J Mater Sci

Review
REVIEW

Enhancing the reactivity of aluminosilicate materials

toward geopolymer synthesis
L. N. Tchadjie1,* and S. O. Ekolu1

1
Department of Civil Engineering Science, University of Johannesburg, PO Box 524, Auckland Park 2006, South Africa

Received: 17 November 2017 ABSTRACT

Accepted: 8 December 2017
 Springer Science+Business
Media, LLC, part of Springer
Nature 2017
Geopolymers are alternative materials to portland cement, obtained by alkaline
activation of aluminosilicates. They exhibit excellent properties and a wide
range of potential applications in the field of civil engineering. Several natural
aluminosilicates and industrial by-products can be used for geopolymer syn-
thesis, but a lot of starting materials have the disadvantage of poor reactivity
and low strength development. This paper presents a comprehensive review of
the main methods used to alter the reactivity of aluminosilicate materials for
geopolymer synthesis, as reported recently in the literature. The methods consist
of mechanical, thermal, physical separation and chemical activation, of which
mechanical activation is the most commonly employed technique. The reactivity
of the activated aluminosilicate materials is mainly related to the activation
method and the treatment parameters. Chemical activation by alkaline fusion is
a promising method allowing preparation of one-part geopolymer materials, an
alternative class of geopolymeric binders. However, the resulting alkaline-fused
geopolymer products are vulnerable to attack by excessive alkalis.

Introduction resistance and low permeability [2, 3]. Geopolymers

Geopolymers are alternative cementitious materials
first proposed in 1972 by Davidovits and have
attracted major research interest worldwide over the
past decade [1]. These materials have a high potential
of minimizing CO2 generation relative to portland
cement. In fact, optimal design of geopolymer cement
requires less energy and could produce 80% less CO2
than portland cement [2]. Moreover, geopolymers
show some attractive properties for specific applica-
tions such as fast hardening, high early strength,
stability under chemical attack, high-temperature
are inorganic polymeric materials which can be syn-
thesized from various aluminosilicate sources in
alkaline or acidic medium condition [1, 4]. Indeed, a
great number of minerals and industrial by-products
have been investigated as raw materials for
geopolymer synthesis, including kaolin, metakaolin,
fly ash, metahalloysite, volcanic scoria, granite and
slag [5–10]. However, some geopolymeric systems
have shown weak performance characteristics such
as long setting time, low mechanical and durability
properties [11–13]. Such poor results arise from weak
reactivity of the starting materials and/or

Address correspondence to E-mail: noumbissi3000@yahoo.fr; leonelt@uj.ac.za

https://doi.org/10.1007/s10853-017-1907-7

inappropriate design of the geopolymer recipe. It is
worth noting that geopolymer synthesis via the con-
ventional route involves two constituents comprising
the solid part (aluminosilicate) and liquid part (al-
kaline solution). It is well known that the properties
of geopolymers are affected by many factors such as
the nature of starting materials which includes min-
eralogical and chemical composition, particle size,
glass content and composition; alkaline solution
composition, liquid-to-solid ratio, mixing procedure
and curing conditions [5, 11, 12, 14–16]. Therefore,
geopolymer properties can be manipulated by
adjusting these parameters.
Given the physical and chemical properties of
geopolymers, some geopolymeric systems have been
successfully used in several applications including
those of industrial scale. In civil engineering, the
development of PYRAMENT cement, an ultra-fast
and high-performance binder is notable. Marketed in
the USA since 1988, it is used for repair and con-
struction of air strips [17]. Recently, 40,000 m3 of
geopolymer concretes was used for construction of
the Brisbane West Wellcamp Airport in Australia,
making it the largest single application of this new
type of concrete worldwide. Heavy duty geopolymer
concrete was used for the turning node, apron and
taxiway pavements in the same project [18]. The
Global Change Institute at the University of
Queensland in Australia has been built using precast
geopolymer panels, representing the first use of sus-
pended geopolymer concrete worldwide [19]. Her-
mann et al. [20] developed a new method for
solidification of sludges containing radio nuclides,
heavy metals and organics, using geopolymeric
matrix. Bai et al. [21] reported that under specific
conditions, highly porous materials with a homoge-
nous structure can be made with geopolymer mate-
rials. Their results showed that the foamed
geopolymers can be used as adsorbents for removal
of copper and ammonium ions from wastewater. The
foams could also be used for thermal insulation due
to their low thermal conductivity. They also designed
geopolymer mixtures that could be printed using
additive manufacturing technology. Geopolymers
can also be used in the field of biomaterials, for bone
restoration. Best results in terms of biological com-
patibility were obtained with a geopolymer matrix
resulting from a mole ratio of K2O/SiO2 = 0.54, heat-
treated at 500 C. In the same biomedical field, Jäm-
storp et al. [22] showed that a sustained drug release
J Mater Sci
delivery system can be made using metakaolin-based
geopolymers. Based on their results, the opioid fen-
tanyl and its structurally similar sedative zolpidem
were embedded into metakaolin-based geopolymer
pellets to provide prolonged release dosage forms,
with mechanical strengths of the same order of
magnitude as that of human teeth. As reported in
several studies on thermal properties of geopolymers,
these materials are highly fire and heat resistant
[23–25]. For instance, fire-resistant geopolymer/car-
bon composites have been developed and used for
racing car manufacture [17]. These advances in
research have provided confidence that geopolymers
may offer similar or better performance to conven-
tional ordinary portland cement [25].
In the literature, several attempts have been made
to improve the geopolymeric reactivity of starting
materials. The purpose of this review was to assess
the different techniques used for increasing reactivity
of aluminosilicate raw materials and in turn improve
engineering properties of resulting geopolymers. An
overview of the main parameters and effects of dif-
ferent activation methods is presented. This study
also sought to identify and highlight new or emerg-
ing developments on the subject so as to promote
future research. The subject is discussed on the basis
of geopolymer chemistry, reactivity of aluminosili-
cate raw materials and mechanical properties of the
resulting geopolymer cement products.
Geopolymer chemistry and product
properties
Synthesis
The traditional process of synthesizing geopolymers
involves mixing a reactive aluminosilicate precursor
powder with highly soluble alkaline usually Na/K
hydroxide solution or soluble Na/K silicate. The
hardening occurs at room temperature or at moder-
ate temperatures below 100 C, depending on reac-
tivity of starting materials [17]. The reaction is a
polymerization process, yielding nanometric macro-
molecules with a three-dimensional matrix made of
tetrahedral AlO4 and SiO4 units linked randomly by
sharing all the oxygen atoms. Alkali metal cations
including Na?, K?, Li?, Cs?, Ca2? provide stabiliza-
tion of the negative charge of the AlO4 tetrahedron,
where the trivalent ion Al3? is four-coordinated. The
J Mater Sci

