Geopolymer technology, from fundamentals to

advanced applications: a review

Behzad Majidi
Geopolymers are inorganic polymers with 3D framework structures having superior mechanical
and physical properties. This new generation of cementitious materials has potential applications
in fire resistant fibre composites, concretes for infrastructure applications, sealants and ceramics.
Geopolymers are environmentally friendly substitutes for Portland cement: geopolymers in many
applications not only reduce greenhouse gas emissions but also consume large volumes of
industrial wastes such as fly ash, mine tailings and metallurgical slag. A brief review is given of
geopolymer fundamentals and technology. Coverage includes structure and preparation, raw
materials and the properties, particularly mechanical properties, of geopolymers. Current and
potential applications of geopolymers and their advantages are introduced and discussed. The
status of the geopolymer industry and the challenges that must be overcome to achieve wide
acceptance and application of these novel cements is considered. Finally, future research topics
are proposed. It is concluded that factors including the conservative view of new materials have
limited application of geopolymers but progress is being made and geopolymers will be an
important part of sustainable development in the twenty-first century.
Keywords: Geopolymers, Geopolymerisation, Cementitious materials, Fibre reinforced composites, Carbon emissions, Calcining, Portland cement

Introduction produce new, high strength, durable cementitious materi-

Geopolymers emerged as a result of attempts to model
the geological formation of zeolites. Zeolites are micro-
porous crystalline solids with well defined structures.
Generally they contain silicon, aluminium and oxygen in
their framework and cations, water and/or other
molecules within their pores. Because of their unique
porous properties, zeolites are used in a variety of
applications such as petrochemical cracking, water
softening and purification, and in separation and
removal of gases and solvents. Many zeolites occur
naturally as minerals, and are extensively mined in many
parts of the world. Others are synthetic, being made
commercially for specific uses, or produced by scientists
trying to understand more about their chemistry.
Victor Glukhovsky1,2 is believed to be the first
researcher to attempt to model the geological process
of zeolite formation, in the 1950s. Zeolites were
synthesised by alkali activation of alumino-silicates
present in industrial materials or wastes. These novel
binders were initially called ‘soil silicates’.1 Some
authors3 believe that zeolitic compounds are the final,
stable phase of a long-term conversion of primary
phases to zeolites. This is in accord with investigations
on ancient Roman cements that have indicated the
presence of amorphous zeolitic compounds.4,5
The outstanding durability of ancient Roman cements
and Glukhovsky’s work created interest in the potential to
Shiz Concrete Industrial Complex, Iran, email behzadmajidi@aut.ac.ir
als. The most comprehensive research in this field was
conducted by J Davidovits,6 who first applied the term
‘geopolymer’ to these alkali activated alumino-silicates.
Geopolymers or ‘inorganic polymers’ are mineral
polymer materials with a structure of 3D cross-linked
polysialate chains.7 Geopolymers are produced by
polymerisation of silicon, aluminium and oxygen species
to form an amorphous three-dimensional framework
structure.8,9 A geopolymer could be made by dissolving
an alumino-silicate material such as kaolinite in highly
alkaline environment such as NaOH or KOH solutions.
Geopolymerisation is a process in which silicon,
aluminium and oxygen atoms create a chain of SiO4
and AlO4 tetrahedra linked alternatively by shared
oxygen atoms.10,11 The water to solid ratio in this
process, if no aggregates are used, ranges12 from 0?3 to
0?4. The products are amorphous to semi-crystalline
materials with superior mechanical behaviour.13–23 The
reactants used to form conventional geopolymers are
usually metakaolin as the Al–Si source and an activator
solution containing reactive silicate anions and alkali
cations.24 The focus of research in this field may be
summarised as follows:
(i) Al–Si source: identifying low cost, readily avail-
able materials suitable to participate in geopoly-
merisation. It has been shown that a wide range
of natural materials and industrial wastes such as
kaolin, fly ash, blast furnace slag, alkali-
feldspars12 and tungsten mine waste13 can be
used to make geopolymers

! 2009 W. S. Maney & Son Ltd.

