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 Geopolymers are alternative materials to portland cement, obtained by alkaline
activation of aluminosilicates. They exhibit excellent properties and a wide
 Springer Science+Business range of potential applications in the field of civil engineering. Several natural
Media, LLC, part of Springer aluminosilicates and industrial by-products can be used for geopolymer syn-
Nature 2017 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

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

Address correspondence to E-mail: [email protected]; [email protected]

https://doi.org/10.1007/s10853-017-1907-7
 J Mater Sci

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

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

design and type of alkaline solutions. Thus, these (Na2CO3) or potash (K2CO3) at temperatures around
parameters can be used to optimize the characteris- 1300 C, followed by dissolution of the resulting
tics of its geopolymer products [27]. Generally, vol- alkali silicate glass in water before or after cooling
canic ash materials are suitable and sustainable raw [54]. Another method of producing silicate solutions
materials for geopolymer synthesis. They are also is by hydrothermal dissolution of a reactive silica
available in huge amounts in certain geographical source in an alkaline solution [55]. Generally, the
regions, are easily accessible which ensures low cost chemical composition of soluble silicates is described
and have low environmental impact [43]. by the SiO2/M2O weight ratio (M = Na, K). For
Use of feldspars and igneous rocks for geopolymer sodium silicates, this SiO2/Na2O weight ratio is quite
syntheses have been reported [5, 10, 46]. Feldspars close to the molar ratio, but both values are quite
are a major constituent of igneous rocks and the most different in potassium silicates [54].
abundant mineral group in the earth’s crust [28]. Although sodium silicate and potassium silicate
Feldspar-based geopolymers generally achieve low solutions appear to have similar properties, the for-
compressive strengths of paste and low degree of mer is less expensive and most commonly used [56].
reaction due to their mineralogical composition, However, potassium silicate solutions present some
which generally consists of high crystalline minerals advantages in their characteristics. For a given SiO2/
that are weakly reactive [5, 10]. M2O ratio, the viscosity of potassium silicate solu-
Several industrial by-products have been used to tions is ten times lower than that of sodium silicate
synthesize geopolymer products. They include fly solutions, which is of benefit in terms of obtaining
ash, slags, palm oil fuel ash, rice husk ash and red good workability with less solution [17]. Also,
mud [6, 31, 47–49]. A lot of research has been done on potassium silicate solutions are less likely to develop
fly ash due to its availability in abundance. The major efflorescence, i.e. formation of alkali carbonate
chemical components in fly ash are SiO2, Al2O3, deposits, which is one of the major issues in sodium-
Fe2O3 and CaO [50, 51]. Much of the published lit- based geopolymers [56, 57]. Finally, materials made
erature has shown major interest in class F fly ash- from potassium silicates present better refractory
based geopolymers. In fact, low calcium content is properties [58, 59]. The Geopolymers Institute rec-
preferable for geopolymers production [2, 6, 11]. ommends the use of low alkaline solution for
Furthermore, the presence of free lime CaO is not geopolymerization as the so called user-friendly
recommended as it generates flash set. Also, a high solution, which typically consists of any soluble sili-
amount of unburnt carbon exceeding 10% inhibits cates with SiO2/M2O ratio greater than 1.40 [17].
geopolymerization [17]. Generally, fly ash geopoly- Such use favours the implementation of resulting
merization exhibits low reactivity, which leads to geopolymer recipes in mass production, which can be
slow setting and low strength development. In fact, easily handled without strong specific safety
the reactivity of fly ash in an alkaline environment is measures.
controlled by various factors such as the natural pH Although the geopolymerization mechanism is not
of the fly ash, particle size distribution, reactive SiO2 fully understood, it generally involves three main
content, glass content and glass composition stages [17, 56].
[11, 52, 53]. However, use of these materials bears the
a. The dissolution of aluminosilicate materials in the
advantage of being economic, with enormous bene-
alkaline medium through the severing of covalent
fits of low cost and limited negative environmental
Si–O–Si and Al–O–Al bonds and formation of
impact [47, 48].
silicate and aluminate species. This process is
initiated by the hydroxyl OH- groups which after
Reaction mechanism and mechanical
bonding to the silicon atom make the Si–O–Si
properties
bond more susceptible to breaking. Dissolution of
In geopolymer synthesis, the alkaline solution usu- reactive aluminosilicates is rapid at high pH [60].
ally consists of a mixture of MOH (M = Na, K) and In metakaolin specifically, the dissolution leads to
alkali metal (M) silicate solution. Soluble silicates or formation of ortho-sialiate molecule ((OH)3Si–O–
water glass is commonly made in industry by alkali Al(OH)- ?
3 Na ), the primary unit in geopolymer-

fusion of purified sand (SiO2) with soda ash ization [17].