term poly (sialate) proposed by Davidovits is used to
describe building units of geopolymer structures
with ‘‘sialate’’’ standing for alkali silicon-oxo-alumi-
nate. The inorganic polymer structure is X-ray
amorphous at room temperature when hardened and
crystallized at high temperatures above 500 C.
Poly(sialate) has the empirical formula Mn(–(SiO2)z–
AlO2)n,wH2O, where M is a cation such as K?, Na?,
Li? or Ca2?; z is 1,2,3 or higher and n is a polymer-
ization degree. Thus, four basic units are derived
from this formula according to the Si/Al atomic ratio
in the molecular structure Si/Al = 1 (sialate), Si/
Al = 2 (sialate-siloxo), Si/Al = 3 (sialate-disiloxo)
and Si/Al [ 3 (sialate link) [17]. Recent studies on
geopolymerization of iron-rich aluminosilicate mate-
rials demonstrated that the iron atom (Fe) can be
incorporated into the geopolymer network, resulting
in ferro–poly(sialate) molecular units [26, 27].
Aluminosilicate raw materials
Generally, materials containing mostly silica (SiO2)
and alumina (Al2O3) are possible sources for
geopolymer synthesis. From this point of view, a
wide range of geological rocks and mineral by-
products can be used, since silicon and aluminium
oxides constitute around 75 wt% of earth’s crust [28].
So far, a great number of raw materials have been
investigated for geopolymer synthesis around the
world. It is worth noting that the choice of materials
for investigations is mainly based on local availabil-
ity. Also, reactivity of starting materials through
geopolymerization in alkaline medium is an impor-
tant parameter and will be discussed further in the
present paper. All aluminosilicate materials may be
classified into two groups comprising natural poz-
zolanic materials and industrial waste by-products.
Table 1 presents the relative abundance of common
oxides in the earth’s crust, their potential source
materials and their effects on the geopolymer
network.
Kaolinite is the major clay mineral often investi-
gated for geopolymer synthesis. It shows low reac-
tivity through geopolymerization in its natural state
and consequently presents low strength development
[12, 32]. Most of the time, kaolinite is transformed
into metakaolin by calcination between 700 and
900 C before being used for geopolymer synthesis
[7, 33–35]. The calcination induces the dehydroxyla-
tion of kaolinite and formation of aluminosilicate
amorphous phase that is highly reactive in alkaline
medium [7, 34, 35]. It is worth noting that besides
kaolinite, other clay minerals such as illite, smectite,
halloysite and calcined laterite may be suitable for
use as raw material for preparation of geopolymer
binders [8, 36, 37].
Volcanic rocks are some of the oldest construction
materials used since the Romans age, due to their
pozzolanic properties. In fact, volcanic materials have
been successfully used in modern construction tech-
nology as supplementary cementitious materials
(SCMs) characterized to ASTM C 618, and as light-
weight aggregate as per to ASTM C 330 [38, 39]. The
most abundant chemical component in most volcano-
related materials is SiO2, which can vary from 35% to
nearly 80 wt%, followed by Al2O3 usually in the
range of 15–20 wt%. Volcanic rocks also may contain
other components such as CaO, Na2O, K2O and
Fe2O3 [39–41]. Several studies have investigated vol-
canic ash pozzolans as aluminosilicate sources for
geopolymer synthesis [13, 24, 42–44]. Volcanic ash
materials generally have fairly low reactivity and are
highly variable in physical properties, chemical and
the mineralogical compositions, depending on its
geological source [44, 45]. It should be noted that
several other factors influence the engineering prop-
erties of volcanic ash-based geopolymers including
the reactivity of volcanic ash, curing conditions, mix

Table 1 Relative abundance of common oxides in the earth’s crust and their involvement in geopolymer chemistry [27–31]

Oxides Abundance Effects on geopolymer Potential sources

(wt%) structure

SiO2 60 Network forming Clay, igneous rock, feldspar, volcanic ash, silica fume, fly ash, rice husk ash,
palm oil fuel ash
Al2O3 15 Network forming Alumina clays, bauxite
Fe2O3 7 Network forming Slag–iron blast furnace, laterite
CaO 5 Network modifier Slag, limestone

design and type of alkaline solutions. Thus, these
parameters can be used to optimize the characteris-
tics of its geopolymer products [27]. Generally, vol-
canic ash materials are suitable and sustainable raw
materials for geopolymer synthesis. They are also
available in huge amounts in certain geographical
regions, are easily accessible which ensures low cost
and have low environmental impact [43].
Use of feldspars and igneous rocks for geopolymer
syntheses have been reported [5, 10, 46]. Feldspars
are a major constituent of igneous rocks and the most
abundant mineral group in the earth’s crust [28].
Feldspar-based geopolymers generally achieve low
compressive strengths of paste and low degree of
reaction due to their mineralogical composition,
which generally consists of high crystalline minerals
that are weakly reactive [5, 10].
Several industrial by-products have been used to
synthesize geopolymer products. They include fly
ash, slags, palm oil fuel ash, rice husk ash and red
mud [6, 31, 47–49]. A lot of research has been done on
fly ash due to its availability in abundance. The major
chemical components in fly ash are SiO2, Al2O3,
Fe2O3 and CaO [50, 51]. Much of the published lit-
erature has shown major interest in class F fly ash-
based geopolymers. In fact, low calcium content is
preferable for geopolymers production [2, 6, 11].
Furthermore, the presence of free lime CaO is not
recommended as it generates flash set. Also, a high
amount of unburnt carbon exceeding 10% inhibits
geopolymerization [17]. Generally, fly ash geopoly-
merization exhibits low reactivity, which leads to
slow setting and low strength development. In fact,
the reactivity of fly ash in an alkaline environment is
controlled by various factors such as the natural pH
of the fly ash, particle size distribution, reactive SiO2
content, glass content and glass composition
[11, 52, 53]. However, use of these materials bears the
advantage of being economic, with enormous bene-
fits of low cost and limited negative environmental
impact [47, 48].
Reaction mechanism and mechanical
properties
In geopolymer synthesis, the alkaline solution usu-
ally consists of a mixture of MOH (M = Na, K) and
alkali metal (M) silicate solution. Soluble silicates or
water glass is commonly made in industry by alkali
fusion of purified sand (SiO2) with soda ash
J Mater Sci
(Na2CO3) or potash (K2CO3) at temperatures around
1300 C, followed by dissolution of the resulting
alkali silicate glass in water before or after cooling
[54]. Another method of producing silicate solutions
is by hydrothermal dissolution of a reactive silica
source in an alkaline solution [55]. Generally, the
chemical composition of soluble silicates is described
by the SiO2/M2O weight ratio (M = Na, K). For
sodium silicates, this SiO2/Na2O weight ratio is quite
close to the molar ratio, but both values are quite
different in potassium silicates [54].
Although sodium silicate and potassium silicate
solutions appear to have similar properties, the for-
mer is less expensive and most commonly used [56].
However, potassium silicate solutions present some
advantages in their characteristics. For a given SiO2/
M2O ratio, the viscosity of potassium silicate solu-
tions is ten times lower than that of sodium silicate
solutions, which is of benefit in terms of obtaining
good workability with less solution [17]. Also,
potassium silicate solutions are less likely to develop
efflorescence, i.e. formation of alkali carbonate
deposits, which is one of the major issues in sodium-
based geopolymers [56, 57]. Finally, materials made
from potassium silicates present better refractory
properties [58, 59]. The Geopolymers Institute rec-
ommends the use of low alkaline solution for
geopolymerization as the so called user-friendly
solution, which typically consists of any soluble sili-
cates with SiO2/M2O ratio greater than 1.40 [17].
Such use favours the implementation of resulting
geopolymer recipes in mass production, which can be
easily handled without strong specific safety
measures.
Although the geopolymerization mechanism is not
fully understood, it generally involves three main
stages [17, 56].
a. The dissolution of aluminosilicate materials in the
alkaline medium through the severing of covalent
Si–O–Si and Al–O–Al bonds and formation of
silicate and aluminate species. This process is
initiated by the hydroxyl OH- groups which after
bonding to the silicon atom make the Si–O–Si
bond more susceptible to breaking. Dissolution of
reactive aluminosilicates is rapid at high pH [60].
In metakaolin specifically, the dissolution leads to
formation of ortho-sialiate molecule ((OH)3Si–O–
Al(OH)- ?
3 Na ), the primary unit in geopolymer-
ization [17].
J Mater Sci
b. Condensation of silicate and aluminate mono-
mers to form a gel, until the solution reaches
saturation with liberation of NaOH which reacts
again [17]. Duxson et al. [60] claimed that there is
coexistence of two types of gel consisting of an
aluminium-rich gel yielding to the geopolymer
matrix and another gel yielding to crystallized
zeolite phases. Also, this process releases the
water that was nominally consumed during the
first step [60].
c. Polycondensation and structural reorganization
of the gel, yielding to the three-dimensional
aluminosilicate network of geopolymers [17, 60].
Geopolymerization yields products with different
physical and/or chemical properties, which depend
on the aluminosilicate source material and synthesis
conditions. Geopolymers present some attractive
properties of interest, including [3, 17]:
• High flexural and compressive strength, such as
compressive strength of paste [ 90 MPa at
28 days
• Fast hardening with some types of geopolymer
cement achieving 70% of their final compressive
strength within 4 h
• High thermal stability with mass loss \ 5% and
strength loss \ 60% at 1000 C
• Effective passivation of reinforcing steel
• Strong adhesion to metallic and non-metallic
surfaces
• Low permeability
• Dimensional stability in service with shrinkage as
low as 0.2–0.4%
• Long-term durability properties
• Low CO2 footprint
Starting materials
It is well known that the properties of geopolymers
are affected by the nature of raw materials such as
their mineralogical and chemical composition, parti-
cle size and glass content [5, 11, 52, 53]. The release
rate of silica and alumina from source materials plays
a significant role in the development of geopolymer
network and its final properties [61, 62]. High silica
availability leads to more contribution from Al in the
geopolymer matrix and promotes more homogenous
geopolymer binder gel [61]. At early stages of the
reaction, rapid release of alumina is shown to impede
the dissolution of silica particles. It is known that a
more homogeneous gel is observed with slower alu-
mina release [63]. Hajimohammadi et al. [62] inves-
tigated the dissolution rate of some geopolymer
precursor materials using a kinetic approach. They
observed that dissolution rates of silica-rich materials
are much higher than those of aluminosilicates. Also,
among the aluminosilicates studied, metakaolin
showed a distinctively higher release of Si species
from the very early hours of dissolution while release
rate of Si and Al species was almost similar in fly ash
and slag. They also demonstrated that milling of fly
ash increases the average dissolution rate of Si spe-
cies much more than for Al species. But the opposite
trend is observed with slag where milling rapidly
increases the release rate of Al while the release rate
of Si is increased only slowly. Generally, highly
crystallized minerals present weak dissolution in
alkaline medium [5, 10, 12]. Heal et al. [12] observed
that kaolin-based geopolymers do not undergo
complete geopolymerization and show slow strength
development, being the limitation by the structure of
kaolin, which has kaolinite stacks and plates of low
surface area.
Fernández-Jiménez et al. [52] investigated the effect
of chemical composition of fly ash on mechanical
properties of resulting geopolymers. They found that
fly ash with a high content of reactive SiO2 and Al2O3
and lower SiO2/Al2O3 ratio showed the best
mechanical strengths. Tennakoon et al. [64] found
that fly ash materials with reactive SiO2/Al2O3 molar
ratio [ 3.3 induced formation of zeolitic phases,
resulting in low strength development. They also
reported that there was a poor correlation between
the total SiO2/Al2O3 ratio and compressive strength
development. De Silva et al. [65] stated that for
metakaolin-based geopolymer, the SiO2/Al2O3 ratio
in the range of 3.4–3.8 showed high strength devel-
opment at later ages. Chindaprasirt et al. [66] repor-
ted that during the geopolymerization of calcium-
rich fly ash (ASTM Class C), the setting process is
controlled by initial calcium–aluminate–silicate–hy-
drate (C–A–S–H) formation while sodium–alumi-
nate–silicate–hydrate gel (N–A–S–H) formation
contributes to strength development. Also, SiO2/
Al2O3 ratio in the range of 3.2–3.7 showed products
with best mechanical properties. Zibouche et al. [67]
studied the influence of secondary minerals on the
geopolymerization reaction of metakaolin. They
showed that kaolin deposits containing up to 30%

