.A.; Provis, J.L.; Nicolas, S.R.; Hamdan, S.; van Deventer, J.S.J. Modification of phase evolution in alkali-
activated blast furnace slag by the incorporation of fly ash. Cem. Concr. Compos. 2014, 45, 125–135.
247. Kumar, S.; Kumar, R.; Mehrotra, S.P. Influence of granulated blast furnace slag on the reaction, structure and properties of fly ash
based geopolymer. J. Mater. Sci. 2010, 45, 607–615. [CrossRef]
248. Yang, T.; Yao, X.; Zhang, Z.; Wang, H. Mechanical property and structure of alkali-activated fly ash and slag blends. J. Sustain.
Cem. Mater. 2012, 1, 167–178. [CrossRef]
249. Piga, F.P.; Stoppa, L. Recovering metals from red mud generated during alumina production. JOM 1993, 45, 55–59. [CrossRef]
250. Fu, Q.; Xu, W.; Zhao, X.; Bu, M.; Yuan, Q.; Niu, D. The microstructure and durability of fly ash-based geopolymer concrete: A
review. Ceram. Int. 2021, 47, 29550–29566. [CrossRef]
J. Compos. Sci. 2022, 6, 219 54 of 59

251. De Vargas, A.S.; Dal Molin, D.C.C.; Vilela, A.C.F.; da Silva, F.J.; Pav~a, B.; Veit, H. The effects of Na2 O/SiO2 molar ratio, curing
temperature and age on compressive strength, morphology and microstructure of alkali-activated fly ash-based geopolymers.
Cem. Concr. Compos. 2011, 33, 653–660. [CrossRef]
252. Helmy, A.I.I. Intermittent curing of fly ash geopolymer mortar. Constr. Build. Mater. 2016, 110, 54–64. [CrossRef]
253. Criado, M.; Palomo, A.; Jimenez, A.M.F. Alkali activation of fly ashes. Part 1: Effect of curing conditions on the carbonation of the
reaction products. Fuel 2005, 84, 2048–2054. [CrossRef]
254. Rattanasak, U.; Chindaprasirt, P. Influence of NaOH solution on the synthesis of fly ash geopolymer. Miner. Eng. 2009,
22, 1073–1078. [CrossRef]
255. Yang, T.; Yao, X.; Zhang, Z. Geopolymer prepared with high-magnesium nickel slag: Characterization of properties and
microstructure. Constr. Build. Mater. 2014, 59, 188–194. [CrossRef]
256. Jang, J.G.; Lee, N.K.; Lee, H.K. Fresh and hardened properties of alkali-activated fly ash/slag pastes with superplasticizers. Constr.
Build. Mater. 2014, 50, 169–176. [CrossRef]
257. Wang, W.-C.; Wang, H.-Y.; Lo, M.-H. The fresh and engineering properties of alkali activated slag as a function of fly ash
replacement and alkali concentration. Constr. Build. Mater. 2015, 84, 224–229. [CrossRef]
258. Deb, P.S.; Nath, P.; Sarker, P.K. The effects of ground granulated blast-furnace slag blending with fly ash and activator content
on the workability and strength properties of geopolymer concrete cured at ambient temperature. Mater. Des. 2014, 62, 32–39.
[CrossRef]
259. Xu, H.; Li, Q.; Shen, L.; Zhang, M.; Zhai, J. Low-reactive circulating fluidized bed combustion (CFBC) fly ashes as source material
for geopolymer synthesis. Waste Manag. 2010, 30, 57–62. [CrossRef] [PubMed]
260. Nazari, A.; Bagheri, A.; Riahi, S. Properties of geopolymer with seeded fly ash and rice husk bark ash. Mater. Sci. Eng. A 2011,
528, 7395–7401. [CrossRef]
261. Songpiriyakij, S.; Kubprasit, T.; Jaturapitakkul, C.; Chindaprasirt, P. Compressive strength and degree of reaction of biomass- and
fly ash-based geopolymer. Constr. Build. Mater. 2010, 24, 236–240. [CrossRef]
262. Zhang, M.; El-Korchi, T.; Zhang, G.P.; Liang, J.Y.; Tao, M.J. Synthesis factors affecting mechanical properties, microstructure, and
chemical composition of red mud-fly ash-based geopolymers. Fuel 2014, 134, 315–325. [CrossRef]
263. Schmucker, M.; Mackenzie, J.D.M. Microstructure of sodium polysialate siloxo geopolymer. Ceram. Int. 2005, 31, 433–440.
[CrossRef]
264. Leung, C.K.Y.; Pheerapha, T. Very high early strength of microwave cured concrete. Cem. Concr. Res. 1995, 25, 136–146. [CrossRef]
265. Somna, K.; Jaturapitakkul, C.; Kajitvichyanukul, P.; Chindaprasirt, P. NaOH-activated ground fly ash geopolymer cured at
ambient temperature. Fuel 2011, 90, 2118–2124. [CrossRef]
266. Nasvi, M.M.; Gamage, R.P.; Jay, S. Geopolymer as well cement and the variation of its mechanical behavior with curing
temperature. Greenh. Gases: Sci. Technol. 2011, 2, 46–58. [CrossRef]
267. Kim, B.-J.; Yi, C.; Kang, K.-I. Microwave curing of alkali-activated binder using hwangtoh without calcination. Constr. Build.