Received 17 March 2009; accepted 1 May 2009
DOI 10.1179/175355509X449355 Materials Technology 2009 VOL 24 NO 2 79
Majidi Geopolymer technology, from fundamentals to advanced applications
1 Polysialate and polysialate-siloxo molecular structures and related frameworks26
(ii) alkali activation: analysing the effects of pH and
alkali ions on process completion and the final
properties of the product, e.g. it has been shown
that K-feldspars show increased dissolution in
NaOH solution compared with KOH solution,
and thus confer higher compressive strength12
(iii) geopolymerisation: the mechanisms of the reac-
tion have yet to be fully understood; the
parameters affecting the process, microstructural
reorganisation of the source materials and the
reaction steps have been studied extensively by
analytical methods.
The unique properties of geopolymers – high early
strength, extraordinary durability, resistance to chemical
attack, ability to immobilise toxic atoms and environ-
mental benefits such as low energy consumption and
carbon dioxide emission in production – make geo-
polymers a strategic material for sustainable develop-
ment and a serious alternative to Portland cement.
Chemical characteristics of geopolymers
The following empirical formula has been postulated by
Davidovits25 to describe geopolymers
Mn ½{(Si{O2 )z {Al{O"n :wH2 O
in which M is an alkali metal, z is 1, 2 or 3 and n is the
degree of polymerisation. Based on the Si/Al ratio, three
monomeric units may be defined:
polysialate : SiO2 =Al2 O3 ~2, (Si{O{Al{O{)
polysialatesiloxo, SiO2 =Al2 O3 ~4,
(Si{O{Al{O{Si{O{)
polysialatedisiloxo, SiO2 =Al2 O3 ~6,
(Si{O{Al{O{Si{O{Si{O{):
These structures are composed of AlO 2 2
4 and SiO 4
tetrahedra. Cations of alkali or alkali earth metals
(Naz, Kz, Ca2z) are required in the structure to
80 Materials Technology 2009 VOL 24 NO 2
balance the negative charge. By dissolving an alumino-
silicate powder in alkali solution such as NaOH, first
AlO 2 2
4 and SiO 4 tetrahedra are created and, according
to the concentration of silicon in the solution, one of the
above monomers is formed. The molecular arrange-
ments in some geopolymer frameworks are shown in
Fig. 1. A reaction mechanism for geopolymerisation
proposed by Davidovits26 involves the chemical reaction
of precursors such as alumino-silicate oxides (Al3z in
IV-fold coordination) with alkali polysilicates, resulting
in polymeric Si–O–Al bonds. To emphasise the IV-fold
coordination of Al in these Al–Si minerals, these
configurations are usually written as (Si2O5.Al2O3)
rather than (2SiO2.Al2O3):
The structure of geopolymers can be amorphous or
semi-crystalline, depending on the condensation tem-
perature. Amorphous polymers are obtained at 20–
90uC, whereas semi-crystalline polymers are obtained at
150–1200uC.27
In geopolymerisation, first alumino-silicate oxides
dissolve in the alkali solution, then dissolved Al and
Si complexes diffuse from the particle surfaces to the
inter-particle spaces. Finally, a gel phase is formed from
the polymerisation of added silicate solution and Al and
Si complexes.