secondary minerals are still suitable for geopolymer
synthesis, under moderate curing temperatures.
Temuujin et al. [68] reported that the reduction in
particle size and change in morphology after milling
led to a higher dissolution rate of fly ash particles,
yielding 80% increase in compressive strength when
compared with the geopolymer mixtures made from
non-milled fly ash.
Reactivity of aluminosilicate raw materials
Properties of geopolymers can be significantly affec-
ted by minor changes in the amount of Si and Al
available for the reaction [62, 64, 65]. Therefore, the
reactivity of aluminosilicate materials through
geopolymerization can be defined by its ability to
suitably release alumina and silica species in alkaline
medium for further development of rigid 3-D
geopolymer network. In geopolymer synthesis,
compressive strength of the resulting product is
commonly used as a quantitative indicator of
geopolymeric reactivity of raw materials [69, 70].
Several attempts have been made to assess reactivity
of aluminosilicate materials and determine their
potential for geopolymerization [29, 64, 71]. Of the
common oxides in geopolymer chemistry, i.e. SiO2,
Al2O3, Fe2O3 and CaO, alumina and silica are the two
major oxides which control the geopolymeric net-
work formation and strength development [29].
Studies have attempted to evaluate source materials
based on their bulk chemical composition but it has
been demonstrated that there is poor correlation
between the total SiO2 or Al2O3 content of the raw
materials and compressive strength development
[12, 29, 44, 64]. This implies that prediction of
geopolymeric reactivity based on the bulk chemical
composition of the starting materials may not be of
much value.
Usually, the interrelationship between chemical
composition and reactivity of individual minerals is
extremely complex [5]. The mineral content, glassy
phase and composition of the starting materials all
play significant roles in geopolymeric reactivity
[44, 71–74]. Tchakoute et al. [75] reported the effects
of mineralogical composition of two volcanic ash
types on their geopolymeric reactivity. They found
that the presence of structural water from muscovite,
which is a clayey mineral, in one type of volcanic ash
was responsible for its higher reactivity. Similarly,
J Mater Sci
Zhan et al. [76] investigated the effects of halloysite in
kaolin on the formation and properties of geopoly-
mers. The isothermal conduction calorimetry (ICC)
results showed that the presence of halloysite in
kaolin led to a higher geopolymerization rate of
metakaolin.
It is widely accepted that amorphous phases are
the reactive components in the geopolymerization
reaction [71, 77, 78]. Usually, most crystalline phases
hardly dissolve during geopolymer reactions
[5, 10, 12, 71]. The bulk amorphous composition can
be determined using a combination of X-ray fluo-
rescence spectroscopy (XRF) and quantitative X-ray
diffraction (QXRD) [78]. Also, quantification of
amorphous content in raw materials can be made
using alkaline or acidic dissolution techniques
[71, 73]. Williams and Van Riessen [78] reported that
the use of amorphous composition for geopolymer
mix design gave products with better compressive
strength than those formulated using the chemical
bulk composition. Djon Li Ndjock et al. [44] investi-
gated the effects of amorphous composition of five
volcanic ash types on properties of resulting
geopolymers. They observed that best compressive
strengths were obtained from samples containing a
high amount of amorphous phase and low SiO2/
Al2O3 molar ratio of amorphous phase. These find-
ings agree with results of similar work done on fly
ash by Fernández-Jiménez et al. [52]. Figure 1 sug-
gests potential uses of volcanic ash, according to
composition and the amount of amorphous phase.
Figure 1 Utilization of volcanic ash based on amount of
amorphous phase and composition [44] (reproduced with permis-
sion from Elsevier).
J Mater Sci
It has also been reported that particle size distri-
bution of aluminosilicate materials is a key factor in
the process of geopolymer synthesis. Generally, the
improvement of geopolymeric reactivity is observed
with reduction in particle size [68, 79–81]. Temuujin
et al. [68] investigated the effects of mechanical acti-
vation of fly ash on physical properties of geopoly-
mers. They observed that a reduction in the median
size (d50) from 14.4 lm for the raw fly ash to 6.8 lm
for the milled fly ash led to 80% increase in com-
pressive strength of the resulting geopolymer paste.
This increase in compressive strength is attributed to
reduction in particle size and change in morphology,
allowing a higher dissolution rate of the fly ash par-
ticles [68]. It is important to note that the aforemen-
tioned factors affecting the geopolymeric reactivity of
aluminosilicate materials are interrelated. Each factor
plays a significant role but may not singularly be
sufficient for good strength development. It is sug-
gested that the effects of these factors may not be
considered individually when a specific raw material
is studied.
Techniques for increasing reactivity
of aluminosilicate raw materials
The geopolymeric reactivity of source materials is a
major parameter for its utilization. A great number of
natural aluminosilicates and industrial by-products
can be used for geopolymer synthesis, as discussed in
section ‘‘Aluminosilicate raw materials’’. Neverthe-
less, a large number of potential starting materials
have poor reactivity and consequently yield products
with low mechanical strength. Improving reactivity
of geopolymers is essential for their potential struc-
tural use in concrete, while promoting utilization of
locally available source materials to mitigate envi-
ronmental issues of landfill and disposal of some
industrial wastes. In the literature, several techniques
have been investigated to alter reactivity of alumi-
nosilicate raw materials. These activation methods
may be divided into four categories consisting of
mechanical, thermal, physical separation and chemi-
cal activation, as given in Fig. 2. A combination of
these treatments can be performed.
Mechanical activation
Mechanical activation can be defined as a process
that increases the reactivity of a solid by imparting
mechanical energy, without altering chemical com-
position [82]. If the activation simultaneously leads to
change in composition or structure, it is a
mechanochemical reaction. The increase in reactivity
during mechanical treatment is usually a result of
disordering of the crystal and generation of defects or
other metastable forms that cause decrease in acti-
vation energy barrier for the process [83]. The pri-
mary effect of mechanical activation is the reduction
in particle sizes, causing changes in physical prop-
erties such as particle size distribution, specific sur-
face area, surface energy and phase composition
[84, 85]. The mechanism of transformation occurring
during mechanical activation of materials can be
divided into three main stages, which depend on the
degree of dispersion and grinding time, as illustrated
in Fig. 3 [86].
a. At stage 1, grinding initially leads to relatively
rapid particle size reduction and increase in
specific surface area. The energy consumed dur-
ing grinding is proportional to the particle
surface area produced. This stage is referred to
as Rittinger’s stage.
b. At stage 2, grinding continues and as particles get
finer, they begin to adhere to surfaces of grinding
media and mill, as well as to each other. The
energy used for size reduction is no longer
proportional to the increase in surface area.
Despite this nonlinearity, the increase in disper-
sion can still be remarkable. This is considered to
be the aggregation stage.
c. At stage 3, more grinding does not lead to further
size reduction but may cause decrease in the
degree of dispersion in certain materials. In this
stage of agglomeration, the crystal structure or
even the chemical composition of the material
changes.
During comminution of solid matter, adhesion
phenomena become more and more important with
decreasing particle size causing aggregation,
agglomeration, coating, caking and buildup [87].
Aggregation is a reversible process of particle adhe-
sion due to van der Waals forces. Agglomeration, on
the other hand, takes place following long duration of
grinding. It is caused by strong, irreversible

