e-Polymers 2022; 22: 108–124
Review Article
Hengels Castillo*, Humberto Collado, Thomas Droguett, Mario Vesely, Pamela Garrido, and
Sergio Palma
State of the art of geopolymers: A review
https://doi.org/10.1515/epoly-2022-0015
received August 06, 2021; accepted December 14, 2021
Abstract: Geopolymers emerge as an ecological alterna-
tive for construction materials. These consist of a mixture
of aluminosilicate sources and an alkaline solution that
dissolves the silicon and aluminum monomers that come
from the source to generate a gel called N–A–S–H that
will control the main properties of the geopolymer. The
geopolymer stands out for having good resistance to
compression, as well as good resistance to high tempera-
tures and corrosive environments. They have great poten-
tial as a replacement for classical technologies such as
concrete, however, require further applied research to
determine their feasibility on an industrial scale.
Keywords: geopolymers, gel N–A–S–H, aluminum, silicon,
sodium
1 Introduction
A geopolymer is a semi-crystalline amorphous material
formed through the polymerization reaction between an

* Corresponding author: Hengels Castillo, Department of
Metallurgical and Materials Engineering, Complex Fluids
Laboratory, Federico Santa María Technical University, Santiago,
San Joaquín 8940572, Chile; JRI Ingeniería S.A., Department
of Geotechnics, Santiago, Ñuñoa 7770445, Chile,
e-mail: hcastillo@jri.cl
Humberto Collado: Department of Metallurgical Engineering and
Materials, Complex Fluids Laboratory, Federico Santa María Technical
University, Santiago, San Joaquín 8940572, Chile; JRI Ingeniería S.A.,
Department of Geotechnics, Santiago, Ñuñoa 7770445, Chile
Thomas Droguett: Department of Metallurgical Engineering,
University of Santiago de Chile, Santiago, 9170022, Chile;
Sustainable Mining Research Center CIMS-JRI, Santiago,
La Reina 7850000, Chile
Pamela Garrido: CIMS-JRI Sustainable Mining Research Center,
General Manager, Santiago, La Reina 7850000, Chile
Mario Vesely: JRI Ingeniería S.A., Technical Management, Santiago,
Ñuñoa 7770445, Chile
Sergio Palma: Department of Metallurgical and Materials
Engineering, Complex Fluids Laboratory, Federico Santa María
Technical University, Santiago, San Joaquín 8940572, Chile
Open Access. © 2022 Hengels Castillo et al., published by De Gruyter.
International License.
aluminosilicate source and an alkaline reagent. The poly-
merization process can be induced and/or catalyzed by
the application of heat.
Geopolymers have been studied largely as building
materials. It is a technology being developed in order to
find a more eco-friendly option compared to Portland
cement that forms concretes, bricks, etc. Their great
advantage is that they can be generated through by-pro-
ducts from other industries. The best known example is
fly ash from coal-fired power plants.
Geopolymer precursor materials, both in natural and
by-product forms, are required to be rich in alumina
(Al2O3) and silica (SiO2 ) because the elements present in
these compounds play an important role in the hardening
of geopolymers, since together with other elements they
form the N–A–S–H gel, which is responsible for pro-
viding the characteristic strength of the material.
To produce a geopolymer, an alkaline reagent is also
needed, which is responsible for the dissolution of the alumino-
silicates present in the raw material. There are different reagents
for the activation of geopolymers, the most used are silicate
solutions and alkaline hydroxides. The use of different reagents
produces geopolymers of different characteristics, so the choice
of reagents depends on the properties sought.
During dissolution of the raw material, aluminum
(Al) and silicon (Si) are released, which, preceded by a
polymerization process, generates an initial Al-rich gel.
Subsequently, the Si in the solution reacts with this gel,
which forms the final Si-rich gel. The main product of this
reaction is the N–A–S–H gel.
Geopolymers have been investigated in the construc-
tion area because of their good compressive strength,
good volumetric stability, low permeability, and good
resistance to high temperatures.
Current studies are focused on understanding the
operation of the activation of aluminosilicate sources by
alkaline means to generate these geopolymers. Many
authors have participated in these investigations, even
managed to generate compilation texts (1) that allow
updating and providing a basis for future studies.
This article seeks to compile the studies carried out on
geopolymers, especially on their formation, and also the
most influential variables and the properties they possess.
This work is licensed under the Creative Commons Attribution 4.0

1.1 Definition
The concept of geopolymer is a composition of the prefix
“geo,” which corresponds to “earth” in Greek, referring to
the content of Al and Si both of which are highly present
in the earth’s crust (2). The “polymer” reference corresponds
to its structure made up of various Al and Si monomers.
Geopolymers are formed by the reaction of an alkaline
reagent with a source of aluminosilicates (2). This process
can occur at room temperature and at high temperatures
(e.g., 90°C). The material with aluminosilicates (fly ash,
metakaolin, calcined clay, among others) reacts with an
alkaline activator that contains alkali hydroxides, silicates,
aluminates, carbonates, and/or sulfates (Figure 1).
Sometimes, geopolymers are related as zeolitic precur-
sors. They are so called because they have a three-dimen-
sional (3D) tetrahedron structure formed by aluminates
and silicates. However, they differ in that zeolites have
an ordered crystalline structure and geopolymers have
an amorphous one. In addition, higher pressures and tem-
peratures are used to form zeolites (over 100°C and around
200 kPa, respectively) to achieve the formation of the crys-
talline structure. The reaction process of geopolymers
oriented to the formation of cementitious materials can
be considered as a zeolitization where the crystallization
stage is not achieved (3).
1.2 History
The chemical studies of Joseph Davidovits focused on the
chemistry of organic polymers. After several catastrophic
fires in France between 1970 and 1972, where organic plastic
Figure 1: Diagram of the process of creating a geopolymer.
State of the art of geopolymers  109
was involved, the study of flammable plastic materials
became paramount. In 1972, Davidovits founded a private
research company “Cordi S.A.,” later renamed “Cordi-
Géopolymère.” Davidovits was intrigued that simple hydro-
thermal conditions controlled the synthesis of some organic
plastics in alkaline media, such as feldspars and zeolites.
On the other hand, kaolinite aluminosilicate reacts
with sodium hydroxide (NaOH) at 100–150°C and poly-
condenses into hydrated sodalite.
From the studies covering the synthesis of zeolites
and molecular sieves (essentially in the form of powders)
it was determined that this geochemistry had not been
investigated to produce mineral binders and mineral poly-
mers. As a result, Davidovits proceeded to develop a 3D
material of aluminosilicates between amorphous and semi-
crystalline which he baptized as a geopolymer in 1988.
2 Raw materials
For the formation of geopolymers, the following variables
must be taken into account, which have repercussions on
the final properties of these materials:
− Si/Al,
− Si/M+ (M+: alkaline ion such as Na+, K+, etc.),
− Water/solids.
2.1 Aluminosilicate sources
According to previous research, there are a variety of
sources of aluminosilicates for the manufacture of geo-
polymers, these are classified as follows:
110  Hengels Castillo et al.