Mater. 2015, 98, 465–475. [CrossRef]
268. Chindaprasirt, P.; Rattanasak, U.; Taebuanhuad, S. Role of microwave radiation in curing the fly ash geopolymer. Adv. Powder
Technol. 2013, 24, 703–707. [CrossRef]
269. Lee, B.; Kim, G.; Kim, R.; Cho, B.; Lee, S.; Chon, C.-M. Strength development properties of geopolymer paste and mortar with
respect to amorphous Si/Al ratio of fly ash. Constr. Build. Mater. 2017, 151, 512–519. [CrossRef]
270. Zhuang, X.Y.; Chen, L.; Komarneni, S.; Zhou, C.H.; Tong, D.S.; Yang, H.M.; Yu, W.H.; Wang, H. Fly ash-based geopolymer: Clean
production, properties and applications. J. Clean. Prod. 2016, 125, 253–267. [CrossRef]
271. Zhang, H.Y.; Kodur, V.; Wu, B.; Cao, L.; Wang, F. Thermal behavior and mechanical properties of geopolymer mortar after
exposure to elevated temperatures. Constr. Build. Mater. 2016, 109, 17–24. [CrossRef]
272. Adak, D.; Sarkar, M.; Mandal, S. Effect of nano-silica on strength and durability of fly ash based geopolymer mortar. Constr. Build.
Mater. 2014, 70, 453–459. [CrossRef]
273. Al-Majidi, M.H.; Lampropoulos, A.; Cundy, A.; Meikle, S. Development of geopolymer mortar under ambient temperature for in
situ applications. Constr. Build. Mater. 2016, 120, 198–211. [CrossRef]
274. Collins, F.; Sanjayan, J. Early Age Strength and Workability of Slag Pastes Activated by NaOH and Na2 CO3 . Cem. Concr. Res.
1998, 28, 655–664. [CrossRef]
275. Rangan, B.V. Studies on fly-ash based geopolymer concrete. Malays. Constr. Res. J. 2008, 3, 1–20.
276. Nath, P.; Sarker, P.K. Flexural strength and elastic modulus of ambient-cured blended low-calcium fly ash geopolymer concrete.
Constr. Build. Mater. 2017, 130, 22–31. [CrossRef]
277. Chindaprasirt, P.; Chalee, W. Effect of sodium hydroxide concentration on chloride penetration and steel corrosion of fly ash-based
geopolymer concrete under marine site. Constr. Build. Mater. 2014, 63, 303–310. [CrossRef]
278. Ismail, I.; Bernal, S.A.; Provis, J.L.; Nicolas, R.S.; Brice, D.G.; Kilcullen, A.R.; Hamdan, S.; van Deventer, J.S. Influence of fly ash
on the water and chloride permeability of alkali-activated slag mortars and concretes. Constr. Build. Mater. 2013, 48, 1187–1201.
[CrossRef]
279. Yang, T.; Yao, X.; Zhang, Z.H. Quantification of chloride diffusion in fly asheslag-based geopolymers by X-ray fluorescence (XRF).
Constr. Build. Mater. 2014, 69, 109–115. [CrossRef]
J. Compos. Sci. 2022, 6, 219 55 of 59

280. Bakharev, T. Durability of geopolymer materials in sodium and magnesium sulphate solutions. Cem. Concr. Res. 2005,
35, 1233–1246. [CrossRef]
281. Sukmak, P.; De Silva, P.; Horpibulsuk, S.; Chindaprasirt, P. Sulfate Resistance of Clay-Portland Cement and Clay High-Calcium
Fly Ash Geopolymer. J. Mater. Civ. Eng. 2015, 27, 04014158. [CrossRef]
282. Ismail, I.; Bernal, S.A.; Provis, J.L.; Hamdan, S.; van Deventer, J.S. Microstructural changes in alkali activated fly ash/slag
geopolymers with sulfate exposure. Mater. Struct. 2013, 46, 361–373. [CrossRef]
283. Puligilla, S.; Mondal, P. Role of slag in microstructural development and hardening of fly ash-slag geopolymer. Cem. Concr. Res.
2013, 43, 70–80. [CrossRef]
284. Bakharev, T. Resistance of geopolymer materials to acid attack. Cem. Concr. Res. 2005, 35, 658–670. [CrossRef]
285. Lloyd, R.R.; Provis, J.L.; Van Deventer, J.S.J. Acid resistance of inorganic polymer binders. 1. Corrosion rate. Mater. Struct. 2012,
45, 1–14. [CrossRef]
286. Nguyen, K.; Lee, Y.H.; Lee, J.; Ahn, N. Acid Resistance and Curing Properties for Green Fly Ash-geopolymer Concrete. J. Asian
Arch. Build. Eng. 2013, 12, 317–322. [CrossRef]
287. Chindaprasirt, P.; Rattanasak, U.; Taebuanhuad, S. Resistance to acid and sulfate solutions of microwave-assisted high calcium fly
ash geopolymer. Mater. Struct. 2013, 46, 375–381. [CrossRef]
288. Rickard, W.D.; Williams, R.; Temuujin, J.; van Riessen, A. Assessing the suitability of three Australian fly ashes as an aluminosili-
cate source for geopolymers in high temperature applications. Mater. Sci. Eng. A 2011, 528, 3390–3397. [CrossRef]
289. Razak, S.N.A.; Shafiq, N.; Guillaumat, L.; Farhan, S.A.; Lohana, V.K. Fire-Exposed Fly-Ash-Based Geopolymer Concrete: Effects
of Burning Temperature on Mechanical and Microstructural Properties. Materials 2022, 15, 1884. [CrossRef] [PubMed]
290. Guerrieri, M.; Sanjayan, J.G. Behavior of combined fly ash/slag-based geopolymers when exposed to high temperatures. Fire
Mater. 2010, 34, 163–175. [CrossRef]
291. Rickard, W.D.A.; van Riessen, A.; Walls, P. Thermal character of geopolymers synthesized from Class F fly ash containing high
concentrations of iron and alpha quartz. Int. J. Appl. Ceram. Technol. 2010, 7, 81–88. [CrossRef]
292. Kong, D.L.Y.; Sanjayan, J.G.; Sagoe-Crentsil, K. Comparative performance of geopolymers made with metakaolin and fly ash
after exposure to elevated temperatures. Cem. Concr. Res. 2007, 37, 1583–1589. [CrossRef]
293. Bakharev, T. Thermal behaviour of geopolymers prepared using class F fly ash and elevated temperature curing. Cem. Concr. Res.