Figure 2 Summary of
activation methods.
Figure 3 Theoretical diagram of the grinding process [86]
(reproduced with permission from Elsevier).
interparticle bonds [84]. Adhesion during grinding is
always undesirable as it diminishes the effect of
grinding, lengthens the grinding time and increases
the energy requirement [87]. While aggregation
mostly influences the progression and effectiveness
of the grinding process, agglomeration has a detri-
mental effect on certain properties of the ground
material [86]. However, adhesion can be avoided by
using dispersion agents, also called grinding aids
[84, 87].
Mechanical activation is usually carried out using
devices called mills, which may be of different char-
acteristics. Several types of mills have been designed
J Mater Sci
for specific purposes related to particle size reduction
of products and to milling efficiency. For instance,
mills used for fine grinding operations to particle
sizes below 100 lm include roller mills, impact mills,
ball mills, agitation mills, jet mills, shear-type mills
and colloid mills [88]. Depending on the type of mill,
the stresses occurring during milling may include
compression, shear (attrition), stroke impact and
collision impact [82]. Ball mills are commonly used in
the laboratory and industry for particle size reduction
of most aluminosilicate materials such as rocks, ores,
cement, fly ash. It has been reported that vibratory
mills, characterized by high energy density, provide a
higher rate and extent of grinding efficiency com-
pared to the normal rotary ball mills [89].
The efficiency of milling can be affected by many
factors such as type of mill, types of grinding media
such as balls, rods or other shapes, material of milling
media, e.g. stainless steel, tungsten carbide, zirco-
nium oxide, aluminium oxide, silicon nitride, grind-
ing atmosphere such as air, inert gas, reductive gas,
wet or dry milling atmosphere, fill level of the milling
chamber, ball-to-powder ratio (BPR), grinding tem-
perature, speed of the mill and grinding time [82].
Mechanical activation has been found to improve
the reactivity of solids in many materials processing
operations such as extractive metallurgy, building
materials, food and chemicals [83, 90–92]. Several
studies have reported the effects of mechanical
J Mater Sci
activation of raw materials on properties of
geopolymers [11, 80, 81, 85, 93–97]. From reported
data, the geopolymeric reactivity of mechanically
activated materials depends on factors such as type
of mill, milled material, milling time and milling
atmosphere [80, 95, 96, 98]. Kumar et al. [99] prepared
geopolymer materials from mechanically activated
fly ash. The alkaline activator was a solution with
20% NaOH concentration, and the liquid/solid ratio
was 0.5. They found that geopolymerization of
mechanically activated fly ash occurred at a lower
temperature and setting time, as compared to the
reaction of raw fly ash. The effect of mechanical
activation was influenced by the mill type. Moreover,
ground materials from vibratory mill achieved better
compressive strength than those obtained using
attrition mill. The improvement in compressive
strength was found to be related to increased reac-
tivity and the resulting formation of compact
microstructure. Compressive strength of upto
120 MPa was obtained with 50 mm cube geopolymer
pastes made using mechanically activated fly ash.
These results were in agreement with findings of
Temuujin et al. [68], who also observed increased
reactivity in mechanically activated fly ash during the
synthesis of geopolymers cured at ambient tempera-
ture. In their study, a mixture of 14 M NaOH and
sodium silicate solution was used as activator. Their
results indicated that mechanical activation led to
reduction in particle size and change in particle
shape, allowing a higher dissolution rate of the fly
ash particles. Mechanical activation led to 80%
increase in compressive strength of 25 9 50 mm
paste cylinders over strengths of geopolymers
obtained from raw fly ash. On the other hand,
mechanical activation of the fly ash destroyed some
of its spherical morphology and reduced the ‘‘ball
Figure 4 Morphology of raw (a) and milled fly ash particles (b) [68] (reproduced with permission from Elsevier).
bearing effect’’ which reduces workability. Figure 4a,
b shows the microstructure of raw fly ash and milled
fly ash, respectively. Also, faster setting was observed
with mechanically activated fly ash. This was miti-
gated by addition of extra water in the starting
mixture.
Mucsi et al. [96] investigated the correlation
between grinding process, ground materials and
geopolymer properties. A 6 M solution of NaOH was
used as activator with a mix of 0.65 liquid/solid ratio.
Mechanical activation was carried out using three
different types of laboratory scale mills comprising
the conventional tumbling ball mill, vibratory mill
and stirred media mill. The finest ground product
produced with lowest energy input was obtained
using the stirred media mill. It was reported that the
compressive strength of the geopolymer samples
strongly depended on the type of mill and milling
time. The compressive strengths of paste obtained
from the fly ash that was activated in stirred media
mill, vibratory mill and ball mill were 22, 16 and
15 MPa, respectively. The superiority in strength of
the geopolymer product from activated fly ash that
was milled using stirred media mill was attributed to
its particle size distribution, which reportedly varied
from superfine particles of\ 1 lm to coarser particles
of size 200–300 lm. Its median particle size was
5.2 lm. Finer particles exhibit better solubility
resulting in more geopolymer gel while coarser par-
ticles behave as ‘‘aggregate’’ in the geopolymer
matrix. Also, the filler effect of the superfine unre-
acted size fraction \ 1 lm leads to a more compact
microstructure.
Kumar and Kumar [11] investigated the effects of
milling duration conducted at 5, 10, 20, 30, 45, 60 and
90 min on the reaction kinetics of geopolymerization
as well as on the characteristics of resulting products.