− By-products from other industries, such as fly ash,

average (g·t−1) average (g·t−1)

low calcium slags (4), and mining wastes (5–7) (e.g.,
copper tailings).

67.00
74.00

12.00
40.30

38.92

37.50
89.33
14.25
− Natural reagents: volcanic glass, silica gel diagnosed

Ni
from acidic environments (8), and clays (9,10).
− Heat-treated aluminosilicates: heat-treated clays or
metakaolin.

46.00
140.00

342.67
51.50

63.58
56.65

73.75
238.14
Pb
These materials share the characteristic of having

Table 1: Percentage by weight of chemical compounds present in different tailing deposits in central Chile (based on data from the Sernageomin cadastre)
large amounts of silica and Al. Some of the materials
that have been most researched will be described in the

average
following paragraphs.

67.00
116.00

51.00
57.40

55.83

106.67
51.65

90.75
(g·t−1)
Cr
2.1.1 Tailings

average (%)
Tailings are flotation discards performed for crushed and

0.80
1.20

1.47
SO3

1.15

—
—
ground sulfide processing. In Chile, most tailings come
from copper mining. These are mostly deposited in dams,

average (%)
because of the large surface area they use due to the high
quantities (in tons) that are handled. Between 1949 and

4.09

1.96
4.03
2.39

3.93
5.47
4.77

2.31
K2O
2017, 2.4 billion tons of tailings were generated; however,
in 2013 China alone generated 319 million (11).
average (%)

The tailings are advantageous for having a great

variety of mineralogy and chemistry, with the prominent
Na2O

3.86

2.89
1.44
0.94

1.34

2.43
0.70

1.37
presence of Si, iron, and aluminum oxides. Table 1 shows
the average data for the most relevant chemical species in
tailings deposits located in central Chile. The high pre-
average (%)

sence of silica can be clearly seen, which covers at least

half of the tailings by weight. It also accounts for between
3.63

4.29
7.34
0.85

0.56
3.59
5.31

2.51
CaO

10% and 20% of aluminum oxides. Iron oxides are on

average below 7%, except in the case of Atacama Kozan
average (%)

where it is seen that iron corresponds to more than 20%

of the tailings deposit.
9.66
8.84
6.96

6.99
Fe2O3

23.24

6.87
18.27

9.41

2.1.2 Fly ash

average (%)

Fly ash is a waste from coal combustion in power plants.

15.00

17.04
Al2O3

19.67
11.23
16.59

14.95

16.18
12.51

The composition of coke defined the fly ash composition.

As stated in the ASTM C 618 standard, there are two
average (%)

classifications for fly ash: Type F, low in calcium and type

C, high in calcium. F-type fly ash is relevant for the pro-
49.46

50.44
60.30
55.43
48.22

49.31
52.15
62.15
SiO2

duction of geopolymers.
The coal burning process and the rate of cooling of
the combustion gas influence the phase formation in fly
Las Cenizas Cabildo
Los Bronces (Anglo
Candelaria (Lundin

El Soldado (Anglo

Minera San Pedro

Andina (Codelco)

(Nittetsu Mining)

ash. The ashes consist mainly of an amorphous phase of

Atacama Kozan

aluminosilicate glasses, considered as the reactive phase

Minera Valle
Central S.A.
American)

American)

(12). However, some of the molten contaminating minerals

Mining)