2006, 36, 1134–1147. [CrossRef]
294. Rickard, W.D.A.; van Riessen, A. Performance of solid and cellular structured fly ash geopolymers exposed to a simulated fire.
Cem. Concr. Compos. 2014, 48, 75–82. [CrossRef]
295. Dombrowski, K.; Buchwald, A.; Weil, M. The influence of calcium content on the structure and thermal performance of fly ash
based geopolymers. J. Mater. Sci. 2006, 42, 3033–3043. [CrossRef]
296. Sarker, P.K.; Kelly, S.; Yao, Z. Effect of fire exposure on cracking, spalling and residual strength of fly ash geopolymer concrete.
Mater. Des. 2014, 63, 584–592. [CrossRef]
297. Hobbs, D. Concrete deterioration: Causes, diagnosis, and minimising risk. Int. Mater. Rev. 2001, 46, 117–144. [CrossRef]
298. Temuujin, J.; Minjigmaa, A.; Davaabal, B.; Bayarzul, U.; Ankhtuya, A.; Jadambaa, T.; MacKenzie, K.J.D. Utilization of radioactive
high-calcium Mongolian fly ash for the preparation of alkali-activated geopolymers for safe use as construction materials. Ceram.
Int. 2014, 40, 16475–16483. [CrossRef]
299. Sun, P.J.; Wu, H.C. Chemical and freezeethaw resistance of fly ash-based inorganic mortars. Fuel 2013, 111, 740–745. [CrossRef]
300. Brooks, R.; Bahadory, M.; Tovia, F.; Rostami, H. Properties of alkali-activated fly ash: High performance to lightweight. Int. J.
Sustain. Eng. 2010, 3, 211–218. [CrossRef]
301. Pacheco-Torgal, F.; Jalali, S. Influence of sodium carbonate addition on the thermal reactivity of tungsten mine waste mud based
binders. Constr. Build. Mater. 2010, 24, 56–60. [CrossRef]
302. Duxson, P.; Provis, J.L.; Lukey, G.C.; van Deventer, J.S.J. 39K NMR of free potassium in geopolymers. Ind. Eng. Chem. Res. 2006,
45, 9208–9210.
303. Bortnovsky, O.; Dědeček, J.; Tvaruzkova, Z.; Sobalík, Z.; Šubrt, J. Metal Ions as Probes for Characterization of Geopolymer
Materials. J. Am. Ceram. Soc. 2008, 91, 3052–3057. [CrossRef]
304. Zhang, Z.; Provis, J.L.; Reid, A.; Wang, H. Fly ash-based geopolymers: The relationship between composition, pore structure and
efflorescence. Cem. Concr. Res. 2014, 64, 30–41. [CrossRef]
305. Lloyd, R.R.; Provis, J.L.; van Deventer, J.S. Pore solution composition and alkali diffusion in inorganic polymer cement. Cem.
Concr. Res. 2010, 40, 1386–1392. [CrossRef]
306. Schneider, M.; Romer, M.; Tschudin, M.; Bolio, H. Sustainable cement production—Present and future. Cem. Concr. Res. 2011,
41, 642–650. [CrossRef]
307. Habert, G.; de Lacaillerie, J.D.E.; Roussel, N. An environmental evaluation of geopolymer based concrete production: Reviewing
current research trends. J. Clean. Prod. 2011, 19, 1229–1238. [CrossRef]
308. Reddy, D.V.; Edouard, J.B.; Sobhan, K. Durability of fly ashebased geopolymer structural concrete in the marine environment. J.
Mater. Civ. Eng. 2013, 25, 781–787. [CrossRef]
309. Kupwade-Patil, K.; Allouche, E.N. Impact of Alkali Silica Reaction on Fly Ash-Based Geopolymer Concrete. J. Mater. Civ. Eng.
2013, 25, 131–139. [CrossRef]
J. Compos. Sci. 2022, 6, 219 56 of 59

310. Topark-Ngarm, P.; Chindaprasirt, P.; Sata, V. Setting Time, Strength, and Bond of High-Calcium Fly Ash Geopolymer Concrete. J.
Mater. Civ. Eng. 2015, 27, 04014198. [CrossRef]
311. Kong, D.L.; Sanjayan, J.G. Effect of elevated temperatures on geopolymer paste, mortar and concrete. Cem. Concr. Res. 2010,
40, 334–339. [CrossRef]
312. Sata, V.; Wongsa, A.; Chindaprasirt, P. Properties of pervious geopolymer concrete using recycled aggregates. Constr. Build. Mater.
2013, 42, 33–39. [CrossRef]
313. Nuaklong, P.; Sata, V.; Chindaprasirt, P. Influence of recycled aggregate on fly ash geopolymer concrete properties. J. Clean. Prod.