A solution of 6 M NaOH concentration was used as
the alkaline activator. The reactivity of fly ash
increased with reduction in median particle size and
with increase in milling time. Mechanical activation
enhanced the rate of geopolymeric reactivity and
decreased the setting time when the median particle
size was reduced to less than 5–7 lm. Results of
isothermal conduction calorimetry studies conducted
at 27 C showed evidence of geopolymerization of
mechanically activated fly ash, characterized by a
broad exothermic peak. The improvement in physical
properties of the geopolymer products was correlated
with median particle size reduction and change in
reactivity of fly ash. Similarly, Djobo et al. [80] stud-
ied the effects of extended milling of volcanic ash
done using vibratory mill on geopolymeric reactivity.
The alkaline activator used was sodium silicate
solution with SiO2/Na2O molar ratio of 1.45. X-ray
diffraction (XRD) results showed that mechanical
activation considerably reduced the degree of crys-
tallinity for samples that were milled for 90 min. This
was followed by change in the mineralogy of samples
milled for 120 min. The rate and extent of geopoly-
merization increased with milling time. A 100%
increase in compressive strength was observed after
the mechanical treatment. Thus, mechanical activa-
tion may be considered as a suitable method for
improving the reactivity of raw volcanic ash. Wei
et al. [81] showed that the silicon and aluminium
species from mechanically activated materials
increasingly dissolved in alkaline medium the longer
the milling time, as shown in Fig. 5. It was reported
that the development of strength for milled material-
Figure 5 Content of active Si and Al in tailings subjected to
different milling times [81] (reproduced with permission from
Elsevier).
J Mater Sci
based geopolymers was related to the amount of
reactive species, i.e. Si and Al, in the ground mate-
rials. Higher dissolution of Si and Al species sub-
stantially improved the compressive strength. Other
studies have reported the negative effect of pro-
longed grinding. Mucsi et al. [100] claimed that
during mechanical activation of lignite fly ash in
stirred media mill, the compressive strength of the
geopolymer samples increased with milling time up
to certain fineness. After that, further grinding led to
decrease in compressive strength. Earlier work by
Mucsi et al. [96] gave similar results. Figure 6 shows
that indeed the strength enhancing effect of grinding
is only effective to a certain level of material fineness
achieved. Extreme fineness, due to a prolonged
duration of grinding, may not improve mechanical
properties any further. Prior to using a starting
material as a geopolymer, it seems essential that this
optimum fineness should be determined to avoid
potential adverse effects of over-grinding.
Mechanical activation was also found to be effec-
tive for less-reactive kaolin, achieving products with
good compressive strengths [32, 101]. Hounsi et al.
[32] observed the partial amorphization of kaolin
during mechanical activation, as indicated by inten-
sity reduction in main characteristic peaks of XRD
patterns for the milled samples. Thus, milling chan-
ged the crystallinity degree of the raw kaolin and
promoted geopolymerization reaction, leading to
increase in compressive strength. Results showed
that without mechanical activation, the optimal cur-
ing condition was 24 h at 70 C for which the com-
pressive strength of 50 mm cube pastes after 28 days
Figure 6 Variation of compression strength as a function of
grinding time (constructed with data from Ref. [96]).
J Mater Sci
of curing was 15 MPa. Mechanical activation led to
35% strength increase for the same curing and testing
conditions. The alkaline activator used was a mixture
of sodium silicate solution and 8 M NaOH solution at
the Na2SiO3/NaOH mass ratio of 0.32. Heah et al.
[101] conducted scanning electron microscopy (SEM)
study and reported that the plate-like structure of
kaolin reduced after mechanical treatment. In their
study, the milled kaolin showed a smoother surface
and exhibited edge distortion of particles. Mechanical
activation improved the geopolymerization process.
Extended milling time increased compressive
strength while the microstructure of the geopolymer
products became more compact and denser. Figure 7
shows the micrographs of milled kaolin geopolymers
[101].
Milling atmosphere is also an important parameter
that affects the geopolymeric reactivity of milled
materials. Preliminary studies by Kalinkin et al. [102]
have shown that mechanical activation of Cu–Ni slag
in CO2 gives higher compressive strength for the
geopolymer samples, compared to its mechanical
activation in air. Sodium silicate solution with a
SiO2/Na2O ratio of 1.5 was used as alkaline activator.
The higher geopolymeric reactivity of samples milled
in CO2 was attributed to chemisorption of CO2
molecules in the form of distorted carbonate ions
during mechanical activation. This phenomenon
promoted more intensive interaction of alkaline
solution with activated slag particles. After 360 days,
compressive strength was 89.5 and 119.0 MPa for
14.1 mm cube geopolymer mortars prepared using
slag that was activated in air and in CO2, respectively
[102]. A similar trend in which greater compressive
strength of geopolymer mortars was obtained using
Figure 7 SEM micrograph of mechanically activated kaolin geopolymers for different milling times a 1 h, b 3 h, c 5 h [101] (reproduced
with permission from Ref. [101]).
CO2-milled slag relative to air-milled slag was
reported for zinc slag [98].
A recent study investigated the influence of
mechanical activation of fly ash on the micro- and
nano-structure of geopolymers using transmission
electron microscopy (TEM–EDS). They found that
milling mostly decreased the amount of the amor-
phous aluminosilicate rather than crystalline phases
present in fly ash, as shown in Fig. 8 [103]. Thermo-
dynamically, glass has higher free energy than crys-
talline phases, thus the introduction of additional
energy by milling results in more particle breakage
and alteration. A minor effect was observed on
mullite that is at nanometric scale and is embedded
in the amorphous phase. It was demonstrated that
mechanical activation promoted the formation of
geopolymer gel, mainly N–A–S–H gel with an
increase in its nano-pore size. Also, isothermal con-
duction calorimetric study showed that the early
reaction corresponding to dissolution/precipitation
had a linear relationship with milling time, but not
with median particle size. A conceptual mechanism
of the reaction was also proposed, as illustrated in the
schematic diagram of Fig. 9 [103].
Generally, mechanical activation of the raw mate-
rial leads to a reduction in particle size, increase in
specific surface area, decrease in crystallinity, change
in the mineralogical composition and increase in the
amorphous phase. These effects promote greater
dissolution of the milled materials in alkaline solu-
tion, consequently enhancing the geopolymerization
reaction [11, 80, 94, 104]. As a result, there is
improvement in properties of products made from
mechanically activated geopolymer materials
[93, 95, 97]. Therefore, mechanical activation can be