2 Effect of calcination temperature and duration on release of silicate and aluminate monomers in alkali solution30
To produce geopolymer from kaolin or other clay
materials three main steps are necessary:
(i) thermal activation, the aim of which is to obtain
a clay material with high chemical activity. In
this process dehydroxylation of clay mineral
leads to an unstable amorphous solid
(ii) alkali activation: activated alumino-silicate
material is dissolved in highly alkaline solution
to produce silicate and aluminate monomers28
(iii) reactive setting or polycondensation, in which
the silicate and aluminate monomers condense to
a stable polymer network.29
To obtain a well structured geopolymer with acceptable
mechanical properties, it is necessary to enhance the
activity and solubility of Al–Si source materials in alkali
solution. Thermal activation of the source material is
one way to meet this condition and several investiga-
tions have examined the thermal activation process and
its effects on final properties.
Kaps and Buchwald30 used Fourier transform
infrared spectroscopy to analyse the microstructural
changes of kaolin during calcination. On calcining
kaolin at 500uC, two distinct microstructural
changes were observed: first the peaks corresponding
to O–H bonding vibration (,3600 cm21) start to
broaden, and completely disappear after 180 min.
Simultaneously, aluminium coordination with oxygen
changes and the peak corresponding to [Al–O]VI
vibration disappears.
X-ray diffraction analysis was also used to determine
the results of calcination. Two distinct peaks could be
usually identified in the XRD pattern of kaolinite-based
clays: kaolinite and quartz. On calcining the material at
500–800uC, kaolinite crystals are completely broken
down to an amorphous phase, metakaolin. Quartz
crystals are also usually present in calcined clay, and
the quartz peaks do not disappear from the XRD
pattern of the calcined clay untile the calcining
temperature is increased to 1400uC. However, in this
case kaolinite, by losing SiO2, transforms to mullite
instead of forming metakaolin, which decreases the
Majidi Geopolymer technology, from fundamentals to advanced applications
solubility of the material in alkali solution. The
behaviour of crystalline SiO2 in geopolymerisation and
the microstructural effect of free quartz particles on the
mechanical behaviour of the final product are not fully
understood and need to be investigated further.
The duration and temperature of thermal activation
directly affect the solubility of the clay in alkali
solution.31,32 It has been shown30 that increasing the
temperature of calcination increases the release of
silicate and aluminate monomers in alkaline solution.
As can be seen in Fig. 2, release of Al and Si monomers
in NaOH solution for kaolin dehydroxylated at 750uC is
greater than for that calcined at 500uC: the same
solubility is observed for 500uC after 180 min as for
750uC after 60 min.
Kinetics of geopolymerisation
Determining the key parameters in the kinetics of
geopolymerisation is essential to better control setting
time and microstructural development of geopolymeric
gels. Geopolymerisation consists of dissolution and
hydrolysis followed by a condensation step in an
alkaline silicate plus alumino-silicate system.
Experimental techniques such as calorimetry have
been frequently used by researchers33–37 to investigate
geopolymerisation kinetics. This technique is useful in
determining the reactivity of calcined materials in alkali
environments and so could help to optimise calcination.
Rahier et al.38–40 used quasi-isothermal modulated
differential scanning calorimetry to observe the changes
in heat flow and heat capacity during the setting of
geopolymeric gels. They showed that the reaction
consists of at least two steps – dissolution and
polymerisation – and that the second step is autocata-
lytic. It has been shown that the rate of condensation
between silicate species is lower than that between
aluminate and silicate species.41–43 The role of Al2O3
and SiO2 in geopolymerisation and its kinetics has been
studied by De Silva et al.44 They concluded that the
geopolymerisation kinetics and setting rate of geopoly-
meric gel are controlled principally by Al2O3, whereas
Materials Technology 2009 VOL 24 NO 2 81
Majidi Geopolymer technology, from fundamentals to advanced applications
3 Proposed reaction sequence for geopolymerisation47
the Si content is responsible for later strength develop-
ment of the product.44 Similar results have been
reported by Provis et al.,45 who also showed that high
silica systems react more slowly with a ‘pause’ in the
latter stages of the reaction before further reaction
occurs. The mechanism of Al speciation in accelerating
the condensation step of geopolymer formation by
means of calculation of the partial charge of aluminate
and silicate species has been investigated by Weng
et al.,46 who concluded that varying the particle size of
metakaolin has a significant effect on the properties of
hardened geopolymer. They reported that milled meta-
kaolin powders with high specific surface area have
shorter setting time, higher strength and a more
homogeneous microstructure due to improved Al
availability, as predicted by the partial charge model.
Recently, Provis at al.47 have developed a model
based on the work of Faimon48 to study the chemical
reaction sequence and kinetics of geopolymerisation.
They propose the reaction sequence for geopolymerisa-
tion indicated in Fig. 3. By postulating reactions for
each step and corresponding kinetic expressions for each
reaction, assuming that the stoichiometry of the reaction
predicts the kinetics, they developed a comprehensive
kinetic model for geopolymerisation. Applying the
model to experimental data from the literature, they
showed that the model could be used to determine the
rate of geopolymerisation reaction and setting time for a
wide range of Si/Al ratios in raw materials.
Mechanical properties of geopolymers
Mechanical behaviour is a basic property in assessing an
engineering material for a specific application. For
geopolymers as novel cementitious materials, compres-
sive strength is an important factor. Ever since their
invention in the 1950s, the better compressive strength,
setting time and durability of geopolymers over conven-
tional cements have been perceived as advantages.
However, the compressive behaviour of geopolymers
varies according to the raw materials and processing
method used.
To obtain a geopolymer with high compressive
strength, a high strength gel phase and high ratio of
gel to non-polymeric phases are required. These factors
relate directly to the type and molar ratios of oxides in
the Al–Si source, type and pH of alkali solution and
solubility of raw materials in the activator solution.49,50
Davidovits51 introduced three ‘key parameters’ for
producing high strength geopolymers. Based on
research on kaolinite-based geopolymers, he defined
82 Materials Technology 2009 VOL 24 NO 2
the following ratios:
0:2vNa2 O=SiO2 v0:28
3:5vSiO2 =Al2 O3 v4:5
15vH2 O=Na2 Ov17:5
Zuhua et al.52 investigated the role of structural water in
the compressive strength of kaolinite geopolymers. They
showed that final strength of products increases on
increasing the calcination temperature of kaolinite. This
result seems to be due to higher activity of the clay
calcined at higher temperature and also a lower
structural water content (which has a negative effect
on the strength of the product).
In view of the importance of the dissolution of Al–Si
species in alkali solution and of the polymerisation
reaction, it is unsurprising that the characteristics of the
alkali solution directly affect the microstructural re-
organisation of the calcined clay and so the final
mechanical properties of the product. It has been
shown53 that flexural strength, compressive strength
and apparent density of geopolymers increase as NaOH
solution concentration increases from 4 to 12 mol L21
and the higher the concentration of NaOH, the higher
the amorphous content of the products. Similar results
have been reported previously.54
Although dissolution of Al–Si species increases on
increasing the concentration of alkali solution, excessive
amounts of NaOH or KOH in the aqueous phase
decrease the SiO2/Na2O ratio and so inhibit polycon-
densation. Therefore, there is a limit for alkali hydroxide
concentration in the activator solution to obtain a high
strength gel phase (Fig. 4).55 The geopolymer properties
reported in Fig. 4 were obtained on specimens aged for
7 days; for a simple comparison, a typical 7 day
compressive strength of type-I Portland cement concrete
is 19?0 MPa.
It has been also shown55 that KOH provides more
inorganic polymer precursors than NaOH since the
larger Kz cation favours the formation of longer silicate
oligomers, with which Al(OH) 2 4 prefers to bind; thus
better setting and higher compressive strength is
acquired (Fig. 4).
Using alkali solution composed of alkali hydroxide and
dissolved silicate has been found to be beneficial for
compressive strength relative to alkali hydroxide alone.
Dissolved silica not only balances the SiO2/Al2O3 and
Na2O/SiO2 ratios in the mixture but also catalyses
polycondensation by providing SiO 2 4 monomers and by
initiating polymerisation between AlO 2 4 and SiO 2 4
tetrahedral units. Therefore, higher compressive strength
may be obtained using an activator composed of soluble
silicate and alkali hydroxide. Investigations30 on kaolinite
based geopolymers have shown that addition of 25 wt-%
(additional SiO2/solid material) sodium silicate solution
increases 14 day compressive strength from 13 to
38 MPa. Similar results have been reported recently on
ferronickel slag based geopolymers.55
It should be noted that, again, there is a limit for
addition of silicates to the mixture (Si/Al51?90) and
very high ratios of Si/Al are not advisable due to the
negative effect on mechanical properties.56 High Si/Al
ratios increase the porosity of the structure and also
content of unreacted species, and these factors directly
decrease compressive strength of the geopolymer.
 Majidi Geopolymer technology, from fundamentals to advanced applications