2016, 112, 2300–2307. [CrossRef]
314. Nematollahi, B.; Sanjayan, J. Effect of different superplasticizers and activator combinations on workability and strength of fly
ash based geopolymer. Mater. Des. 2014, 57, 667–672. [CrossRef]
315. Nasvi, M.; Ranjith, P.; Sanjayan, J. The permeability of geopolymer at down-hole stress conditions: Application for carbon dioxide
sequestration wells. Appl. Energy 2013, 102, 1391–1398. [CrossRef]
316. Nasvi, M.; Ranjith, P.; Sanjayan, J.; Bui, H.H. Effect of temperature on permeability of geopolymer: A primary well sealant for
carbon capture and storage wells. Fuel 2014, 117, 354–363. [CrossRef]
317. Hardjito, D.; Wallah, S.E.; Sumajouw, D.M.J.; Rangan, B.V. Fly Ash Based Geopolymer Concrete. Aust. J. Struct. Eng. 2005,
6, 77–86. [CrossRef]
318. Lloyd, N.A.; Rangan, B.V. Geopolymer Concrete with Fly Ash. In Proceedings of the Second International Conference on
Sustainable Construction Materials and Technologies, Ancone, Italy, 28–30 June 2010.
319. Panias, D.; Giannopoulou, I.P.; Perraki, T. Effect of synthesis parameters on the mechanical properties of fly ash-based geopolymers.
Colloids Surf. A Phys. Chem. Eng. Asp. 2007, 301, 246–254. [CrossRef]
320. Sofi, M.; Deventer, J.; Mendis, P.; Lukey, G.C. Engineering Properties of Inorganic Polymer Concretes (IPCs). Cem. Concr. Res.
2007, 37, 251–257. [CrossRef]
321. Rangan, B.V.; Wallah, S.E. Low Calcium y Ash Based Geopolymer Concrete: Long Term Properties; Research Report GC2; Faculty of
Engineering Curtin University of Technology: Perth, Australia, 2006.
322. Fernandez, J.; Palomo, A. Characterization of Fly Ash: Potential Reactivity Alkaline Cements. Fuel 2003, 82, 2259–2265. [CrossRef]
323. Neville, A.M. Properties of Concrete, 4th and Final ed.; Pearson Education, Longman Group: Essex, UK, 2000.
324. Hardjito, D.; Wallah, S.E.; Sumajouw, D.M.; Rangan, B.V. Introducing Fly Ash-Based Geopolymer Concrete: Manufacture and
Engineering Properties. In Proceedings of the Our World in Concrete and Structures International Conference, Singapore, 23–24
August 2005.
325. Cheema, D.S.; Lloyd, N.A.; Rangan, B.V. Durability of Geopolymer Concrete Box Culverts—A Green Alternative. In Proceedings
of the 34th Conference on OurWorld in Concrete and Structures, Singapore, 16–18 August 2009.
326. Adam, A.A.; Molyneaux, T.C.K.; Patnaikuni, I.; Law, D.W. Strength, sorptivity and carbonation of geopolymer concrete. In
Challenges, Opportunities and Solutions in Structural Engineering and Construction; CRC Press: Boca Raton, FL, USA, 2009.
327. Thokchom, S.; Ghosh, P.; Ghosh, S. Performance of Fly ash Based Geopolymer Mortars in Sulphate Solution. J. Eng. Sci. Technol.
Rev. 2010, 3, 36–40. [CrossRef]
328. Anurag, M. Deepika, Namrata, Manish, Nidhi and Durga, Effect of concentration of alkaline liquid and Curing time on strength
and water absorption Of geopolymer concrete. ARPN J. Eng. Appl. Sci. 2008, 3, 14–18.
329. Song, S.; Jennings, H.M. Pore solution chemistry of alkali-activated ground granulated blast-furnace slag. Cem. Concr. Res. 1999,
29, 159–170. [CrossRef]
330. Sathia, R.; Babu, K.G.; Santhanam, M. Durability study of low calcium fly ash geopolymer concrete. In Proceedings of the 3rd
ACF International Coference ACF, Ho Chi Minh City, Vietenam, 11–13 November 2008.
331. Bakharev, T. Heat resistance of geopolymer materials prepared using class F fly ash. J. Aust. Ceram. Soc. 2006, 42, 34–44.
332. Wallah, S.E.; Hardjito, D.; Sumajouw, D.M.; Rangan, B.V. Sulfate and acid resistance of fly ash-based geopolymer concrete.
In Proceedings of the Australian Structural Engineering Conference 2005, Newcastle, NSW, Australia, 11–14 September 2005;
pp. 733–742.
333. Bakharev, T.; Sanjayan, J.G.; Cheng, J.B. Resistance of alkali-activated slag concrete to acid attack. Cem. Concr. Res. 2003,
33, 1607–1611. [CrossRef]
334. Song, X.J.; Marosszeky, M.M.; Munn, R. Durability of y ash-based Geopolymer concrete against sulphuric acid attack. In
Proceedings of the International Conference on Durability of Building Materials and Components, Lyon, France, 17–20 April 2005.
335. Olivia, M.; Nikraz, H. Corrosion Performance of Embedded Steel in Fly Ash Geopolymer Concrete by Impressed Voltage Method.
In Proceedings of the 21st Australian Conference on the Mechanics of Structures and Materials, Melbourne, VIC, Australia, 7–10
December 2010; pp. 781–786.
336. Roy, D.M. Alkali-activated cements Opportunities and challenges. Cem. Concr. Res. 1999, 29, 249–254. [CrossRef]
337. Wallah, S.E.; Rangan, B.V. Low-Calcium fly Ash-Based Geopolymer Concrete: Long Term Properties; Reserch Report GC3; Faculty of
Engineering, Curtain University: Perth, Australia, 2006.
338. Rashad, A.M.; Zeedan, S.R. The effect of activator concentration on the residual compressive strength of alkali- activated fly ash
paste subjected to thermal load. Constr. Build. Mater. 2011, 25, 3098–3107. [CrossRef]
339. Kong, D.L.Y.; Sanjayan, J.G. Damage behavior of geopolymercomposites exposed to elevated temperatures. Cem. Concr. Compos.