crystallize or separate during cooling, which causes small

amounts of quartz and mullite to form, in addition to

phases rich in iron and calcium. The aluminosilicates
that make up these phases are considered to be non-
reactive (13).
According to its composition and structure, fly ash is
a non-homogeneous material. Because there are different
phases in a fly ash particle, in addition, each fly ash
particle has a different composition. Finally, each plant
produces fly ash of different compositions; moreover,
within a plant, fly ash of different compositions is pro-
duced due to the low homogeneity of natural carbon. Due
to this complexity in its composition, it is difficult to use
for a specific geopolymer design; however, it is sought to
use it equally due to the positive environmental and eco-
nomic impact that is brought by reusing this waste.
2.1.3 Metakaolin
Kaolins are rocks formed mainly by minerals from the
kaolin group such as kaolinite, dickite, nacrite, and hal-
loysite, accompanied by impurities of quartz, anatase
mica, rutile, ilmenite, and small amounts of tourmaline,
zircon, and other heavy minerals.
Kaolinite (Al 4Si 4O10(OH)8) structurally corresponds
to a clay mineral of the 1:1 type, that is formed by a layer
of silicon tetrahedra combined with another layer of alu-
mina octahedra through hydroxyl groups that are shared
between the two sheets (14).
Metakaolin (2SiO2 Al2O3) is the product of a structural
transformation of kaolinite when subjected to heat treat-
ment. It is an amorphous and highly reactive aluminosili-
cate, which when mixed with cement in mortars or concrete
provides better resistance to compression and durability
compared to using cement alone (14).
From the study carried out by Torres et al. (14), it was
evident that, at temperatures of 700°C, kaolin samples with
an amount of kaolinite greater than 50% were transformed
100% to metakaolin, preserving the quartz impurities pre-
sent in the sample. It is also evident that metakaolin pre-
sents high reactivity at early ages, based on the index of
resistant activity (ratio between the strength of the material
and the strength of a standard mortar) (14).
The synthesis conditions of inorganic polymers based
on metakaolin can be controlled to obtain materials with
certain properties, such as their mechanical resistance,
permeability, rheology, etc. The particle size of metakaolin
can vary in some orders but is generally less than 5 µm.
Although the dispersion of particles during mixing may
slightly affect the rheological behavior and the degree of
reaction (15), parameters such as the amount of soluble
silicates and the type of alkaline cation in the activating
State of the art of geopolymers  111
solution affect the extension of the reaction to a greater
measure (16).
2.2 Alkaline activators
As mentioned above, an alkaline reagent is also needed,
which is responsible for the dissolution of the alumino-
silicates present in the raw material. There are different
reagents for the activation of geopolymers, the most
used are silicate solutions and alkaline hydroxides. The
use of different reagents produces geopolymers of dif-
ferent characteristics, so the choice of reagents depends
on the properties sought (17). There are currently studies
that analyze the performance of calcium hydroxide as an
activator.
2.2.1 Alkali hydroxide solutions
Due to their high availability, the most used alkaline
hydroxides are NaOH and potassium hydroxide (KOH).
Other hydroxides used in minority are LiOH, RbOH,
and CsOH.
NaOH is cheaper than (KOH), but has certain dis-
advantages, such as lower solubility at low temperatures
(54 wt% at 25°C and 30 wt% at 0°C). In contrast, solutions
based on NaOH are more viscous than those of KOH in
similar concentrations, which affects the rheological prop-
erties of the mixture (18). The amount of hydroxides is
mentioned in relation to their molar concentration (M),
which corresponds to the number of moles of solutes (in
this case hydroxides) present in 1 L of solution.
Increased activator concentration has been shown to
lead to increased compressive strength (19).
Both activators allow the formation of crystalline zeo-
litic structures, appearing faster with NaOH, which are
usually associated with loss of resistance (20).
It should be noted that activation by alkaline hydro-
xides has risks at the time of use due to their corrosive
nature and the increase in temperature associated with
their dissolution when they are to be concentrated (20),
so the use of alkali silicates is preferred. Other disadvan-
tages are the increase in viscosity with increasing con-
centration (20). On the other hand, the reagent can react
when it comes into contact with CO2 in the air, generating
precipitation of salts on the surface of the geopolymer
(20). This carbonation can be controlled by keeping the
relative humidity under observation during curing, avoiding
when working at a humidity of 90% (21).
112  Hengels Castillo et al.

If solutions with high concentrations of NaOH are 3 Composition and synthesis

used at low temperatures, the possible precipitates that
may form must be considered (20).
3.1 Composition

A geopolymer is created from AlO−4 and SiO−4 tetrahedra,

2.2.2 Alkali silicate solutions
each of which is attached at its four (or less) corners to
another tetrahedron by bonding of atoms of oxygen,
Another alkaline activator that can be considered is alkali
forming a 3D structure. The structure of the geopolymer
silicate solution (also referred to as soluble glasses for
is mostly amorphous, although it may also have some
those based on sodium), which is composed of a mixture
amounts of zeolitic phases. The amorphous component
of Si2 O, Na2O or K2O, and H2 O. In these solutions, the
of the geopolymer is called N–A–S–H gel, due to the
silica polymerizes into different species that are difficult
final composition of the geopolymerization product
to distinguish. The usual way to analyze these species is
(Na2O − Al2O3 − SiO2 − H2 O).
by 29Si NMR (22).
Geopolymers are inorganic polymeric materials obtained
The viscosity of these solutions increases exponentially
by mixing a dry solid (aluminosilicate) with an alkaline solu-
as the Si/Na ratio increases. As with hydroxides, the potas-
tion and other reactives. The most relevant component is the
sium variant shows less viscosity than water glass (20).
source material, which must be rich in Si and Al (25).
According to Criado et al. (23), the formation of zeo-
For the solidification of the geopolymer to occur, Al is
litic phases is reduced when the Si/M+ factor rises. His
essential. Mixtures with high concentrations of alkali sili-
work shows the phases present in a geopolymer with
cates are commonly metastable. This is because the silica
different SiO2 / Na2O ratios (N = 0; W15 = 0.19, W50 = 0.69,
tetrahedra are attacked by water, which generates an
and W84 = 1.17). In the study, it was observed that the glassy
adjacent pair of silanol (Si–OH) (Eq. 1) until reaching
phase is decreasing, which is consistent since it corresponds
an equilibrium and forming Si(OH)4 , but being in an alka-
to the fact that the fly ash dissolves and delivers silicates and
line environment, the reaction shown in Eq. 2 occurs,
aluminates for the formation of the geopolymer. In mixtures
which causes the remaining oxygen bonds to weaken
with a higher content of soluble silica, it was observed that
and continue being attacked by water until the silicate
dissolution is slower due to the saturation of silica species in
is completely dissolved (26). Therefore, soluble silica
the mixture (23).
alone is not sufficient to produce a chemically hardened
Provis showed the precipitation isotherms of hydrated
material.
sodium silicates (SSs) based on the proportion of silica and
sodium base (Na2O). It was noted that the vast majority of | | |
commercial SS solutions fall in the region where they pre- O O O
cipitate as Na2SiO3 ⋅ 9H2 O (20). | | |
In addition, Provis in his study presented a ternary − O− Si − O− Si − O− +H2 O⇄ − O− Si − OH HO
phase diagram for hydrated SS solutions (20), where the | | |
most important regions for the synthesis of geopolymers O O O
were indicated. Region A corresponds to the area where | | |
(1)
solutions with low amounts of silica behave in a meta- |
stable way (therein, it is not able to maintain its structure O
if there are changes in its environment [e.g., pH] and it |
dissolves again). Region B is where the vast majority of − Si − O−
commercial solutions precipitate. Region C has the poten- |
tial for precipitating metastable phases and region D O
between high viscosity mixtures. |
The combined use of NaOH and SS is the most common
Si(OH)4 + OH− ⇄ Si(OH)3O− + H2 O (2)
practice in terms of cost effectiveness to produce geopoly-
mers with good compressive strength rather than the sole Silicon–oxygen–silicon bonds and silicon–oxygen–
use of alkali silicate or hydroxide. The ratio SS/NaOH can be aluminum bonds are formed due to the bonding of alumi-
a critical parameter for strength development (24). nate and silicate tetrahedra. On the other hand, because