J Mater Sci

b. Condensation of silicate and aluminate mono- the dissolution of silica particles. It is known that a
mers to form a gel, until the solution reaches more homogeneous gel is observed with slower alu-
saturation with liberation of NaOH which reacts mina release [63]. Hajimohammadi et al. [62] inves-
again [17]. Duxson et al. [60] claimed that there is tigated the dissolution rate of some geopolymer
coexistence of two types of gel consisting of an precursor materials using a kinetic approach. They
aluminium-rich gel yielding to the geopolymer observed that dissolution rates of silica-rich materials
matrix and another gel yielding to crystallized are much higher than those of aluminosilicates. Also,
zeolite phases. Also, this process releases the among the aluminosilicates studied, metakaolin
water that was nominally consumed during the showed a distinctively higher release of Si species
first step [60]. from the very early hours of dissolution while release
c. Polycondensation and structural reorganization rate of Si and Al species was almost similar in fly ash
of the gel, yielding to the three-dimensional and slag. They also demonstrated that milling of fly
aluminosilicate network of geopolymers [17, 60]. ash increases the average dissolution rate of Si spe-
cies much more than for Al species. But the opposite
Geopolymerization yields products with different
trend is observed with slag where milling rapidly
physical and/or chemical properties, which depend
increases the release rate of Al while the release rate
on the aluminosilicate source material and synthesis
of Si is increased only slowly. Generally, highly
conditions. Geopolymers present some attractive
crystallized minerals present weak dissolution in
properties of interest, including [3, 17]:
alkaline medium [5, 10, 12]. Heal et al. [12] observed
• High flexural and compressive strength, such as that kaolin-based geopolymers do not undergo
compressive strength of paste [ 90 MPa at complete geopolymerization and show slow strength
28 days development, being the limitation by the structure of
• Fast hardening with some types of geopolymer kaolin, which has kaolinite stacks and plates of low
cement achieving 70% of their final compressive surface area.
strength within 4 h Fernández-Jiménez et al. [52] investigated the effect
• High thermal stability with mass loss \ 5% and of chemical composition of fly ash on mechanical
strength loss \ 60% at 1000 C properties of resulting geopolymers. They found that
• Effective passivation of reinforcing steel fly ash with a high content of reactive SiO2 and Al2O3
• Strong adhesion to metallic and non-metallic and lower SiO2/Al2O3 ratio showed the best
surfaces mechanical strengths. Tennakoon et al. [64] found
• Low permeability that fly ash materials with reactive SiO2/Al2O3 molar
• Dimensional stability in service with shrinkage as ratio [ 3.3 induced formation of zeolitic phases,
low as 0.2–0.4% resulting in low strength development. They also
• Long-term durability properties reported that there was a poor correlation between
• Low CO2 footprint the total SiO2/Al2O3 ratio and compressive strength
development. De Silva et al. [65] stated that for
Starting materials metakaolin-based geopolymer, the SiO2/Al2O3 ratio
in the range of 3.4–3.8 showed high strength devel-
It is well known that the properties of geopolymers opment at later ages. Chindaprasirt et al. [66] repor-
are affected by the nature of raw materials such as ted that during the geopolymerization of calcium-
their mineralogical and chemical composition, parti- rich fly ash (ASTM Class C), the setting process is
cle size and glass content [5, 11, 52, 53]. The release controlled by initial calcium–aluminate–silicate–hy-
rate of silica and alumina from source materials plays drate (C–A–S–H) formation while sodium–alumi-
a significant role in the development of geopolymer nate–silicate–hydrate gel (N–A–S–H) formation
network and its final properties [61, 62]. High silica contributes to strength development. Also, SiO2/
availability leads to more contribution from Al in the Al2O3 ratio in the range of 3.2–3.7 showed products
geopolymer matrix and promotes more homogenous with best mechanical properties. Zibouche et al. [67]
geopolymer binder gel [61]. At early stages of the studied the influence of secondary minerals on the
reaction, rapid release of alumina is shown to impede geopolymerization reaction of metakaolin. They
showed that kaolin deposits containing up to 30%
 J Mater Sci

secondary minerals are still suitable for geopolymer Zhan et al. [76] investigated the effects of halloysite in
synthesis, under moderate curing temperatures. kaolin on the formation and properties of geopoly-
Temuujin et al. [68] reported that the reduction in mers. The isothermal conduction calorimetry (ICC)
particle size and change in morphology after milling results showed that the presence of halloysite in
led to a higher dissolution rate of fly ash particles, kaolin led to a higher geopolymerization rate of
yielding 80% increase in compressive strength when metakaolin.
compared with the geopolymer mixtures made from It is widely accepted that amorphous phases are
non-milled fly ash. the reactive components in the geopolymerization
reaction [71, 77, 78]. Usually, most crystalline phases
hardly dissolve during geopolymer reactions
Reactivity of aluminosilicate raw materials [5, 10, 12, 71]. The bulk amorphous composition can
be determined using a combination of X-ray fluo-
Properties of geopolymers can be significantly affec- rescence spectroscopy (XRF) and quantitative X-ray
ted by minor changes in the amount of Si and Al diffraction (QXRD) [78]. Also, quantification of
available for the reaction [62, 64, 65]. Therefore, the amorphous content in raw materials can be made
reactivity of aluminosilicate materials through using alkaline or acidic dissolution techniques
geopolymerization can be defined by its ability to [71, 73]. Williams and Van Riessen [78] reported that
suitably release alumina and silica species in alkaline the use of amorphous composition for geopolymer
medium for further development of rigid 3-D mix design gave products with better compressive
geopolymer network. In geopolymer synthesis, strength than those formulated using the chemical
compressive strength of the resulting product is bulk composition. Djon Li Ndjock et al. [44] investi-
commonly used as a quantitative indicator of gated the effects of amorphous composition of five
geopolymeric reactivity of raw materials [69, 70]. volcanic ash types on properties of resulting
Several attempts have been made to assess reactivity geopolymers. They observed that best compressive
of aluminosilicate materials and determine their strengths were obtained from samples containing a
potential for geopolymerization [29, 64, 71]. Of the high amount of amorphous phase and low SiO2/
common oxides in geopolymer chemistry, i.e. SiO2, Al2O3 molar ratio of amorphous phase. These find-
Al2O3, Fe2O3 and CaO, alumina and silica are the two ings agree with results of similar work done on fly
major oxides which control the geopolymeric net- ash by Fernández-Jiménez et al. [52]. Figure 1 sug-
work formation and strength development [29]. gests potential uses of volcanic ash, according to
Studies have attempted to evaluate source materials composition and the amount of amorphous phase.
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, Figure 1 Utilization of volcanic ash based on amount of
which is a clayey mineral, in one type of volcanic ash amorphous phase and composition [44] (reproduced with permis-
was responsible for its higher reactivity. Similarly, sion from Elsevier).
J Mater Sci