2008, 30, 986–991. [CrossRef]
J. Compos. Sci. 2022, 6, 219 57 of 59

340. Luhar, S.; Chaudhary, S.; Luhar, I. Thermal resistance of fly ash based rubberized geopolymer concrete. J. Build. Eng. 2018,
19, 420–428. [CrossRef]
341. Pan, Z.; Sanjayan, J.G.; Rangan, B.V. An investigation of the mechanisms for strength gain or loss geopolymer mortar after
exposure to elevated temperature. J. Mater. Sci. 2009, 44, 1873–1880. [CrossRef]
342. Ranjbar, N.; Mehrali, M.; Alengaram, U.J.; Metselaar, H.S.C.; Jummat, M.Z. Compressive strength and microstructural analysis
of fly ash/palm oil fuel ash based geopolymer mortar under elevated temperatures. Constr. Build. Mater. 2014, 65, 114–121.
[CrossRef]
343. Kong, D.L.Y.; Sanjayan, J.G.; Crentsil, K.S. Factors affecting the performance of metakaolingeopolymers to elevated temperatures.
J. Mater. Sci. 2008, 43, 824–831. [CrossRef]
344. Pan, Z.; Sanjayan, J.G.; Collins, F. Effect of transient creep on compressive strength of geopolymer concrete for elevated
temperature exposure. Cem. Concr. Res. 2014, 56, 182–189. [CrossRef]
345. Hussain, M.W.; Bhutta, M.A.R.; Azreen, M.; Ramadhansyah, P.J.; Mirza, J. Performance of blended ash geopolymer concrete at
elevated temperature. Mater. Struct. 2015, 48, 709–720. [CrossRef]
346. Fan, F. Mechanical and Thermal Properties of Fly Ash-Based Geopolymer Cement. Master’s Thesis, Louisiana State University,
Baton Rouge, LA, USA, 2014.
347. Omar, A.A.; Bakri, A.M.; Kamarudin, H.; Nizar, I.K.; Saif, A.A. Effect of elevated temperatures on the thermal behaviour and
mechanical performance of fly ash geopolymer paste, mortar and lightweight concrete. Constr. Build. Mater. 2014, 50, 377–387.
348. Zhang, Y.; Sun, W.; Li, Z. Infrared spectroscopy study of structural nature of geopolymeric products. J. Wuhan Univ. Technol. Sci.
Ed. 2008, 23, 522–527. [CrossRef]
349. Chindaprasirt, P.; Chareerat, T.; Sirivivatnanon, V. Workability and strength of coarse high calcium fly ash geopolymer. Cem.
Concr. Compos. 2007, 29, 224–229. [CrossRef]
350. Jumrat, S.; Chatveera, B.; Rattanadecho, P. Dielectric properties and temperature profile of fly ash-based geopolymer mortar. Int.
Commun. Heat Mass Transf. 2011, 38, 242–248. [CrossRef]
351. Sukmak, P.; Horpibulsuk, S.; Shen, S.L. Strength development in clay–fly ash geopolymer. Constr. Build. Mater. 2013, 40, 566–574.
[CrossRef]
352. Rifaai, Y.; Yahia, A.; Mostafa, A.; Aggoun, S.; Kadri, E.H. Rheology of fly ash-based geopolymer: Effect of NaOH concentration.
Constr. Build. Mater. 2019, 223, 583–594. [CrossRef]
353. Patankar, S.V.; Ghugal, Y.M.; Jamkar, S.S. Effect of Concentration of Sodium Hydroxide and Degree of Heat Curing on Fly
Ash-Based Geopolymer Mortar. Indian J. Mater. Sci. 2014, 2014, 938789. [CrossRef]
354. Bhowmick, A.; Ghosh, S. Effect of synthesizing parameters on workability and compressive strength of fly ash based geopolymer
mortar. Int. J. Civ. Struct. Eng. 2012, 3, 168–177.
355. Malkawi, A.B.; Nuruddin, M.F.; Fauzi, A.; Almattarneh, H.; Mohammed, B.S. Effects of Alkaline Solution on Properties of the
HCFA Geopolymer Mortars. Procedia Eng. 2016, 148, 710–717. [CrossRef]
356. Lee, N.; Kim, E.; Lee, H. Mechanical properties and setting characteristics of geopolymer mortar using styrene-butadiene (SB)
latex. Constr. Build. Mater. 2016, 113, 264–272. [CrossRef]
357. Sathonsaowaphak, A.; Chindaprasirt, P.; Pimraksa, K. Workability and strength of lignite bottom ash geopolymer mortar. J.
Hazard. Mater. 2009, 168, 44–50. [CrossRef] [PubMed]
358. Li, Q.; Chen, C.; Shen, L.; Zhai, J. Manufacturing F-fly ash based geopolymer mortars using CFBC bottom ash as fine aggregates.
J. Chem. Soc. Pak. 2013, 35, 314–319.
359. Huseien, G.F.; Mirza, J.; Ismail, M.; Hussin, M.W. Influence of different curing temperatures and alkali activators on properties of
GBFS geopolymer mortars containing fly ash and palm-oil fuel ash. Constr. Build. Mater. 2016, 125, 1229–1240. [CrossRef]
360. Islam, A.; Alengaram, U.J.; Jumaat, M.Z.; Bashar, I.I. The development of compressive strength of ground granulated blast furnace
slag-palm oil fuel ash-fly ash based geopolymer mortar. Mater. Des. 2014, 56, 833–841. [CrossRef]
361. Phoo-ngernkham, T.; Hanjitsuwan, S.; Li, L.Y.; Damrongwiriyanupap, N.; Chindaprasirt, P. Adhesion characterisation of Portland
cement concrete and alkali-activated binders. Adv. Cem. Res. 2019, 31, 69–79. [CrossRef]
362. Temuujin, J.; van Riessen, A.; MacKenzie, K.J.D. Preparation and characterization of fly ash based geopolymer mortars. Constr.