they are not energetically stable, no aluminum–oxygen–
aluminum bonds are formed, which implies that the Si/Al
ratio can reach a minimum value of 1. On the other hand,
the amount of Al must be sufficient so that the dissolution
of silica does not occur (26).
Due to the alkalinity caused by the activating solu-
tion, which raises the pH values, dissolution of the alumino-
silicates present in the raw material occurs. Subsequently,
during molecular organization, the Si tetrahedra can be
replaced by Al tetrahedra, which results in the Al tetra-
hedron being negatively charged. This negative charge is
counteracted by the positive charge of the alkaline cations,
so that these cations from the activating solution become
part of the network (27).
Regarding the elements present in the N–A–S–H gel,
Fernández-Jiménez and Palomo (28) provide the following
information in this regard (the study focuses on fly ash):
− Si mainly participates in the gel based on the zeolitic
nuclei. It has a fundamental role in the control and
kinetics of the formation of this gel in the early stages,
especially if the alkaline activator to be used is water
glass (SS), since it undergoes a dissolution in the
initial stages of polymerization, due to which the first
monomers are delivered to form the silica-rich gel. If
this silicate has many dimers in its composition, the
gel formation will be faster, but it will also imply that
it is more metastable, so the Si/Al ratio cannot be
increased indefinitely.
− Al has an active role in the beginning of chemical reac-
tions, if the source has a large amount of alumina, large
amounts of Al are released into the solution, which
increases the reactivity of the source, otherwise, the con-
tent of Al that is released will be consumed quickly and
will reduce the reactivity of the source. It is speculated
that the Al content in the source should correspond to at
least 20% of this. An excess of Al can lead to the reaction
of the crystalline products. Dissolved Al enters the struc-
ture of the Si-rich gel, which gives it better stability.
− Sodium plays a role as a load balancer, either to bal-
ance the Al monomers present within the gel, which
accordingly ends up giving greater stability to the gel,
or to the Al present in the solution at low Si/Al ratios,
filling the pores of mixtures with zeolitic products. The
Na+ coordination tends to be the same in all systems
and binds oxygen and water molecules.
When activating the sources of aluminosilicates, the
Al species undergo transformations, the majority being
transformed to Al(IV) (or Al(OH)−4 ); therefore, if there is
still the presence of Al(VI) (or Al(OH)63−), one can have a
State of the art of geopolymers  113
notion of the amount of aluminosilicate that did not
react (16).
Davidovits (29) and Rowles and O’Connor (30) have
observed the formation of phases described as semi-crys-
talline or polycrystalline. These crystalline phases are
generally zeolites and their content increases when the
synthesis is carried out under hydrothermal conditions in
alkaline media with a lesser degree of soluble silica con-
tent (31). The hydrothermal reaction in alkaline media of
kaolin, metakaolin, fly ash, and other sources of alumino-
silicates leads to the formation of zeolites with different
structures depending on the reaction conditions (tempera-
ture, nature of the alkali cations, Si/Al ratio, etc.).
A high water content allows the species in the
mixture to be fully hydrated, with small interactions
between ion pairs. Although the silicate and aluminate
species depend on the concentration and the Si/Al ratio
of the mixture, this dilution of the medium improves
the transport of these species and their subsequent
reorganization in the gel. Under these conditions, the
growth of the gel precipitates takes place without
hindrance.
María (31) presented in his study a diffractogram
based on a gel with NaAlSiO4 composition, synthesized
at 40°C from metakaolin. Although the material initially
appears amorphous, the formation of crystalline zeolites
is observed after 7 days, which indicates that their for-
mation is favored by the reaction time.
Duxson (16) showed an X-ray diffractogram of a
metakaolin-derived polymer with nominal composition
KAlSiO4 , which was cured at temperatures of 70°C, 90°C,
and 120°C for 24 h. A new crystalline phase could be
observed at a temperature of 120°C, showing that even
mild increase in the synthesis temperature leads to visible
increase in the crystallinity.
3.2 Synthesis
The synthesis mechanisms that occur from ingredient
mixing to hardened geopolymer are very complex and
remain poorly understood at this moment in time.
Murayama et al. (32) described zeolitization starting
with a solution of Si and Al monomers from the reactant
aluminosilicate, followed by a condensation of silicate
and aluminate ions where the aluminosilicate gel precip-
itates and ends with the crystallization of zeolite. The
geopolymerization process is similar to that of zeolitiza-
tion, except that the former does not complete the crystal-