It has also been reported that particle size distri- Mechanical activation
bution of aluminosilicate materials is a key factor in
the process of geopolymer synthesis. Generally, the Mechanical activation can be defined as a process
improvement of geopolymeric reactivity is observed that increases the reactivity of a solid by imparting
with reduction in particle size [68, 79–81]. Temuujin mechanical energy, without altering chemical com-
et al. [68] investigated the effects of mechanical acti- position [82]. If the activation simultaneously leads to
vation of fly ash on physical properties of geopoly- change in composition or structure, it is a
mers. They observed that a reduction in the median mechanochemical reaction. The increase in reactivity
size (d50) from 14.4 lm for the raw fly ash to 6.8 lm during mechanical treatment is usually a result of
for the milled fly ash led to 80% increase in com- disordering of the crystal and generation of defects or
pressive strength of the resulting geopolymer paste. other metastable forms that cause decrease in acti-
This increase in compressive strength is attributed to vation energy barrier for the process [83]. The pri-
reduction in particle size and change in morphology, mary effect of mechanical activation is the reduction
allowing a higher dissolution rate of the fly ash par- in particle sizes, causing changes in physical prop-
ticles [68]. It is important to note that the aforemen- erties such as particle size distribution, specific sur-
tioned factors affecting the geopolymeric reactivity of face area, surface energy and phase composition
aluminosilicate materials are interrelated. Each factor [84, 85]. The mechanism of transformation occurring
plays a significant role but may not singularly be during mechanical activation of materials can be
sufficient for good strength development. It is sug- divided into three main stages, which depend on the
gested that the effects of these factors may not be degree of dispersion and grinding time, as illustrated
considered individually when a specific raw material in Fig. 3 [86].
is studied. a. At stage 1, grinding initially leads to relatively
rapid particle size reduction and increase in
specific surface area. The energy consumed dur-
Techniques for increasing reactivity ing grinding is proportional to the particle
of aluminosilicate raw materials surface area produced. This stage is referred to
as Rittinger’s stage.
The geopolymeric reactivity of source materials is a
b. At stage 2, grinding continues and as particles get
major parameter for its utilization. A great number of
finer, they begin to adhere to surfaces of grinding
natural aluminosilicates and industrial by-products
media and mill, as well as to each other. The
can be used for geopolymer synthesis, as discussed in
energy used for size reduction is no longer
section ‘‘Aluminosilicate raw materials’’. Neverthe-
proportional to the increase in surface area.
less, a large number of potential starting materials
Despite this nonlinearity, the increase in disper-
have poor reactivity and consequently yield products
sion can still be remarkable. This is considered to
with low mechanical strength. Improving reactivity
be the aggregation stage.
of geopolymers is essential for their potential struc-
c. At stage 3, more grinding does not lead to further
tural use in concrete, while promoting utilization of
size reduction but may cause decrease in the
locally available source materials to mitigate envi-
degree of dispersion in certain materials. In this
ronmental issues of landfill and disposal of some
stage of agglomeration, the crystal structure or
industrial wastes. In the literature, several techniques
even the chemical composition of the material
have been investigated to alter reactivity of alumi-
changes.
nosilicate raw materials. These activation methods
may be divided into four categories consisting of During comminution of solid matter, adhesion
mechanical, thermal, physical separation and chemi- phenomena become more and more important with
cal activation, as given in Fig. 2. A combination of decreasing particle size causing aggregation,
these treatments can be performed. 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
 J Mater Sci

Figure 2 Summary of
activation methods.

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
Figure 3 Theoretical diagram of the grinding process [86] higher rate and extent of grinding efficiency com-
(reproduced with permission from Elsevier). pared to the normal rotary ball mills [89].
The efficiency of milling can be affected by many
interparticle bonds [84]. Adhesion during grinding is factors such as type of mill, types of grinding media
always undesirable as it diminishes the effect of such as balls, rods or other shapes, material of milling
grinding, lengthens the grinding time and increases media, e.g. stainless steel, tungsten carbide, zirco-
the energy requirement [87]. While aggregation nium oxide, aluminium oxide, silicon nitride, grind-
mostly influences the progression and effectiveness ing atmosphere such as air, inert gas, reductive gas,
of the grinding process, agglomeration has a detri- wet or dry milling atmosphere, fill level of the milling
mental effect on certain properties of the ground chamber, ball-to-powder ratio (BPR), grinding tem-
material [86]. However, adhesion can be avoided by perature, speed of the mill and grinding time [82].
using dispersion agents, also called grinding aids Mechanical activation has been found to improve
[84, 87]. the reactivity of solids in many materials processing
Mechanical activation is usually carried out using operations such as extractive metallurgy, building
devices called mills, which may be of different char- materials, food and chemicals [83, 90–92]. Several
acteristics. Several types of mills have been designed studies have reported the effects of mechanical
J Mater Sci