Build Mater 2010, 24, 1906–1910. [CrossRef]
363. Zejak, R.; Nikolic, I.; Blecic, D.; Radmilovic, V.; Radmilovic, V. Mechanical and microstructural properties of the fly-ash-based
geopolymer paste and mortar. Mater. Technol. 2013, 47, 535–540.
364. Zhang, P.; Kang, L.; Zheng, Y.; Zhang, T.; Zhang, B. Influence of SiO2 /Na2 O molar ratio on mechanical properties and durability
of metakaolin-fly ash blend alkali-activated sustainable mortar incorporating manufactured sand. J. Mater. Res. Technol. 2022,
18, 3553–3563. [CrossRef]
365. Kotwal, A.R.; Kim, Y.J.; Hu, J.; Sriraman, V. Characterization and Early Age Physical Properties of Ambient Cured Geopolymer
Mortar Based on Class C Fly Ash. Int. J. Concr. Struct. Mater. 2014, 9, 35–43. [CrossRef]
366. Görhan, G.; Kürklü, G. The influence of the NaOH solution on the properties of the fly ash-based geopolymer mortar cured at
different temperatures. Compos. Part B Eng. 2014, 58, 371–377. [CrossRef]
367. Bashar, I.I.; Alengaram, U.J.; Jumaat, M.Z.; Islam, A. The effect of variation of molarity of alkali activator and fine aggregate
content on the compressive strength of the fly ash: Palm oil fuel ash based geopolymer mortar. Adv. Mater. Sci. Eng. 2014,
2014, 245473. [CrossRef]
J. Compos. Sci. 2022, 6, 219 58 of 59

368. Okba, S.H.; Nasr, E.S.A.; Helmy, A.I.; Yousef, I.A.L. Effect of thermal exposure on the mechanical properties of polymer adhesives.
Constr. Build. Mater. 2017, 135, 490–504. [CrossRef]
369. Li, X.; Ma, X.; Zhang, S.; Zheng, E. Mechanical Properties and Microstructure of Class C Fly Ash-Based Geopolymer Paste and
Mortar. Materials 2013, 6, 1485–1495. [CrossRef] [PubMed]
370. Adam, A.A.; Horianto, X. The Effect of Temperature and Duration of Curing on the Strength of Fly Ash Based Geopolymer
Mortar. Procedia Eng. 2014, 95, 410–414. [CrossRef]
371. Narayanan, A.; Shanmugasundaram, P. An Experimental Investigation on Flyash-based Geopolymer Mortar under different
curing regime for Thermal Analysis. Energy Build. 2017, 138, 539–545. [CrossRef]
372. Mallikarjuna Rao, G.; Gunneswara Rao, T.D. Final setting time and compressive strength of fly ash and GGBS-based geopolymer
paste and mortar. Arab. J. Sci. Eng. 2015, 40, 3067–3074. [CrossRef]
373. Algaifi, H.A.; Mustafa Mohamed, A.; Alsuhaibani, E.; Shahidan, S.; Alrshoudi, F.; Huseien, G.F.; Bakar, S.A. Optimisation of
GBFS, Fly Ash, and Nano-Silica Contents in Alkali-Activated Mortars. Polymers 2021, 13, 2750. [CrossRef] [PubMed]
374. Chuah, S.; Duan, W.; Pan, Z.; Hunter, E.; Korayem, A.; Zhao, X.; Collins, F.; Sanjayan, J. The properties of fly ash based geopolymer
mortars made with dune sand. Mater. Des. 2016, 92, 571–578. [CrossRef]
375. Guades, E.J. Experimental investigation of the compressive and tensile strengths of geopolymer mortar: The effect of sand/fly
ash (S/FA) ratio. Constr. Build. Mater. 2016, 127, 484–493. [CrossRef]
376. Cyr, M.; Idir, R.; Poinot, T. Prpoerties of inorganic polymer (geopolymer) mortars made of glass cullet. J. Mater. Sci. 2012,
47, 2782–2797. [CrossRef]
377. Atis, C.D.; Gorur, E.B.; Karahan, O.; Bilim, C.; Ilkentapar, S.; Luga, E. Very high strength (120 MPa) class F fly ash geopolymer
mortar activated at different NaOH amount, heat curing temperature and heat curing duration. Constr. Build Mater. 2015,
96, 673–678. [CrossRef]
378. Satya, Y.S.D.; Saputra, E.; Olivia, M. Performance of Blended Fly Ash (FA) and Palm Oil Fuel Ash (POFA) Geopolymer Mortar in
Acidic Peat Environment. Mater. Sci. Forum 2016, 841, 83–89. [CrossRef]
379. Olivia, M.; Wulandari, C.; Sitompul, I.R.; Darmayanti, L.; Djauhari, Z. Study of Fly Ash (FA) and Palm Oil Fuel Ash (POFA)
Geopolymer Mortar Resistance in Acidic Peat Environment. Mater. Sci. Forum 2016, 841, 126–132. [CrossRef]
380. Sreevidya, V.; Anuradha, R.; Thomas, T.; Venkatasubramani, R. Duribility studies on fly ash geopolymer mortar under in ambient
curing condition. Asian J. Chem. 2013, 25, 2497–2499. [CrossRef]
381. Abdollahnejad, Z.; Pacheco-Torgal, F.; Aguiar, J.; Jesus, C. Durability Performance of Fly Ash Based One-Part Geopolymer
Mortars. Key Eng. Mater. 2015, 634, 113–120. [CrossRef]
382. Thokchom, S.; Ghosh, P.; Ghosh, S. Acid resistance of fly ash based geopolymer mortars. Int. J. Recent Trends Eng. Technol. 2009,
1, 36–40.