lization stage (33). In geopolymers, crystallization is mainly
114  Hengels Castillo et al.
attributed to the low water content and high alkalinity of
the systems.
Davidovits (29) proposed a nomenclature to describe
the connections of the structure through polysialates, based
on the following empirical formula: Mp{(SiO2 )z AlO2 }pw H2 O,
where p is the degree of polycondensation; z is between the
values 1, 2, and 3; w is the water contained; and M corre-
sponds to the alkali ion.
Despite giving clarity on how the geopolymer structures
are formed based on the monomers from the aluminosili-
cate source, it assumes that the construction is two-dimen-
sional, with the geopolymer structure being 3D.
Subsequently, a more suitable annotation emerged to
characterize the 3D structure of aluminosilicate systems,
including glasses, gels, zeolites, and minerals (16). Tetra-
hedral structures are designated Q n , in which n is the link
to other tetrahedra. In the case of aluminosilicates, a
component is added to indicate how many of the bonds
are attached to Al tetrahedra (Q n(mAl)) (20).
Polymerization can be represented schematically as
follows (34):
w Na2O ⋅ x SiO2 ⋅ y H2 O + Al2O3 ⋅ SiO2
< 100 °C
(3)
⎯⎯⎯⎯⎯⎯⎯→ w Na2O ⋅ Al2O3 ⋅ (2 + x )SiO2 ⋅ z H2 O
Glukhovsky (35) proposed a polymerization model
consisting of three stages: (1) destruction–coagulation,
(2) coagulation–condensation, and (3) condensation–
crystallization.
3.2.1 First stage: destruction–coagulation
The high amount of OH ions causes the dissolution of the
aluminosilicates in the raw material and, more specifi-
cally, breaks the bonds that form these aluminosilicates
(28). The appearance of the ≡Si–O−–Na+ bonds prevents
the Si–O–Si bonds from being reformed again. The afore-
mentioned alkali silicate bonds can contribute to the
exchange of ions and types of complexes such as
≡Si–O–Ca–OH. With the Al–O–Si bonds, the same type
of reaction occurs and ends up generating complexes
predominantly of the type Al(OH)−4 . The –Si–O–Na+ com-
plexes are stable in an alkaline medium, so they play a
transport role and allow the development of a coagulated
structure based on the units mentioned above.
3.2.2 Second stage: coagulation–condensation
In the coagulation–condensation stage, due to the high
pH, the Si–O–Si bonds form a hydroxylated complex,
Si(OH)3O− , which condenses to form a new Si–O–Si bond
to generate dimers (28). These particles grow in many direc-
tions, generating colloidal particles.
3.2.3 Third stage: condensation–crystallization
For the condensation–crystallization stage, in addition to
the microparticles formed from the condensation, the
particles of the solid phases from the source indicate
the precipitation of products dependent on the miner-
alogy and chemistry of the initial phase, as well as the
nature of alkaline component and curing conditions.
Duxson et al. (36) made a model where he considered
the formation of zeolite: (1) the stage of formation of the
zeolite precursors (the first two Glukhovsky stages) and
(2) a stage where the zeolite nuclei reach a critical size
and begin to crystallize.
The process, albeit though it seems linear, occurs
simultaneously. The initial contact between the solids
and the alkaline solution causes the dissolution of the
amorphous components, releasing silicates and alumi-
nates generally as monomers. Monomers interact to form
dimers, which interact with other monomers to create
trimers, then tetramers and so on (monomers should be
understood as low molecular weight compounds that can
bind to other compounds, so a dimer would be two mono-
mers joined and so on with the other cases). When the
solution is saturated, the first gel rich in Al is formed
because this element is concentrated in the initial stages
of dissolution (first 4–5 h) (31). As polymerization occurs,
more Si reaches the solution, increasing the concentration
of Si in the solution and in the gel phase of the zeolite
precursor. The system continues to reorganize itself and
the connectivity of the gel network increases accordingly.
The result is the formation of a 3D network of alumino-
silicates. The final stage of polymerization and hardening
determines the microstructure and pore distribution of the
hardened geopolymer, which is crucial for the physical
properties of the resulting mixture (28).
The geopolymerization process is often approximated
by the following highly simplified conceptual reactions: (i)
the raw materials are dissolved in alkali solutions, such as
NaOH and KOH, to release the reactive aluminate and
silicate monomers and (ii) the aluminosilicate oligomers
polymerize in the alkali environment to form geopolymer
gels. Because of the charge deficiency in Al (which has a
3+ charge compared to Si having 4+), cations of Na or K are
needed to balance the presence of Al. Water is consumed
during the dissolution of raw materials and released in the
polymerization processes (37) which are schematically
represented by Eqs. 4 and 5 (Figure 2).
 State of the art of geopolymers  115