activation of raw materials on properties of bearing effect’’ which reduces workability. Figure 4a,
geopolymers [11, 80, 81, 85, 93–97]. From reported b shows the microstructure of raw fly ash and milled
data, the geopolymeric reactivity of mechanically fly ash, respectively. Also, faster setting was observed
activated materials depends on factors such as type with mechanically activated fly ash. This was miti-
of mill, milled material, milling time and milling gated by addition of extra water in the starting
atmosphere [80, 95, 96, 98]. Kumar et al. [99] prepared mixture.
geopolymer materials from mechanically activated Mucsi et al. [96] investigated the correlation
fly ash. The alkaline activator was a solution with between grinding process, ground materials and
20% NaOH concentration, and the liquid/solid ratio geopolymer properties. A 6 M solution of NaOH was
was 0.5. They found that geopolymerization of used as activator with a mix of 0.65 liquid/solid ratio.
mechanically activated fly ash occurred at a lower Mechanical activation was carried out using three
temperature and setting time, as compared to the different types of laboratory scale mills comprising
reaction of raw fly ash. The effect of mechanical the conventional tumbling ball mill, vibratory mill
activation was influenced by the mill type. Moreover, and stirred media mill. The finest ground product
ground materials from vibratory mill achieved better produced with lowest energy input was obtained
compressive strength than those obtained using using the stirred media mill. It was reported that the
attrition mill. The improvement in compressive compressive strength of the geopolymer samples
strength was found to be related to increased reac- strongly depended on the type of mill and milling
tivity and the resulting formation of compact time. The compressive strengths of paste obtained
microstructure. Compressive strength of upto from the fly ash that was activated in stirred media
120 MPa was obtained with 50 mm cube geopolymer mill, vibratory mill and ball mill were 22, 16 and
pastes made using mechanically activated fly ash. 15 MPa, respectively. The superiority in strength of
These results were in agreement with findings of the geopolymer product from activated fly ash that
Temuujin et al. [68], who also observed increased was milled using stirred media mill was attributed to
reactivity in mechanically activated fly ash during the its particle size distribution, which reportedly varied
synthesis of geopolymers cured at ambient tempera- from superfine particles of\ 1 lm to coarser particles
ture. In their study, a mixture of 14 M NaOH and of size 200–300 lm. Its median particle size was
sodium silicate solution was used as activator. Their 5.2 lm. Finer particles exhibit better solubility
results indicated that mechanical activation led to resulting in more geopolymer gel while coarser par-
reduction in particle size and change in particle ticles behave as ‘‘aggregate’’ in the geopolymer
shape, allowing a higher dissolution rate of the fly matrix. Also, the filler effect of the superfine unre-
ash particles. Mechanical activation led to 80% acted size fraction \ 1 lm leads to a more compact
increase in compressive strength of 25 9 50 mm microstructure.
paste cylinders over strengths of geopolymers Kumar and Kumar [11] investigated the effects of
obtained from raw fly ash. On the other hand, milling duration conducted at 5, 10, 20, 30, 45, 60 and
mechanical activation of the fly ash destroyed some 90 min on the reaction kinetics of geopolymerization
of its spherical morphology and reduced the ‘‘ball as well as on the characteristics of resulting products.

Figure 4 Morphology of raw (a) and milled fly ash particles (b) [68] (reproduced with permission from Elsevier).
 J Mater Sci

A solution of 6 M NaOH concentration was used as based geopolymers was related to the amount of
the alkaline activator. The reactivity of fly ash reactive species, i.e. Si and Al, in the ground mate-
increased with reduction in median particle size and rials. Higher dissolution of Si and Al species sub-
with increase in milling time. Mechanical activation stantially improved the compressive strength. Other
enhanced the rate of geopolymeric reactivity and studies have reported the negative effect of pro-
decreased the setting time when the median particle longed grinding. Mucsi et al. [100] claimed that
size was reduced to less than 5–7 lm. Results of during mechanical activation of lignite fly ash in
isothermal conduction calorimetry studies conducted stirred media mill, the compressive strength of the
at 27 C showed evidence of geopolymerization of geopolymer samples increased with milling time up
mechanically activated fly ash, characterized by a to certain fineness. After that, further grinding led to
broad exothermic peak. The improvement in physical decrease in compressive strength. Earlier work by
properties of the geopolymer products was correlated Mucsi et al. [96] gave similar results. Figure 6 shows
with median particle size reduction and change in that indeed the strength enhancing effect of grinding
reactivity of fly ash. Similarly, Djobo et al. [80] stud- is only effective to a certain level of material fineness
ied the effects of extended milling of volcanic ash achieved. Extreme fineness, due to a prolonged
done using vibratory mill on geopolymeric reactivity. duration of grinding, may not improve mechanical
The alkaline activator used was sodium silicate properties any further. Prior to using a starting
solution with SiO2/Na2O molar ratio of 1.45. X-ray material as a geopolymer, it seems essential that this
diffraction (XRD) results showed that mechanical optimum fineness should be determined to avoid
activation considerably reduced the degree of crys- potential adverse effects of over-grinding.
tallinity for samples that were milled for 90 min. This Mechanical activation was also found to be effec-
was followed by change in the mineralogy of samples tive for less-reactive kaolin, achieving products with
milled for 120 min. The rate and extent of geopoly- good compressive strengths [32, 101]. Hounsi et al.
merization increased with milling time. A 100% [32] observed the partial amorphization of kaolin
increase in compressive strength was observed after during mechanical activation, as indicated by inten-
the mechanical treatment. Thus, mechanical activa- sity reduction in main characteristic peaks of XRD
tion may be considered as a suitable method for patterns for the milled samples. Thus, milling chan-
improving the reactivity of raw volcanic ash. Wei ged the crystallinity degree of the raw kaolin and
et al. [81] showed that the silicon and aluminium promoted geopolymerization reaction, leading to
species from mechanically activated materials increase in compressive strength. Results showed
increasingly dissolved in alkaline medium the longer that without mechanical activation, the optimal cur-
the milling time, as shown in Fig. 5. It was reported ing condition was 24 h at 70 C for which the com-
that the development of strength for milled material- pressive strength of 50 mm cube pastes after 28 days