383. Kürklü, G. The effect of high temperature on the design of blast furnace slag and coarse fly ash-based geopolymer mortar. Compos.
Part B Eng. 2016, 92, 9–18. [CrossRef]
384. Djobo, J.N.Y.; Elimbi, A.; Tchakouté, H.K.; Kumar, S. Mechanical properties and durability of volcanic ash based geopolymer
mortars. Constr. Build. Mater. 2016, 124, 606–614. [CrossRef]
385. Abdulkareem, O.A.; Al Bakri, A.M.; Kamarudin, H.; Nizar, I.K.; Saif, A.A. Strength and porosity characterizations of blended
biomass wood ash-fly ash-based geopolymer mortar. AIP Conf. Proc. 2018, 2045, 020096.
386. Kumar, E.M.; Ramamurthy, K. Influence of production on the strength, density and water absorption of aerated geopolymer
paste and mortar using Class F fly ash. Constr. Build. Mater. 2017, 156, 1137–1149. [CrossRef]
387. Ling, Y.; Wang, K.; Fu, C. Shrinkage behavior of fly ash based geopolymer pastes with and without shrinkage reducing admixture.
Cem. Concr. Compos. 2019, 98, 74–82. [CrossRef]
388. Zuda, L.; Pavlík, Z.; Rovnanikova, P.; Bayer, P.; Černý, R. Properties of Alkali Activated Aluminosilicate Material after Thermal
Load. Int. J. Thermophys. 2006, 27, 1250–1263. [CrossRef]
389. Saha, S.; Rajasekaran, C. Enhancement of the properties of fly ash based geopolymer paste by incorporating ground granulated
blast furnace slag. Constr. Build. Mater. 2017, 146, 615–620. [CrossRef]
390. Chindaprasirt, P.; De Silva, P.; Sagoe-Crentsil, K.; Hanjitsuwan, S. Effect of SiO2 and Al2 O3 on the setting and hardening of high
calcium fly ash-based geopolymer systems. J. Mater. Sci. 2012, 47, 4876–4883. [CrossRef]
391. Alonso, S.; Palomo, A. Calorimetric study of alkaline activation of calcium hydroxide–metakaolin solid mixtures. Cem. Concr. Res.
2001, 31, 25–30. [CrossRef]
392. Puertas, F.; Amat, T.; Vázquez, T. Behaviour of alkaline cement mortars reinforced with acrylic and polypropylene fibres. Mater.
Constru. 2000, 50, 69–84. [CrossRef]
393. Fernández-Jiménez, A.; Palomo, A. Composition and microstructure of alkali activated fly ash binder: Effect of the activator. Cem.
Concr. Res. 2005, 35, 1984–1992. [CrossRef]
394. Liu, G.; Florea, M.V.A.; Brouwers, H.J.H. Waste glass as binder in alkali activated slag–fly ash mortars. Mater. Struct. 2019, 52, 101.
[CrossRef]
395. Chindaprasirt, P.; Rattanasak, U.; Vongvoradit, P.; Jenjirapanya, S. Thermal treatment and utilization of Al-rich waste in high
calcium fly ash geopolymeric materials. Int. J. Miner. Met. Mater. 2012, 19, 872–878. [CrossRef]
396. Fletcher, R.A.; MacKenzie, K.J.; Nicholson, C.L.; Shimada, S. The composition range of aluminosilicate geopolymers. J. Eur. Ceram.
Soc. 2005, 25, 1471–1477. [CrossRef]
J. Compos. Sci. 2022, 6, 219 59 of 59

397. De Silva, P.; Sagoe-Crenstil, K.; Sirivivatnanon, V. Kinetics of geopolymerization: Role of Al2 O3 and SiO2 . Cem. Concr. Res. 2007,
37, 512–518. [CrossRef]
398. Temuujin, J.; Van Riessen, A.; Williams, R. Influence of calcium compounds on the mechanical properties of fly ash geopolymer
pastes. J. Hazard. Mater. 2009, 167, 82–88. [CrossRef]
399. Guo, X.; Shi, H.; Dick, W.A. Compressive strength and microstructural characteristics of class C fly ash geopolymer. Cem. Concr.
Compos. 2010, 32, 142–147. [CrossRef]
400. Mehta, P.K.; Monteiro, P.J. Concrete Microstructure, Properties and Materials; McGraw-Hill Education: New York, NY, USA, 2017.
401. Van Deventer, J.S.; San Nicolas, R.; Ismail, I.; Bernal, S.A.; Brice, D.G.; Provis, J.L. Microstructure and durability of alkali-activated
materials as key parameters for standardization. J. Sustain. Cem. Mater. 2015, 4, 116–128. [CrossRef]
402. Weir, A.J.; Abrams, G.; Adolphsen, C.E.; Alexander, J.P.; Alvarez, M.; Amidei, D.; Baden, A.R.; Barish, B.C.; Barklow, T.; Barnett,
B.A.; et al. A reanalysis of B0-B̄0 mixing in e+ e− annihilation at 29 GeV. Phys. Lett. B 1990, 240, 289–296. [CrossRef]
403. Brouwers, H.J.H.; Van Eijk, R.J. Fly ash reactivity: Extension and application of a shrinking core model and thermodynamic
approach. J. Mater. Sci. 2002, 37, 2129–2141. [CrossRef]
404. Phoo-ngernkham, T.; Chindaprasirt, P.; Sata, V.; Hanjitsuwan, S.; Hatanaka, S. The effect of adding nano-SiO2 and nano-Al2 O3 on
properties of high calcium fly ash geopolymer cured at ambient temperature. Mater. Des. 2014, 55, 58–65. [CrossRef]
405. Wongsa, A.; Boonserm, K.; Waisurasingha, C.; Sata, V.; Chindaprasirt, P. Use of municipal solid waste incinerator (MSWI) bottom
ash in high calcium fly ash geopolymer matrix. J. Clean. Prod. 2017, 148, 49–59. [CrossRef]
406. Adak, D.; Sarkar, M.; Mandal, S. Structural performance of nano-silica modified fly-ash based geopolymer concrete. Constr. Build.