Figure 2: Conceptual design of geopolymerization process.

n(Si2O5,Al2O2 ) + 2nSiO2 + 4nH2 O concentration to 9 M it was possible to reduce the induc-

Al(−) − O− Si − (OH) tion time, then the time increases again due to the excess
3) (4)
NaOH,KOH
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ n((OH)3 − Si − O− | of NaOH that can lead to precipitation. After this time has
(OH)2 elapsed, all concentrations present a similar gel formation
ratio.
Al(−) Additionally, it was suggested that the presence of
n((OH)3 − Si − O− | − O− Si − (OH)3) zeolite crystals as nuclei allows it to reduce the induction
(OH)2 time. Provis and Rees (38) showed that this hypothesis is
⎛ | | | ⎞ correct, where the gel formation in the presence of crys-

NaOH,KOH
⎜ Si Al(−) Si
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ (Na, K)(3+) − ⎜ | − O− | − O− | − O−
⎜O O O
⎜ | | |
⎝ ⎠
+ ⋯ + 4nH2 O
It is hypothesized that the polymerization process
includes a series of reactions which are intertwined with
each other: (i) aluminate and silicate monomers are first
polymerized to form oligomers with different sizes, (ii)
large clusters and ring structures are subsequently formed
by the gelation of the oligomers, and (iii) cross-linked
structures are finally formed via the condensation of the
clusters and rings (37).
Provis and Rees (38) conducted a study on the kinetics
of the synthesis of geopolymers based on the use of fly ash
and caustic soda, where it was observed that at low con-
centrations of the activator (3 M NaOH), the induction time
(period in which the reagents come into contact, hence a
gel has not yet formed) increases, then by increasing the
⎟ (5) tals is immediate, and after some time a similar formation
⎟ ratio is maintained in both cases.
⎟ Later it was proven that the presence of Al also
⎟ reduces this induction time in cases where crystals are
not present (39).
4 Properties of geopolymers
4.1 Mechanical strength
The early and final strength depends on the composition
of the geopolymer, more specifically on the ratios that
define the geopolymer mixtures, and the reactivity of
the aluminosilicate source.
Lahoti et al. (40) analyzed four design variables for
metakaolin-based geopolymers (water/solid ratio, Si/Al
ratio, Al/Na ratio, and water/Na ratio). Their results
116  Hengels Castillo et al.
revealed a trend, where the highest compressive strengths
obtained were with Si/Al ratios close to 2. It also showed
the dependence of compressive strength on water/solid
ratio, while a general trend showed that the strength
decreases with increasing water/solid ratio, strong varia-
tion in compressive strength at the same water/solids is
also observed. The results of the variation in the Al/Na
ratio indicated that with a value close to 1, the highest
compressive strengths are obtained. Finally, the variation
in the water/Na ratio showed no trend.
Subsequently, the same author made an analysis of
the relevance of the reasons previously studied. From this
it was obtained that the most important variable for the
formulation of geopolymers is the Si/Al ratio.
The general improvement in compressive strength is
mainly due to the improvement in the microstructure of the
polymer, which becomes denser and less porous (27,41,42).
A compilation of information on compressive strength
obtained with different Si/Al ratios collected from previous
research on geopolymers from various sources is pre-
sented in Figure 3. From this it was observed that most
authors used Si/Al ratios between 1.5 and 2 to obtain the
highest compressive strengths. In spite of this, the com-
pressive strength of geopolymers also depends on other
variables, such as the raw material used, the type of alka-
line agent, among others.
The curing temperature of geopolymers has an impor-
tant effect on the occurrence of geopolymerization reactions,
Figure 3: Graph compiling compressive strength vs Si/Al ratio data obtained from previous investigations (16,40,71–75).
because it increases the kinetics of the reactions that occur,
as well as increases the reaction between the alkaline agent
and the raw material. On the other hand, it has been
observed that longer curing times produce higher compres-
sive strengths.
According to previous studies, elevated curing tem-
peratures produce increase in the compressive strength
of the geopolymers (43), due to the increase in the speed
of the reactions that occur, in addition to the increase in
the interaction between the components of the geo-
polymer, which favors geopolymerization. This effect can be
observed in Figure 4, where the variation in the compressive
strength of the geopolymers with the curing temperature is
shown. In most cases, it was observed that the optimum
curing temperature varied between 80°C and 90°C.
An important development in the compressive strength
of geopolymers is due to the concentration of the alkaline
activator, within this topic, the SS/NaOH ratio is one of the
most influential parameters in the development of good
compressive strength of geopolymers. Therefore, Figure 5
shows a compilation of data obtained from previous stu-
dies, which analyzed the effect of the SS/NaOH ratio on the
compressive strength of geopolymers. No trends were found
when varying the SS/NaOH ratio, because the authors had
very different results. It should be considered that the type
of raw material used for the manufacture of geopolymers is
an important parameter, so the variation in the compressive
strength of geopolymers also depends on this factor, within
 State of the art of geopolymers  117

Figure 4: Compressive strength as a function of curing temperature data obtained from previous investigations (11,76–80).

this, it has been observed that geopolymers created based
on fly ash have higher compressive strengths than those
made based on copper tailings. It should be noted that in
most cases it is preferred to use both alkaline reagents
together to obtain geopolymers with denser matrices.
Because the initial water content in geopolymer blends
has an important effect on the compressive strength of geo-
polymers, data were collected on previous studies of geo-
polymers that analyzed the effect of water content, more
precisely, the water/solid ratio.
From the information collected on the variation in
the water/solid ratio, it was observed that higher values
of this ratio led to geopolymers with lower compressive
strengths (Figure 6). However, very low values of this
ratio, i.e., low water content can lead to lower compres-
sive strengths. On the other hand, it should be mentioned
that the necessary water content depends on the type of
compounds used for the formation of the geopolymer.
Optimizing the water content is an important parameter
for the generation of geopolymers, because the

Figure 5: Graph compiling compressive strength data vs Na2SiO3/NaOH ratio obtained from previous investigations (80–82).
118  Hengels Castillo et al.