Figure 5 Content of active Si and Al in tailings subjected to

different milling times [81] (reproduced with permission from Figure 6 Variation of compression strength as a function of
Elsevier). grinding time (constructed with data from Ref. [96]).
J Mater Sci

of curing was 15 MPa. Mechanical activation led to CO2-milled slag relative to air-milled slag was
35% strength increase for the same curing and testing reported for zinc slag [98].
conditions. The alkaline activator used was a mixture A recent study investigated the influence of
of sodium silicate solution and 8 M NaOH solution at mechanical activation of fly ash on the micro- and
the Na2SiO3/NaOH mass ratio of 0.32. Heah et al. nano-structure of geopolymers using transmission
[101] conducted scanning electron microscopy (SEM) electron microscopy (TEM–EDS). They found that
study and reported that the plate-like structure of milling mostly decreased the amount of the amor-
kaolin reduced after mechanical treatment. In their phous aluminosilicate rather than crystalline phases
study, the milled kaolin showed a smoother surface present in fly ash, as shown in Fig. 8 [103]. Thermo-
and exhibited edge distortion of particles. Mechanical dynamically, glass has higher free energy than crys-
activation improved the geopolymerization process. talline phases, thus the introduction of additional
Extended milling time increased compressive energy by milling results in more particle breakage
strength while the microstructure of the geopolymer and alteration. A minor effect was observed on
products became more compact and denser. Figure 7 mullite that is at nanometric scale and is embedded
shows the micrographs of milled kaolin geopolymers in the amorphous phase. It was demonstrated that
[101]. mechanical activation promoted the formation of
Milling atmosphere is also an important parameter geopolymer gel, mainly N–A–S–H gel with an
that affects the geopolymeric reactivity of milled increase in its nano-pore size. Also, isothermal con-
materials. Preliminary studies by Kalinkin et al. [102] duction calorimetric study showed that the early
have shown that mechanical activation of Cu–Ni slag reaction corresponding to dissolution/precipitation
in CO2 gives higher compressive strength for the had a linear relationship with milling time, but not
geopolymer samples, compared to its mechanical with median particle size. A conceptual mechanism
activation in air. Sodium silicate solution with a of the reaction was also proposed, as illustrated in the
SiO2/Na2O ratio of 1.5 was used as alkaline activator. schematic diagram of Fig. 9 [103].
The higher geopolymeric reactivity of samples milled Generally, mechanical activation of the raw mate-
in CO2 was attributed to chemisorption of CO2 rial leads to a reduction in particle size, increase in
molecules in the form of distorted carbonate ions specific surface area, decrease in crystallinity, change
during mechanical activation. This phenomenon in the mineralogical composition and increase in the
promoted more intensive interaction of alkaline amorphous phase. These effects promote greater
solution with activated slag particles. After 360 days, dissolution of the milled materials in alkaline solu-
compressive strength was 89.5 and 119.0 MPa for tion, consequently enhancing the geopolymerization
14.1 mm cube geopolymer mortars prepared using reaction [11, 80, 94, 104]. As a result, there is
slag that was activated in air and in CO2, respectively improvement in properties of products made from
[102]. A similar trend in which greater compressive mechanically activated geopolymer materials
strength of geopolymer mortars was obtained using [93, 95, 97]. Therefore, mechanical activation can be

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]).
 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
Figure 8 Quantitative phase analysis showing variation of crys- study the effects of separation method of activation
talline and amorphous phases with milling time [103] (reproduced on the properties of geopolymers. Kumar et al. [114]
with permission from Elsevier).
argued that the geopolymeric reactivity of fly ash was
altered by air classification using a laboratory classi-
considered as an effective technique for improving
fier operated at 10,000 rev/min. An increase in the
the properties of geopolymer products. The tech-
glass content of finer fractions obtained by air clas-
nique may be employed to beneficially utilize less-
sification was observed relative to raw fly ash,
reactive waste materials that are typically disposed
resulting in increase in compressive strength of its
off as landfills [81, 85, 96].
geopolymer pastes. Chindaprasirt et al. [115] also
observed that after separation of high-calcium fly ash
Activation by physical separation
using air classifier, the amorphous phase content in
This process which gives unmodified particles is the fine fraction was higher than in the coarser frac-
based on physical properties of the materials such as tion. A mixture of Na2SiO3 solution and 10 M NaOH
density, particle size, shape, surface properties, elec- solution was used as alkali activator. It was demon-
trical and magnetic properties [105, 106]. Activation strated that the setting time of geopolymer pastes
by physical separation of particle fractions includes decreased with an increase in fly ash fineness. There