Figure 8 Quantitative phase analysis showing variation of crys-
talline and amorphous phases with milling time [103] (reproduced
with permission from Elsevier).
considered as an effective technique for improving
the properties of geopolymer products. The tech-
nique may be employed to beneficially utilize less-
reactive waste materials that are typically disposed
off as landfills [81, 85, 96].
Activation by physical separation
This process which gives unmodified particles is
based on physical properties of the materials such as
density, particle size, shape, surface properties, elec-
trical and magnetic properties [105, 106]. Activation
by physical separation of particle fractions includes
Figure 9 Conceptual
mechanism of the effect of
milling on fly ash particle
characteristics and
geopolymerization [103]
Q = Quartz, M = Mullite,
G = Glass (reproduced with
permission from Elsevier).
J Mater Sci
use of techniques such as air classifier, flotation,
sieving, sorting, clarification and magnetic separa-
tion. [87, 106, 107] The method is widely used in
mineral processing for beneficiation purposes
[108, 109]. It has been shown that fly ash behaviour
can be tailored by sieving and magnetic separation
[110]. For instance, blended portland cement from
magnetic and non-magnetic fly ash fractions displays
different characteristics [107, 111]. The beneficial
effects of employing the separation method have
been reported in relation to use of fine fractions of fly
ash in preparing blended portland cement [112, 113].
Several attempts have been made in recent decades to
study the effects of separation method of activation
on the properties of geopolymers. Kumar et al. [114]
argued that the geopolymeric reactivity of fly ash was
altered by air classification using a laboratory classi-
fier operated at 10,000 rev/min. An increase in the
glass content of finer fractions obtained by air clas-
sification was observed relative to raw fly ash,
resulting in increase in compressive strength of its
geopolymer pastes. Chindaprasirt et al. [115] also
observed that after separation of high-calcium fly ash
using air classifier, the amorphous phase content in
the fine fraction was higher than in the coarser frac-
tion. A mixture of Na2SiO3 solution and 10 M NaOH
solution was used as alkali activator. It was demon-
strated that the setting time of geopolymer pastes
decreased with an increase in fly ash fineness. There
J Mater Sci
was improvement in workability, strength and dry-
ing shrinkage properties of mortars made using the
fine fly ash. Geopolymer mortars giving 28-day
compressive strength of up to 86.0 MPa were
obtained using 50 mm-size cube specimens.
Nugteren et al. [116] prepared geopolymer pastes
using six different size fractions of fly ash obtained by
air classification. The alkaline solution used was
potassium silicate solution with SiO2/K2O molar
ratio of 1.25. They found that physical separation
affected the pH, bulk chemical and mineralogical
composition of the fractions, as well as their particle
size distributions. The pH obtained for the various
size fractions varied from 10.2 for the finest fraction
to 12.5 for the raw sample. The workability and set-
ting time of the paste were also influenced by size
fractions. However, the relationship between particle
size and strength was not well established, although
the variations in chemistry and pH of the different
fractions could play a role in strength development.
Compressive strengths of over 100 MPa for cylinder
specimen of sizes 29 mm diameter 9 25 mm height
were obtained in this study. It is worth noting that
when the different size fractions of the fly ash were
obtained by grinding, their pH values, bulk chemical
and mineralogical compositions showed no
notable differences. Kumar et al. [117] investigated
the geopolymerization activity for different fractions
of fly ash, separated into various sizes then drawn
from hoppers of an electrostatic precipitator. They
found that the different size fractions of fly ash col-
lected showed marked variations in chemistry, min-
eralogy, particle size distribution and glass content.
From chemical analyses, the SiO2/Al2O3 ratio
increased with increase in fineness, whereas Fe2O3,
CaO and loss on ignition decreased in finer fractions.
A linear correlation between geopolymeric reactivity
and glass content was observed. Strength develop-
ment was attributed to the combined effects of SiO2/
Al2O3 ratio, particle size and glass content.
Microstructural studies done using SEM–EDS on
hardened geopolymer pastes revealed the presence of
more reaction products (i.e. N–A–S–H gel) in finer
fractions while unreacted particles were prevalent in
coarser fractions.
Chemical activation
Chemical activation is a method of improving reac-
tivity of a material system by addition of admixtures.
Concrete admixtures are materials other than
hydraulic cement, water or aggregates that are added
immediately before or during mixing [118]. These
admixtures enhance the properties of portland
cement concrete in the fresh and/or hardened state
[119]. There are several types of admixtures used in
concrete technology, broadly categorized as chemical
or mineral admixtures [118]. Chemical admixtures
are generally water soluble and are added in small
amounts to control various properties of fresh or
hardened concrete. The different types of chemical
admixtures include accelerators, water reducers,
superplasticizers and retarders [118].
Mineral admixtures are fine ground solid materials
usually categorized as filler materials, pozzolans or
SCMs, latent hydraulic materials [120]. The most
common SCMs are fly ash, ground granulated blast
furnace slag, natural pozzolans and silica fume [119].
Incorporation of mineral admixtures as SCMs in
concrete may reduce or increase strength, improve
durability, decrease the heat of hydration in mass
concretes, reduce cost [119, 120]. Numerous studies
have reported the use of chemical and mineral
admixtures in the synthesis of geopolymers and their
effects on properties [121–124]. The present literature
review is limited to ingredients that may be used to
improve the geopolymeric reactivity of the raw alu-
minosilicate materials. The activation of geopolymer
materials using chemical admixtures is usually car-
ried out using two methods, namely blending and
alkaline fusion.
Blending technique
The conventional blending technique involves com-
bining the raw material with a chemical additive by
mixing the two. This technique adjusts the bulk
chemical composition of the raw material, causing a
change in its geopolymeric reactivity. The composi-
tional changes typically involve modification in the
amount of mainly SiO2, Al2O3 and CaO oxides. Ola-
lekan et al. [125] investigated the effects of Al(OH)3
addition on the properties of slag/ultrafine palm oil
fuel ash geopolymer system. A combination of 10 M
NaOH solution and Na2SiO3 solution was used as
alkaline activator. The mass ratio of sodium silicate to
NaOH of 2.5 was employed. They found that the
inclusion of Al(OH)3 in the range of 2–6 wt% led to
change in SiO2/Al2O3, H2O/Na2O ratios and com-
pressive strength of the geopolymer products.
 J Mater Sci

Microstructural analysis revealed that there was

increase in Si–Al substitution, amorphous gels and
carbonation with the inclusion of Al(OH)3 in the
mixture. Compressive strength increased with addi-
tion of up to 4 wt% Al(OH)3. A 3-day compressive
strength of 42 to 49.5 MPa was achieved with addi-
tion of 3–4 wt% Al(OH)3. Similar response of volcanic
ash geopolymer to addition of alumina (Al2O3) has
been reported [126]. In the study, a mixture of Na2-
SiO3 solution and 12 M NaOH solution at Na2SiO3/
NaOH mass ratio of 2.0 was used as alkaline activa-
tor. It was found that adding Al2O3 at an optimal
value of 40 wt% improved the extent of geopoly-
merization and led to a 32.4% increase in the 28-day Figure 10 Compressive strength of nano-silica modified
compressive strength of 31 mm diameter 9 62 mm geopolymer (12GC6), heat-cured geopolymer concrete
(12GC0H) and control cement concrete (CC) at varied ages
height cylindrical paste specimens [126].