Figure 6: Graph compiling compressive strength data vs water/solids ratio obtained from previous investigations (80,83,84).

concentration of the alkaline reagents depends on the
water content in the mixture.
4.2 Permeability
In order to assess the durability and enhance the useful
life of alkali-activated geopolymers as a construction
material, the understanding of water transport and its cor-
relation with microstructure parameters is a crucial step.
Water transport, pore structure characteristics, and
relevant ion transport are closely linked to permeability,
especially for reinforced geopolymer concrete structures.
It is well known that water can be a carrier of Cl−, SO24−, or
CO2 that can penetrate into the geopolymer material and
interact with the reaction products. The result is an
altered matrix microstructure and corrosion initiation
which will further lead to degradation of the reinforce-
ment (44).
The most important parameter that influences the
water and ion permeability is the material pore structure,
particularly the pore volume, pore size distribution, con-
nectivity, and shape of the pores. It was observed that the
increase in the total porosity, effective porosity, and pore
diameter produces an increase in the geopolymer perme-
ability (44).
Lower porosity leads to a more compact microstruc-
ture, and therefore lower permeability (45). In Figure 7,

Figure 7: Viscosity–hydraulic gradient for a copper tailing-based geopolymer.


the hydraulic conductivity test by flexible wall is pre-
sented for a test piece compacted with a tamper for a
sample of a copper tailing-based geopolymer dried in
an oven at 90°C and cured for a period of 7 days. The
mixture presented a behavior like soil, since in the mea-
surement of the Skempton variable, which measures the
degree of saturation of the sample that must reach a
minimum of 95% to carry out the test, it very quickly
reached 93% but the remaining 2% took more than a
week. The test result indicated that the copper flotation
tailings have a permeability of 7.0 × 10−7 cm·s−1. Com-
pared to a tailings dam with permeability values of
1.0 × 10−5 cm·s−1, it can be indicated that the copper tail-
ings geopolymers is more impermeable than other tailings.
4.3 Rheology
The rheology of geopolymer pastes depends mainly on
the raw material used, the amount of initial water, and
the alkaline solution used. SS solutions are generally
more viscous than NaOH solutions (46–48).
Riffai et al. (48) conducted an investigation on the
influence of NaOH concentration on rheology during
the formation of geopolymers from fly ash. From this it
wasobtained that the yield strength of the geopolymeric
pastesincreased with the concentration of the activator,
where itwas maximal at a concentration of 8 M NaOH
(49), then decreases to below 4 Pa and increases gradu-
ally. The viscosity increases to a concentration of 3.5 M.
After decreasing, the viscosity increases again from a
Figure 8: Yield stress for a copper tailing-based geopolymer paste at different times after mixing.
State of the art of geopolymers  119
concentration of 8 M NaOH, as a result of the increase
in the viscosity of the NaOH solution at high concentra-
tions (48).
In an analysis carried out in which the composition
of the alkaline activator used for the production of geo-
polymers based on copper tailings was varied, it was
found that an increase in the SS content produced a
decrease in the yield strength of the geopolymer pastes.
It should be noted that the 100% SS sample showed a
different behavior from the others. Figure 8 shows the
yield stress of a copper tailing-based geopolymer paste
at different times after mixing.
From Figure 9, it can be seen that the longer the time
after shaking, the higher the yield strength of the geo-
polymeric paste, increasing from 1,140 Pa at time 0 to
1,370 Pa at 4 h after mixing. The sample was dried in an
oven at 90°C and cured for a period of 7 days.
4.4 Acid resistance
Acidic media cause damage to the geopolymers, which is
due to the proton exchange with the alkaline cations, in
addition to producing a loss of Al in the initial gel (18).
The resistance of geopolymers under acid condition
depends on multiple factors: the acid solution concentra-
tion, exposure period, and environmental condition, such
as pressure and temperature. The acid resistance also
depends on the type of the alkaline activator and the
mineralogical composition of the raw materials (50).
It has been shown that ordinary Portland cement
(OPC) has a worse resistance to acidic media than
120  Hengels Castillo et al.
Figure 9: Rheological curves of a geopolymer paste based on copper glues with different compositions of alkaline activators.
geopolymers (51). This was also observed in a study car-
ried out by Neven et al. (52), where it was estimated that
the degradation rate of geopolymers in acidic environ-
ments is at least half of that of OPC.
In order to obtain greater durability, studies of geo-
polymers in recent years have been based on studying
the addition of different natural aggregates in order to
improve resistance to acids, forming more compact matrices,
which prevents these acids from penetrating the structure of
the geopolymer.
4.5 Resistance to alkali–aggregate
reaction (AAR)
Previous studies have shown that the basic reaction of
silica is due to the calcium present in the aluminosilicate
sources, for this reason, in fly ash-based geopolymers
this effect is rarely seen.
In one of the studies (53), the authors compared the
expansion of Portland cement mortar prisms (OPC) with
fly ash cement activated with NaOH and soluble silica.
Soluble silica-activated fly ash and Portland cement
prisms exceed the 16-day expansion limit (this limit indi-
cated by ASTM C1260-94 indicates that if it exceeds 0.1%
expansion within the first 16 days of the mixture there is a
potential detrimental effect caused by the AAR). In con-
trast, the NaOH-activated fly ash geopolymer exceeds the
limit at around 4 months. The expansion of both the
geopolymers can be attributed to an “alkali–silica reac-
tion” gel formation (a gel that is formed by the hydration
of sodium silicate [NSH] in the activator solution and that
expands when more water is absorbed) and the crystal-
lization of zeolite (51).
4.6 High temperature resistance
Geopolymer is a novel material that has a wide range of
applications, including its use in structures. Protection of
structures from fire is of extreme importance, this is why
many studies have been carried out lately to analyze the
properties of geopolymers after being exposed to high
temperatures.
Different authors have found several ways to improve
the strength of geopolymers after exposure to high tempera-
tures. Geopolymers activated with KOH showed improve-
ments in compressive strength (30–40%) in contrast to
those activated with NaOH (54). Geopolymers created with
50% metakaolin and 50% fly ash have shown that this
composition is optimal for obtaining better bending and
compressive strengths both at room temperature and after
exposure to high temperatures (55). Other authors have
added natural aggregates to obtain geopolymers with better
properties after exposure to high temperatures, such as
sand plus glass powder (56) and dolomite (57).
4.7 Retention of hazardous and radioactive
waste
Because polymers are compounds of amorphous alumino-
silicates similar to zeolites and thus possess similar