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

was improvement in workability, strength and dry- Concrete admixtures are materials other than
ing shrinkage properties of mortars made using the hydraulic cement, water or aggregates that are added
fine fly ash. Geopolymer mortars giving 28-day immediately before or during mixing [118]. These
compressive strength of up to 86.0 MPa were admixtures enhance the properties of portland
obtained using 50 mm-size cube specimens. cement concrete in the fresh and/or hardened state
Nugteren et al. [116] prepared geopolymer pastes [119]. There are several types of admixtures used in
using six different size fractions of fly ash obtained by concrete technology, broadly categorized as chemical
air classification. The alkaline solution used was or mineral admixtures [118]. Chemical admixtures
potassium silicate solution with SiO2/K2O molar are generally water soluble and are added in small
ratio of 1.25. They found that physical separation amounts to control various properties of fresh or
affected the pH, bulk chemical and mineralogical hardened concrete. The different types of chemical
composition of the fractions, as well as their particle admixtures include accelerators, water reducers,
size distributions. The pH obtained for the various superplasticizers and retarders [118].
size fractions varied from 10.2 for the finest fraction Mineral admixtures are fine ground solid materials
to 12.5 for the raw sample. The workability and set- usually categorized as filler materials, pozzolans or
ting time of the paste were also influenced by size SCMs, latent hydraulic materials [120]. The most
fractions. However, the relationship between particle common SCMs are fly ash, ground granulated blast
size and strength was not well established, although furnace slag, natural pozzolans and silica fume [119].
the variations in chemistry and pH of the different Incorporation of mineral admixtures as SCMs in
fractions could play a role in strength development. concrete may reduce or increase strength, improve
Compressive strengths of over 100 MPa for cylinder durability, decrease the heat of hydration in mass
specimen of sizes 29 mm diameter 9 25 mm height concretes, reduce cost [119, 120]. Numerous studies
were obtained in this study. It is worth noting that have reported the use of chemical and mineral
when the different size fractions of the fly ash were admixtures in the synthesis of geopolymers and their
obtained by grinding, their pH values, bulk chemical effects on properties [121–124]. The present literature
and mineralogical compositions showed no review is limited to ingredients that may be used to
notable differences. Kumar et al. [117] investigated improve the geopolymeric reactivity of the raw alu-
the geopolymerization activity for different fractions minosilicate materials. The activation of geopolymer
of fly ash, separated into various sizes then drawn materials using chemical admixtures is usually car-
from hoppers of an electrostatic precipitator. They ried out using two methods, namely blending and
found that the different size fractions of fly ash col- alkaline fusion.
lected showed marked variations in chemistry, min-
eralogy, particle size distribution and glass content. Blending technique
From chemical analyses, the SiO2/Al2O3 ratio
increased with increase in fineness, whereas Fe2O3, The conventional blending technique involves com-
CaO and loss on ignition decreased in finer fractions. bining the raw material with a chemical additive by
A linear correlation between geopolymeric reactivity mixing the two. This technique adjusts the bulk
and glass content was observed. Strength develop- chemical composition of the raw material, causing a
ment was attributed to the combined effects of SiO2/ change in its geopolymeric reactivity. The composi-
Al2O3 ratio, particle size and glass content. tional changes typically involve modification in the
Microstructural studies done using SEM–EDS on amount of mainly SiO2, Al2O3 and CaO oxides. Ola-
hardened geopolymer pastes revealed the presence of lekan et al. [125] investigated the effects of Al(OH)3
more reaction products (i.e. N–A–S–H gel) in finer addition on the properties of slag/ultrafine palm oil
fractions while unreacted particles were prevalent in fuel ash geopolymer system. A combination of 10 M
coarser fractions. NaOH solution and Na2SiO3 solution was used as
alkaline activator. The mass ratio of sodium silicate to
Chemical activation NaOH of 2.5 was employed. They found that the
inclusion of Al(OH)3 in the range of 2–6 wt% led to
Chemical activation is a method of improving reac- change in SiO2/Al2O3, H2O/Na2O ratios and com-
tivity of a material system by addition of admixtures. 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 observed that the partial replacement of natural
effect of blast furnace slag grades on fly ash-based pozzolans by metakaolin of up to 20 wt% signifi-
geopolymer waste. Their results showed that at a cantly improved the compressive strength of the
higher grade, GGBS generated more hydration heat, mixtures. This enhancement of mechanical properties
suggesting higher reactivity and geopolymerization. was attributed to an increase in the amount of
Davidovits et al. [142] developed slag–fly ash- amorphous SiO2 and Al2O3. The addition of meta-
based geopolymer cement that hardened at room kaolin promoted the formation of a more
temperature. Potassium silicate solution with the stable geopolymeric gel with lower porosity. A
SiO2/K2O molar ratio of 1.25 was used as alkaline combination of NaOH solution and sodium silicate
reagent. They showed that the main contributors to solution was employed as activator with different
the geopolymer matrix, which are consequently SiO2/Na2O molar ratio in the range of 0.55–2.78. A
responsible for the compressive strength develop- 28-day compressive strength of up to 68 MPa was
ment, were the glassy fly ash particles supplying Si obtained under room temperature curing on 20 mm
and Al, the high Ca slag supplying Ca and the alka- cube pastes. These results agree with those obtained
line solution providing K-silicate. The geopolymer by Djobo et al. [9] who claimed that the reactivity of
cement produced in their study [142] showed com- volcanic scoria could be altered by its partial
pressive strengths of 29 mm diameter 9 25 mm replacement by metakaolin to compensate for the
height cylinder pastes of up to 95 MPa after 28 days deficiency of amorphous SiO2 and Al2O3 in the vol-
of curing. It also exhibited long-term durability canic scoria. The alkaline activator used in the study
properties. Similarly, Salih et al. [143] demonstrated was a mixture of 12 M NaOH solution and Na2SiO3
that high-strength geopolymer binders made using solution with two SiO2/Na2O molar ratios of 1.1 and
palm oil fuel ash (POFA) and GGBS could be syn- 1.4. In their study, 5–25% metakaolin was added,
thesized at ambient temperature. In the study, a resulting in higher dissolution of Al2O3 and SiO2
combination of Na2SiO3 and NaOH was used as species, polycondensation, increase in compressive
activator. Addition of GGBS as partial replacement of strength and decrease in setting time. The compres-