[130] (reproduced with permission from Elsevier).
Recently, it has been shown that incorporation of
nanoparticles can significantly enhance the properties
low strengths at elevated curing temperature of
of geopolymer materials [127, 128]. For example,
70 C. Calcium hydroxide seemed to be a more ben-
adding 1–2% nano-SiO2 and nano-Al2O3 as additive
eficial additive than calcium oxide [134].
to fly ash-based geopolymers produced additional
Phummiphan et al. [135] showed that recycled
calcium–silicate–hydrate (C–S–H) or C–A–S–H and
calcium carbide (CaC2) residue can be used to
N–A–S–H phases, which shortened the setting time
develop geopolymer binders. It was found that CaC2
and improved mechanical properties [129]. Also,
promoted geopolymerization and improved early
Adak et al. [130] reported that the addition of nano-
strength. To obtain the highest 90-day compressive
silica to fly ash-based geopolymer concrete enhanced
strength of fly ash-based geopolymers, optimum
the geopolymerization process at ambient tempera-
CaC2 replacement limited to 20% was recommended.
ture, by increasing the dissolution rate of Si and Si–Al
Phetchuay et al. [136] also investigated the effects of
phases. A 12 M NaOH solution mixed with Na2SiO3
CaC2 addition into fly-based geopolymers. Use of
solution at Na2SiO3/NaOH mass ratio of 1.75 was
12% CaC2 addition improved the strength of the
used to prepare the alkaline activator. The nano-silica
geopolymer products by up to 1.5 times.
modified geopolymer concrete showed better struc-
As mentioned previously, geopolymer reactivity of
tural performance than heat-cured geopolymer con-
raw materials can also be modified by mineral
crete containing conventional cement concrete
additive. Generally, it is a reactive material such as
samples, as shown in Fig. 10. It has been suggested
metakaolin or slag, which is added to a less-reactive
that heat curing of fly ash-based geopolymers to
geopolymeric system. This process also influences the
achieve desired strength could be avoided by addi-
bulk chemical composition of the geopolymer pre-
tion of appropriate amount of nano-silica in the
cursor. Several successful attempts have been repor-
mixture [130].
ted on the beneficial effects of mineral admixtures to
The potential use of calcium-based compounds to
geopolymerization enhancement [6]. It has been
enhance geopolymerization has also been investi-
found that adding ground granulated blast furnace
gated [131–133]. It has been suggested that adding a
slag (GGBS) to fly ash altered the reactivity of the
small proportion of CaO or Ca(OH)2 to class F fly ash
latter, resulting in reduction in the setting time and
may improve the dissolution of the fly ash in the
increase in compressive strength of the resulting
alkaline medium, which in turn increases the rate and
geopolymer composite [137–139]. The improvement
extent of geopolymerization reaction but this effect is
in compressive strength and setting time with slag
dependent on curing temperature. Addition of 3 wt%
addition was attributed to the formation of C–A–S–H
CaO or 3 wt% Ca(OH)2 increased the 7-day com-
and N–A–S–H gel phases, which coexist. Also,
pressive strengths from 11.8 MPa to 22.8 or 29.2 MPa,
development of a compact microstructure was
respectively, at ambient temperature but gave very
J Mater Sci
observed [6, 139–141]. Xu et al. [137] investigated the
effect of blast furnace slag grades on fly ash-based
geopolymer waste. Their results showed that at a
higher grade, GGBS generated more hydration heat,
suggesting higher reactivity and geopolymerization.
Davidovits et al. [142] developed slag–fly ash-
based geopolymer cement that hardened at room
temperature. Potassium silicate solution with the
SiO2/K2O molar ratio of 1.25 was used as alkaline
reagent. They showed that the main contributors to
the geopolymer matrix, which are consequently
responsible for the compressive strength develop-
ment, were the glassy fly ash particles supplying Si
and Al, the high Ca slag supplying Ca and the alka-
line solution providing K-silicate. The geopolymer
cement produced in their study [142] showed com-
pressive strengths of 29 mm diameter 9 25 mm
height cylinder pastes of up to 95 MPa after 28 days
of curing. It also exhibited long-term durability
properties. Similarly, Salih et al. [143] demonstrated
that high-strength geopolymer binders made using
palm oil fuel ash (POFA) and GGBS could be syn-
thesized at ambient temperature. In the study, a
combination of Na2SiO3 and NaOH was used as
activator. Addition of GGBS as partial replacement of
POFA increased the compressive strength at all ages.
Up to 65% increase in compressive strength of 50 mm
cube paste samples was achieved when 50% of POFA
was replaced with GGBS. Ye et al. [144] investigated
the properties of geopolymers synthesized by
blending 70% calcined tailings and 30% slag. The
alkaline solution consisted of Na2SiO3 solution
modified using NaOH to SiO2/Na2O molar ratio of
1.8. The microstructure and strength development for
the geopolymer mortars cured at ambient tempera-
ture were monitored over a period of 6 years. Results
indicated that hardened geopolymer mortars became
more compact with advancing age, due to progres-
sive geopolymerization attributed to formation of
coexisting C–A–S–H and N–A–S–H gels. Compres-
sive strength of 40 9 40 9 160 mm prismatic mortars
significantly increased from 50.0 MPa at 28 days to
75.0 MPa at 6 years. Carbonation was observed in
both the early-age and long-term geopolymers, but
deterioration of the system was inhibited by the
stable N–A–S–H gels which were the predominant
geopolymeric products.
The influence of highly reactive metakaolin as
substitute in less-reactive geopolymeric system has
been widely investigated. Robayo-salazar et al. [145]
observed that the partial replacement of natural
pozzolans by metakaolin of up to 20 wt% signifi-
cantly improved the compressive strength of the
mixtures. This enhancement of mechanical properties
was attributed to an increase in the amount of
amorphous SiO2 and Al2O3. The addition of meta-
kaolin promoted the formation of a more
stable geopolymeric gel with lower porosity. A
combination of NaOH solution and sodium silicate
solution was employed as activator with different
SiO2/Na2O molar ratio in the range of 0.55–2.78. A
28-day compressive strength of up to 68 MPa was
obtained under room temperature curing on 20 mm
cube pastes. These results agree with those obtained
by Djobo et al. [9] who claimed that the reactivity of
volcanic scoria could be altered by its partial
replacement by metakaolin to compensate for the
deficiency of amorphous SiO2 and Al2O3 in the vol-
canic scoria. The alkaline activator used in the study
was a mixture of 12 M NaOH solution and Na2SiO3
solution with two SiO2/Na2O molar ratios of 1.1 and
1.4. In their study, 5–25% metakaolin was added,
resulting in higher dissolution of Al2O3 and SiO2
species, polycondensation, increase in compressive
strength and decrease in setting time. The compres-
sive strengths of 31 mm diameter 9 62 mm height
cylinder pastes at 28 days were up to 68.8 MPa.
Similarly, Ogundiran and Kumar [146] investi-
gated the effects of calcined clay addition to fly ash
reactivity, physical and mechanical properties of
geopolymer composite. A mixture of 8 M NaOH
solution and Na2SiO3 solution at NaOH/Na2SiO3
mass ratio of 1 was used as activator. It was found
that calcined clay addition accelerated dissolution/
hydrolysis of fly ash, while fly ash controlled the
exothermic reaction that accompanied alkaline dis-
solution and hydrolysis of calcined clay. Addition of
25 wt% calcined clay improved the early- and late-
age strengths of the geopolymer pastes. They con-
cluded that the rate of geopolymer formation and the
compressive strength of the less-reactive silica-rich
geopolymer source materials can be improved by the
addition of calcined kaolin clay.
Alkaline fusion
Geopolymeric reactivity can be also improved by
alkaline fusion of the raw materials. In this method,
the mixture of raw material and sodium hydroxide is
calcined at a temperature higher than the melting
 J Mater Sci