cation-exchange properties, geopolymers have been suc-
cessfully used to remove toxic metals and organic dyes
from aqueous solutions.
Geopolymers have been shown to be capable of
retaining hazardous wastes such as lead, boron, copper,
arsenic, and ammonium (58,59). The first two cannot be
stabilized in Portland cements as they tend to inhibit the
hydration process of the cement. However, chromium
cannot be retained in fly ash-based geopolymeric matrices
due to the formation of soluble salts.
In addition, geopolymers can retain radioactive ele-
ments, such as cesium, molybdenum, and strontium
(60–62).
Geopolymers appear to act like zeolites by retaining
certain cations (60).
4.8 Carbonation and corrosion
Geopolymers can passivate the steel structure of con-
crete. The duration of this passivating layer depends on
the activating solution used (51).
Carbonation at early age is expected to reduce the
extent of reaction by limiting the availability of alkalis,
which are needed for the reaction process to continue,
and so this may be damaging to the performance of the
material. The influence of carbonation on the mechanical
integrity of the binder phases also needs to be examined,
as there are indications that a loss of strength may take
place during carbonation (21,22,63).
Carbonation can also induce a loss of strength and an
increase in pore volume in alkali-activated concretes (60).
4.9 Volume stability
Kuenzel et al. (64) investigated the amount of water in
moles necessary to avoid a chemical contraction by altering
the Si/Al ratio, therein observing that the mixture became
more sensitive on raising the Si/Al ratio. There are possible
reasons to explain this increase and the greater gel forma-
tion, and again a possible increase in porosity and/or
changes in the ion pairs Na+:AlO−4 due to changes in Al
content in the gel (64).
Increasing the Na content dramatically increases the
amount of water needed to prevent shrinkage. This implies
that the hydration of Na+ cations has an important role in
the stability of the mixture (64).
On the other hand, when geopolymers are used as
construction materials, they are expected to maintain
State of the art of geopolymers  121
their volumetric stability under different circumstances,
such as high temperatures, high humidity, aggressive
chemical environments, etc.
A study by Lahoti et al. (65) showed that the variation
in the Si/Al ratio of geopolymers based on metakaolin
presents different properties in geopolymers affected by
high temperatures. It was observed that a Si/Al ratio of 2
is the optimal one for obtaining good resistance and volu-
metric stability after heat treatment.
Luhar et al. (66) also obtained improvements in the
volumetric stability of geopolymers by varying the com-
position of the raw material. In this case, the addition of
20% of glass wastes produced a significant reduction in
the weight loss of the geopolymer when it was subjected
to sulfate attack, compared to the case without the addi-
tion of this aggregate.
4.10 Ecological advantages
The action of reusing waste from other industries for the
generation of geopolymers and thus avoid their deposi-
tion in landfills is an ecological advantage.
Duxson et al. (67) and Komnitsas and Zahraki (68)
contrasted the generation of CO2 for the production of
geopolymers with the generation of CO2 for the genera-
tion of cement, where it was obtained that the emissions
of this greenhouse gas are reduced to 20–80%.
However, in order to reach a verdict on the ecological
advantages of geopolymers, more in-depth studies must
be carried out to analyze variables that have not yet been
taken into account.
4.11 Applications
Geopolymers have been manufactured for the production
of different materials and uses, among which the fol-
lowing stand out (2) (69):
− Geopolymer cement molds.
− Thermal insulation materials.
− Coatings to strengthen structures.
− Cement-like construction material.
Despite the wide range of uses in which they can be
used, they have only been applied on a large scale as
construction materials, such as:
(1) Geopolymer cement was produced on a large scale
using the name “Pyrament.” The production lasted
122  Hengels Castillo et al.
only 4 years due to financial problems of the com-
pany (2).
(2) Train sleepers based on geopolymers were produced
with good results, mainly due to the physical char-
acteristics of the geopolymers (70).
(3) In Australia, geopolymer cements are produced, where
they sell prefabricated geopolymer parts under the
name “E-crete,” where they are used for different
structural purposes. In addition, this company has
reported that its carbon dioxide emissions are up to
80% lower than those of cement.
From the examples, geopolymers are made for cer-
tain market sectors, but not for the entire CPO market.
More pilot plants are needed to develop more applica-
tions for geopolymers, in order to make maximum use
of this environmentally friendly material.
5 Conclusion
Therein, it was identified that the final characteristics of
the geopolymer depend on its chemical formation, where
the chemical elements Na, Al, Si, and H2O play a funda-
mental role in generating the N–A–S–H gel that accordingly
dominates the chemical properties of the geopolymer.
In terms of the application, it is now evident that
there is huge potential for an alternative and sustainable
solution to other more traditional technologies such as
concrete, albeit requiring a greater amount of applied
research around the geopolymer, therein to ensure its
feasibility of use at an industrial level.
Acknowledgments: We are grateful for the support of this
research project provided by the Consulting Company
JRI Engineering from Chile (https://www.jri.cl/, access
on 30 December 2021) and the Center for Research in
Sustainable Mining CIMS-JRI (https://www.cimsjri.cl/,
access on 30 December 2021).
Funding information: Authors state no funding involved.
Author contributions: Hengels Castillo: writing – review
and editing, investigation, project administration, resources,
supervision, and validation; Humberto Collado: writing –
review and editing and investigation; Thomas Droguett:
writing – review and editing and investigation; Mario
Vesely: resources, supervision, and validation; Pamela
Garrido: resources, supervision, and project administration;
Sergio Palma: writing – review and editing, investigation,
validation, and supervision.
Conflict of interest: Authors state no conflict of interest.
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