POFA increased the compressive strength at all ages. sive strengths of 31 mm diameter 9 62 mm height
Up to 65% increase in compressive strength of 50 mm cylinder pastes at 28 days were up to 68.8 MPa.
cube paste samples was achieved when 50% of POFA Similarly, Ogundiran and Kumar [146] investi-
was replaced with GGBS. Ye et al. [144] investigated gated the effects of calcined clay addition to fly ash
the properties of geopolymers synthesized by reactivity, physical and mechanical properties of
blending 70% calcined tailings and 30% slag. The geopolymer composite. A mixture of 8 M NaOH
alkaline solution consisted of Na2SiO3 solution solution and Na2SiO3 solution at NaOH/Na2SiO3
modified using NaOH to SiO2/Na2O molar ratio of mass ratio of 1 was used as activator. It was found
1.8. The microstructure and strength development for that calcined clay addition accelerated dissolution/
the geopolymer mortars cured at ambient tempera- hydrolysis of fly ash, while fly ash controlled the
ture were monitored over a period of 6 years. Results exothermic reaction that accompanied alkaline dis-
indicated that hardened geopolymer mortars became solution and hydrolysis of calcined clay. Addition of
more compact with advancing age, due to progres- 25 wt% calcined clay improved the early- and late-
sive geopolymerization attributed to formation of age strengths of the geopolymer pastes. They con-
coexisting C–A–S–H and N–A–S–H gels. Compres- cluded that the rate of geopolymer formation and the
sive strength of 40 9 40 9 160 mm prismatic mortars compressive strength of the less-reactive silica-rich
significantly increased from 50.0 MPa at 28 days to geopolymer source materials can be improved by the
75.0 MPa at 6 years. Carbonation was observed in addition of calcined kaolin clay.
both the early-age and long-term geopolymers, but
deterioration of the system was inhibited by the Alkaline fusion
stable N–A–S–H gels which were the predominant
geopolymeric products. Geopolymeric reactivity can be also improved by
The influence of highly reactive metakaolin as alkaline fusion of the raw materials. In this method,
substitute in less-reactive geopolymeric system has the mixture of raw material and sodium hydroxide is
been widely investigated. Robayo-salazar et al. [145] 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 increased the dissolution of Si species in alkaline
treatment can be affected by several factors such as medium, but Al species solubility was less influ-
heating rate, holding temperature, holding time, enced. In one case, compressive strength of 20 mm
heating atmosphere and the rate of cooling [158–160]. cube pastes increased from 5 MPa for the raw poz-
The heat treatment process is a significant operation zolan to 19.3 MPa for the same pozzolan calcined at
used in manufacturing of various engineering mate- 800 C. Generally, the geopolymeric reactivity of
rials such as steel, ceramics and cement. For instance, calcined natural pozzolans was correlated with their
portland cement is made by thermal activation of a mineralogical composition. Rieger et al. [169] studied
mixture of limestone and clay or other materials of geopolymerization of shale–slag calcined at different
similar bulk composition and sufficient reactivity, at temperatures. An aqueous solution of Na2SiO3 with
a temperature of about 1450 C. Partial fusion of the silica modulus of 1.71 and content of water-soluble
raw mix occurs, and nodules of clinker are produced solids 32.28% was used as activator. The XRD and
[119]. Fourier transform infrared spectroscopy (FTIR)
Various studies have investigated the effect of analysis revealed that the raw material subjected to
thermal activation of raw geopolymer materials on thermal treatment at 600 C provided the most reac-
geopolymerization process, of which thermal activa- tive state, giving the highest compressive strength of
tion of kaolin has been of interest as reported in the geopolymer mortar at 82.5 MPa. However, further
literature [8, 47, 162–164]. Generally, heating of clay firing at temperatures greater than 800 C was
minerals leads to change in its structure, which varies detrimental, due to an increase in the crystalline
for different clay mineral groups [165]. Kaolinite is content and a significant reduction in the alkaline-
transformed into metakaolin through calcination. hardening reaction. Also, other studies have similarly
Due to the high reactivity and purity of metakaolins, reported the negative effect of very high-temperature
it is one of the most explored aluminosilicates for calcination of the raw material on geopolymerization
synthesis of geopolymers [166, 167]. Often, kaolinite [170].
is converted into metakaolin by calcination at tem- Temuujin et al. [170] found that preliminary calci-
peratures between 700 and 900 C, before being used nation of fly ash at 500 and 800 C induced de-car-
for geopolymer synthesis [7, 33–35]. Calcination bonation and also led to some decrease in the
causes the dehydroxylation of kaolinite and forma- amorphous content of the fly ash from 60 to 57%. The
tion of an amorphous phase, which is highly reactive alkaline activator used was 14 M NaOH and Na2SiO3
in alkaline medium [7, 34, 35]. Similar effects of cal- solution. In this case, compressive strength of 25 mm
cination are observed with other aluminosilicate diameter 9 50 mm height cylinder pastes decreased
materials as well. Ye et al. [161] reported that thermal from 55.7 MPa for raw fly ash-based geopolymer to
activation improved the solubility of red mud in 44.3 MPa after calcination at 800 C. The drop in
alkaline solution and promoted geopolymerization. compressive strength of the geopolymer pastes after
The activator was alkaline solution containing calcination was attributed to the partial crystalliza-
sodium silicate prepared by dissolving sodium tion of the aluminosilicates and haematite on the
hydroxide in sodium silicate solution to reach dif- surface of the fly ash particles. It was suggested that
ferent SiO2/Na2O molar ratios. Mineral phases in the such crystallized aluminosilicate (mullite) and hae-
red mud transformed successively with an increase matite prevent dissolution of the aluminate and sili-
in temperature, forming new phases with different cate species in the alkaline solution. Similar findings
solubility. The dissolution efficiencies of alumina and were also reported by Wan et al. [171] who high-
silica reached a maximum when red mud was cal- lighted that recrystallization taking place during
cined at 800 C, resulting in the highest compressive calcination of kaolinite at higher temperatures is
strength of binders. significantly detrimental to the dissolution of result-
Also, Bondar et al. [168] investigated the effect of ing metakaolin during geopolymerization. Figure 12
thermal activation at 700, 800 and 900 C on the shows the compressive strength of the 25 mm
geopolymeric reactivity of five natural pozzolans. A diameter 9 50 mm height cylinder geopolymer
mixture of Na2SiO3 solution with SiO2/Na2O molar pastes for metakaolin heated to various high
ratio of 2.1 and KOH solution was used as the acti- temperatures.
vators. It was found that calcination significantly
 J Mater Sci