Mater. 2017, 135, 430–439. [CrossRef]
407. Salih, M.A.; Ali, A.A.A.; Farzadnia, N. Characterization of mechanical and microstructural properties of palm oil fuel ash
geopolymer cement paste. Constr. Build. Mater. 2014, 65, 592–603. [CrossRef]
408. Swanepoel, J.; Strydom, C. Utilisation of fly ash in a geopolymeric material. Appl. Geochem. 2002, 17, 1143–1148. [CrossRef]
409. Ghani, U.; Hussain, S.; Imtiaz, M.; Khan, S.A. Role of calcination on geopolymerization of lateritic clay by alkali treatment. J.
Saudi Chem. Soc. 2021, 25, 101198. [CrossRef]
410. Gao, K.; Lin, K.L.; Wang, D.; Hwang, C.L.; Shiu, H.S.; Chang, Y.M.; Cheng, T.W. Effects SiO2 /Na2 O molar ratio on mechanical
properties and the microstructure of nano-SiO2 metakaolin-based geopolymers, Constr. Build. Mater. 2014, 53, 503–510. [CrossRef]
411. Zawrah, M.; Gado, R.; Feltin, N.; Ducourtieux, S.; Devoille, L. Recycling and utilization assessment of waste fired clay bricks
(Grog) with granulated blast-furnace slag for geopolymer production. Process Saf. Environ. Prot. 2016, 103, 237–251. [CrossRef]
412. Duan, P.; Yan, C.; Zhou, W.; Luo, W. Fresh properties, mechanical strength and microstructure of fly ash geopolymer paste
reinforced with sawdust. Constr. Build. Mater. 2016, 111, 600–610. [CrossRef]
413. Okoye, F.; Durgaprasad, J.; Singh, N. Mechanical properties of alkali activated flyash/Kaolin based geopolymer concrete. Constr.
Build. Mater. 2015, 98, 685–691. [CrossRef]
414. Cai, J.; Jiang, J.; Gao, X.; Ding, M. Improving the Mechanical Properties of Fly Ash-Based Geopolymer Composites with PVA
Fiber and Powder. Materials 2022, 15, 2363. [CrossRef]
415. Kaze, C.R.; Adesina, A.; Lecomte-Nana, G.L.; Assaedi, H.; Alomayri, T.; Kamseu, E.; Melo, U.C. Physico-mechanical and
microstructural properties of geopolymer binders synthesized with metakaolin and meta-halloysite as precursors. Clean. Mater.
2022, 4, 100070. [CrossRef]
416. Ramli, M.I.I.; Salleh, M.A.A.M.; Abdullah, M.M.A.B.; Aziz, I.H.; Ying, T.C.; Shahedan, N.F.; Kockelmann, W.; Fedrigo, A.; Sandu,
A.V.; Vizureanu, P.; et al. The Influence of Sintering Temperature on the Pore Structure of an Alkali-Activated Kaolin-Based
Geopolymer Ceramic. Materials 2022, 15, 2667. [CrossRef] [PubMed]
417. Kalombe, R.M.; Ojumu, V.T.; Eze, C.P.; Nyale, S.M.; Kevern, J.; Petrik, L.F. Fly Ash-Based Geopolymer Building Materials for
Green and Sustainable Development. Materials 2020, 13, 5699. [CrossRef]
418. Luhar, S.; Chaudhary, S.; Dave, U.V. Effect of different type of curing on fly ash and Slag based geopolymer concrete. Int. J. Civ.
Struct. Environ. Infrastr. Eng. Res. Dev 2016, 69–78. Available online: https://www.researchgate.net/publication/309766349_
Effect_of_Different_type_of_curing_on_fly_ash_and_slag_based_geopolymer_concrete (accessed on 20 April 2022).
419. Sanni, S.H.; Khadiranaikar, R.B. Performance of geopolymer concrete under severe environmental conditions. Int. J. Civ. Struct.
Eng. 2012, 3, 396.
420. Luhar, S. Fly Ash and Slag Based Geopolymer Concrete: Experimental Facts; LAP Lambert Academic Publishing: Sunnyvale, CA,
USA, 2016.
421. Cheng, T.W.; Chiu, J.P. Fire-resistant geopolymer produced by granulated blast furnace slag. Miner. Eng. 2003, 16, 205–210.
[CrossRef]
422. World Bank. Solid Waste Manage; The World Bank Group: Washington, DC, USA, 2013.
423. European Union. The EU in the World- Environment, 2020th ed.; European Union, Ed.; Eurostat: Luxembourg City, Luxem-
bourg, 2020.
424. Krautwurst, N.; Nicoleau, L.; Dietzsch, M.; Lieberwirth, I.; Labbez, C.; Fernandez- Martinez, A.; Van Driessche, A.E.S.; Barton,
B.; Leukel, S.; Tremel, W. Twostep nucleation process of calcium silicate hydrate, the nanobrick of cement. Chem. Mater. 2018,
30, 2895–2904. [CrossRef]
425. Korniejenko, K.; Kozub, B.; Bak, ˛ A.; Balamurugan, P.; Uthayakumar, M.; Furtos, G. Tackling the Circular Economy Challenges—
Composites Recycling: Used Tyres, Wind Turbine Blades, and Solar Panels. J. Compos. Sci. 2021, 5, 243. [CrossRef]