point of NaOH prior to the geopolymerization

[10, 75]. This method involves decomposing of raw
materials during the synthesis of zeolites [147, 148].
Xu et al. [149] found that alkali fusion process pro-
moted the dissolution of Si and Al species from the
low reactive fly ash materials and thus improved
their reactivity. Alkali fusion of fly ash was achieved
by thoroughly mixing the raw material with NaOH
pellets at a low alkali/ash mass ratio of 0.5 in a ball
mill for 10 min, followed by fusing the resulting
mixture in a muffle furnace at 550 C for 2 h at a
heating rate of 15 C/min. The fused fly ash materials
were air cooled to ambient temperature and then Figure 11 Increase in 28-day compressive strength of geopoly-
ground in the ball mill for another 10 min to obtain a mer mortars with addition of various amounts of Na2O used:
homogeneous sodium silicate-rich mixture. Studies MGf1-10%, MGf2-20%, MGf3-30%, MGf4-40%, MGf5-50%,
indicate that alkali fusion modifies the mineralogical MGf6-60% [10] (reproduced with permission from Elsevier).
composition of the raw material and induced the
observed. Replacement of fused materials with up to
formation of an amorphous phase and/or new crys-
60% metakaolin showed the best performance.
talline phases [10, 150].
It is worthwhile mentioning that the development
Tchadjie et al. [10] demonstrated that the amount
of geopolymers as a one-part ‘‘just add water’’ mix-
of reactive phase in the fused geopolymer mixture
ture, as done in portland cement mixtures, has been
significantly increases with increase in the amount of
reported to be possible based on alkali fusion acti-
Na2O added during the fusion process. Na2SiO3
vation of the aluminosilicate materials as precursor.
solution with silica modulus of 3.2 was used as
Usually, in this method, the alkali–thermal treatment
alkaline activator. The results showed that there is an
is carried out at high temperatures of about 900 C.
increase in the geopolymeric reactivity of the alumi-
The resulting geopolymer systems exhibit similar
nosilicate raw material after the treatment. Tests on
performance as conventional geopolymers [153–155].
20 mm cube specimens showed that the compressive
However, there is limited research on this alternative
strengths of resulting geopolymer mortars varied
and promising approach of one-part geopolymeric
between 6.25 and 40.5 MPa, depending on the
materials [151, 156, 157].
amount of Na2O used during the alkali fusion pro-
cess, as shown in Fig. 11. It is worthwhile noting that
Thermal activation
excess amount of Na2O is detrimental to strength
development and durability properties of geopoly- The thermal activation process modifies physico-
mers made from fused materials [150, 151]. Gener- chemical properties of a material through heating
ally, a reactive Al2O3-rich material is used as [158]. The heat treatment is conducted in three major
additional aluminosilicate source to consume the stages consisting of: heating to a specific predeter-
excess alkali from the fusion process [149, 152]. mined temperature (stage 1), maintaining this tem-
Tchakoute et al. [152] investigated the effect of perature for required time (stage 2) and finally
metakaolin addition on geopolymeric reactivity of cooling (stage 3) [159]. During heat treatment, phase
fused volcanic ash. Na2SiO3 solution of silica modu- transformations occur in the material, resulting from
lus of 3.2 was used as alkaline activator. It was found either loss of volatile components or change of
that addition of metakaolin in the range of 30–60% entropy and the reorganization of atomic structures.
increased the amount of reactive phase formed, These changes can be monitored using thermoana-
resulting in the dissolution of more silicon and alu- lytical techniques such as differential thermal analy-
mina species. In turn, geopolymerization was sis (DTA) and thermogravimetric analysis (TGA)
enhanced and compressive strength of the geopoly- [160]. For effective thermal activation, thermoanalyt-
mer product increased. A linear correlation between ical methods can be used to select the appropriate
compressive strength and metakaolin content was holding temperature necessary to achieve desired
J Mater Sci
properties of the heated material [151, 161]. Heat
treatment can be affected by several factors such as
heating rate, holding temperature, holding time,
heating atmosphere and the rate of cooling [158–160].
The heat treatment process is a significant operation
used in manufacturing of various engineering mate-
rials such as steel, ceramics and cement. For instance,
portland cement is made by thermal activation of a
mixture of limestone and clay or other materials of
similar bulk composition and sufficient reactivity, at
a temperature of about 1450 C. Partial fusion of the
raw mix occurs, and nodules of clinker are produced
[119].
Various studies have investigated the effect of
thermal activation of raw geopolymer materials on
geopolymerization process, of which thermal activa-
tion of kaolin has been of interest as reported in the
literature [8, 47, 162–164]. Generally, heating of clay
minerals leads to change in its structure, which varies
for different clay mineral groups [165]. Kaolinite is
transformed into metakaolin through calcination.
Due to the high reactivity and purity of metakaolins,
it is one of the most explored aluminosilicates for
synthesis of geopolymers [166, 167]. Often, kaolinite
is converted into metakaolin by calcination at tem-
peratures between 700 and 900 C, before being used
for geopolymer synthesis [7, 33–35]. Calcination
causes the dehydroxylation of kaolinite and forma-
tion of an amorphous phase, which is highly reactive
in alkaline medium [7, 34, 35]. Similar effects of cal-
cination are observed with other aluminosilicate
materials as well. Ye et al. [161] reported that thermal
activation improved the solubility of red mud in
alkaline solution and promoted geopolymerization.
The activator was alkaline solution containing
sodium silicate prepared by dissolving sodium
hydroxide in sodium silicate solution to reach dif-
ferent SiO2/Na2O molar ratios. Mineral phases in the
red mud transformed successively with an increase
in temperature, forming new phases with different
solubility. The dissolution efficiencies of alumina and
silica reached a maximum when red mud was cal-
cined at 800 C, resulting in the highest compressive
strength of binders.
Also, Bondar et al. [168] investigated the effect of
thermal activation at 700, 800 and 900 C on the
geopolymeric reactivity of five natural pozzolans. A
mixture of Na2SiO3 solution with SiO2/Na2O molar
ratio of 2.1 and KOH solution was used as the acti-
vators. It was found that calcination significantly
increased the dissolution of Si species in alkaline
medium, but Al species solubility was less influ-
enced. In one case, compressive strength of 20 mm
cube pastes increased from 5 MPa for the raw poz-
zolan to 19.3 MPa for the same pozzolan calcined at
800 C. Generally, the geopolymeric reactivity of
calcined natural pozzolans was correlated with their
mineralogical composition. Rieger et al. [169] studied
geopolymerization of shale–slag calcined at different
temperatures. An aqueous solution of Na2SiO3 with
silica modulus of 1.71 and content of water-soluble
solids 32.28% was used as activator. The XRD and
Fourier transform infrared spectroscopy (FTIR)
analysis revealed that the raw material subjected to
thermal treatment at 600 C provided the most reac-
tive state, giving the highest compressive strength of
geopolymer mortar at 82.5 MPa. However, further
firing at temperatures greater than 800 C was
detrimental, due to an increase in the crystalline
content and a significant reduction in the alkaline-
hardening reaction. Also, other studies have similarly
reported the negative effect of very high-temperature
calcination of the raw material on geopolymerization
[170].
Temuujin et al. [170] found that preliminary calci-
nation of fly ash at 500 and 800 C induced de-car-
bonation and also led to some decrease in the
amorphous content of the fly ash from 60 to 57%. The
alkaline activator used was 14 M NaOH and Na2SiO3
solution. In this case, compressive strength of 25 mm
diameter 9 50 mm height cylinder pastes decreased
from 55.7 MPa for raw fly ash-based geopolymer to
44.3 MPa after calcination at 800 C. The drop in
compressive strength of the geopolymer pastes after
calcination was attributed to the partial crystalliza-
tion of the aluminosilicates and haematite on the
surface of the fly ash particles. It was suggested that
such crystallized aluminosilicate (mullite) and hae-
matite prevent dissolution of the aluminate and sili-
cate species in the alkaline solution. Similar findings
were also reported by Wan et al. [171] who high-
lighted that recrystallization taking place during
calcination of kaolinite at higher temperatures is
significantly detrimental to the dissolution of result-
ing metakaolin during geopolymerization. Figure 12
shows the compressive strength of the 25 mm
diameter 9 50 mm height cylinder geopolymer
pastes for metakaolin heated to various high
temperatures.

It is worth noting that calcination temperature is
not the only important parameter that controls the
geopolymeric reactivity of aluminosilicates. The
method of calcination also plays a role in the phase
transformations induced by thermal treatment and in
turn affects reactivity of the calcined geopolymer
material. Kenne et al. [172] studied the effect of cal-
cination rate on the properties of metakaolin-based
geopolymers. In their experiment, kaolinite was cal-
cinated at 700 C for 30 min using different rates of
calcination: 1, 2.5, 5, 10, 15 and 20 C/min. The
alkaline activator used was prepared by mixing
sodium silicate solution and 12 M NaOH to obtain
Na2O/SiO2 molar ratio of 0.7. They reported that
geopolymer pastes with low setting time and high
compressive strength were obtained from metakaolin
calcined at a low rate. Compressive strength of
20 mm cube mortars decreased from 49.4 to
20.8 MPa, when the rate of heating increased from 1
to 20 C/min. Recently, some studies have reported
on the use of flash calcination to produce metakaolin
[167, 173, 174]. In this method, a pulverized material
is heated quickly, held at temperature for a short time
and cooled down at a rate of about 103–105 C per
second [173].
Autef et al. [35] studied geopolymeric reactivity of
three sources of metakaolins produced using three
different processes consisting of a rotary kiln, flash
calcination and oven-heating. The dehydroxylation
temperature was carried out at approximately 750 C
for all metakaolins. It was found that flash-calcined
metakaolin was more reactive than metakaolins
produced through the rotary kiln or oven-heating.
Figure 12 Compressive strength of geopolymer synthesized with
metakaolin samples calcined at temperatures 550–950 C [171]
(reproduced with permission from Elsevier).
J Mater Sci
Similarly, Nicolas et al. [173] compared the geopoly-
meric reactivity of metakaolin obtained using two
different methods of flash calcination and rotary kiln.
For flash calcination, the material was subjected to a
temperature of about 1200 C for few fractions of a
second and rapidly cooled down to 100 C. In the
rotary kiln, the material was calcined between 650
and 700 C for about 3 to 5 h. Their results showed
that traditional rotary-calcined metakaolins tend to
be angular layered particles, whereas flash-calcined
metakaolins contained spherical particles. However,
compressive strength test results showed that the two
methods of calcination produced synthesized
geopolymer materials of comparable properties.
Conclusions
The geopolymeric reactivity of aluminosilicate
materials can be significantly improved by using
several techniques. These activation methods are
classified into four categories of mechanical, thermal,
physical separation and chemical activation which
may be used, singly or in combination. These acti-
vation processes enhance reactivity by increasing the
rate and extent to which silicon and aluminium
species from the activated materials dissolve in
alkaline medium. Consequently, more geopolymeric
gel is formed resulting in the formation of a more
compact microstructure and improved mechanical
properties of the geopolymer products.
While mechanical activation is an effective pre-
dominantly used method, chemical activation by
alkali–thermal fusion has been much less studied
than the other activation methods. Alkali–thermal
fusion presents interesting advantages such as the
production of highly reactive phases with a wide
range of non-reactive raw materials, even with those
where other activation methods are not efficient. This
method allows the synthesis of one-part geopolymer
materials, an alternative and promising approach for
making geopolymeric binders. However, the problem
of mitigating excess alkali in the fused materials
requires incorporation of reactive Al2O3-rich materi-
als as additives, for which further studies are
required.
To alter the reactivity of a given raw material, an
activation method and optimal treatment parameters
need to be suitably selected, considering that the two
factors majorly determine the final properties of the
J Mater Sci
resulting geopolymers. In addition, energy and cost
efficiency of the activation process must be consid-
ered for the purposes of industrial application.
Acknowledgements
This paper is part of the PhD study of Leonel
Noumbissie Tchadjie conducted under the NRF-
TWAS Doctoral Scholarship, Grant No. 99993. The
candidate thanks the National Research Foundation
(NRF) of South Africa for offering him this grant and
study opportunity.
Compliance with ethical standards
Conflict of interest The authors declare that they
have no conflict of interest.
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