It is worth noting that calcination temperature is Similarly, Nicolas et al. [173] compared the geopoly-
not the only important parameter that controls the meric reactivity of metakaolin obtained using two
geopolymeric reactivity of aluminosilicates. The different methods of flash calcination and rotary kiln.
method of calcination also plays a role in the phase For flash calcination, the material was subjected to a
transformations induced by thermal treatment and in temperature of about 1200 C for few fractions of a
turn affects reactivity of the calcined geopolymer second and rapidly cooled down to 100 C. In the
material. Kenne et al. [172] studied the effect of cal- rotary kiln, the material was calcined between 650
cination rate on the properties of metakaolin-based and 700 C for about 3 to 5 h. Their results showed
geopolymers. In their experiment, kaolinite was cal- that traditional rotary-calcined metakaolins tend to
cinated at 700 C for 30 min using different rates of be angular layered particles, whereas flash-calcined
calcination: 1, 2.5, 5, 10, 15 and 20 C/min. The metakaolins contained spherical particles. However,
alkaline activator used was prepared by mixing compressive strength test results showed that the two
sodium silicate solution and 12 M NaOH to obtain methods of calcination produced synthesized
Na2O/SiO2 molar ratio of 0.7. They reported that geopolymer materials of comparable properties.
geopolymer pastes with low setting time and high
compressive strength were obtained from metakaolin
calcined at a low rate. Compressive strength of Conclusions
20 mm cube mortars decreased from 49.4 to
20.8 MPa, when the rate of heating increased from 1 The geopolymeric reactivity of aluminosilicate
to 20 C/min. Recently, some studies have reported materials can be significantly improved by using
on the use of flash calcination to produce metakaolin several techniques. These activation methods are
[167, 173, 174]. In this method, a pulverized material classified into four categories of mechanical, thermal,
is heated quickly, held at temperature for a short time physical separation and chemical activation which
and cooled down at a rate of about 103–105 C per may be used, singly or in combination. These acti-
second [173]. vation processes enhance reactivity by increasing the
Autef et al. [35] studied geopolymeric reactivity of rate and extent to which silicon and aluminium
three sources of metakaolins produced using three species from the activated materials dissolve in
different processes consisting of a rotary kiln, flash alkaline medium. Consequently, more geopolymeric
calcination and oven-heating. The dehydroxylation gel is formed resulting in the formation of a more
temperature was carried out at approximately 750 C compact microstructure and improved mechanical
for all metakaolins. It was found that flash-calcined properties of the geopolymer products.
metakaolin was more reactive than metakaolins While mechanical activation is an effective pre-
produced through the rotary kiln or oven-heating. 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
Figure 12 Compressive strength of geopolymer synthesized with
activation method and optimal treatment parameters
metakaolin samples calcined at temperatures 550–950 C [171] need to be suitably selected, considering that the two
(reproduced with permission from Elsevier). factors majorly determine the final properties of the
J Mater Sci

resulting geopolymers. In addition, energy and cost [10] Tchadjié LN, Djobo JNY, Ranjbar N, Tchakouté HK,
efficiency of the activation process must be consid- Kenne BBD, Elimbi A (2016) Potential of using granite
ered for the purposes of industrial application. waste as raw material for geopolymer synthesis. Ceram Int
42(2):3046–3055
[11] Kumar S, Kumar R (2011) Mechanical activation of fly ash:
Acknowledgements effect on reaction, structure and properties of resulting
geopolymer. Ceram Int 37(2):533–541
This paper is part of the PhD study of Leonel [12] Heah CY et al (2012) Study on solids-to-liquid and alkaline
Noumbissie Tchadjie conducted under the NRF- activator ratios on kaolin-based geopolymers. Constr Build
TWAS Doctoral Scholarship, Grant No. 99993. The Mater 35:912–922
candidate thanks the National Research Foundation [13] Tchakoute HK, Elimbi A, Yanne E, Djangang CN (2013)
(NRF) of South Africa for offering him this grant and Utilization of volcanic ashes for the production of
study opportunity. geopolymers cured at ambient temperature. Cem Concr
Compos 38:75–81
Compliance with ethical standards [14] Komnitsas K, Zaharaki D (2007) Geopolymerisation: a
review and prospects for the minerals industry. Miner Eng
Conflict of interest The authors declare that they
20:1261–1277
have no conflict of interest.
[15] Rattanasak U, Chindaprasirt P (2009) Influence of NaOH
solution on the synthesis of fly ash geopolymer. Miner Eng
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