4 Effect of alkali hydroxide concentration on compressive strength of geopolymers aged for 7 days55

The presence of calcium compounds such as CaO and during alkali activation of alumino-silicates is the shift
Ca(OH)2 has been shown57,58 to improve the compres- of the infrared band for Si–O–Si and Al–O–Si
sive strength of geopolymers; here the effect of Ca(OH)2 asymmetric stretching (950–1200 cm21) to lower
is more pronounced. Precipitation of calcium silicate wavenumbers. It has been shown61,62 that dissolving
hydrate or calcium silicate aluminate phases and alumino-silicates in alkali solution increases the number
catalysis of the dissolution of Al–Si particles in alkali of non-bridging oxygen atoms (NBOs) within the
solution have been proposed as two reasons for the structure. This causes SiO42 and AlO42 units to become
enhanced mechanical behaviour observed in geopoly- isolated and thus lower molecular vibration of Si–O and
mers produced by addition of calcium compounds to Al–O bands is observed. Here, Na cations balance the
raw materials. negative charges created by formation of Al–O–Si bands
or removing NBOs. By means of 29Si and 27Al MAS-
Microstructure of geopolymers NMR, geopolymerisation mechanisms and the progress
and changes in molecular arrangements can be fol-
The mechanical properties discussed above result from
lowed63 (Fig. 5). As the reaction continues, the coordi-
changes in the geopolymer microstructure. Analytical
nation of Al (IV,V,VI) in metakaolin changes almost
techniques such as XRD, XRF, magic angle spinning
completely to IV in the final product.63 The effect of
nuclear magnetic resonance (MAS-NMR), SEM/EDS,
temperature in accelerating the reaction can also be seen
TEM/EDS, Fourier transform infrared spectroscopy
in Fig. 5.
(FTIR) and thermogravimetry (TG) have been used to
clarify the microstructural features of geopolymers.
X-ray diffraction and TG tests are very useful to Geopolymer composites
detect structural changes during calcination of raw
In recent years advanced composite materials using
materials. Characteristic peaks in the XRD pattern of
geopolymer matrices have attracted significant atten-
kaolinite based clays correspond to kaolinite, quartz,
tion. In 1996, Lyon et al.64 reported information on
mullite and illite. After calcination at 500–800uC,
geopolymer carbon fibre reinforced composites, includ-
broadened XRD peaks are observed. Quartz crystals
ing their fire resistance. On the basis of ASTM E-162
usually remain in calcined clay but kaolin crystals may
be completely broken down to an amorphous alumino- tests, the flame spread index for geopolymer matrix
silicate phase. Combining XRD analysis and TG enables composites reinforced with glass or carbon fibres was
the process to be optimised. Zuhua et al.52 reported from superior to that of composites with thermoset, phenolic
TG tests on calcined kaolin that the mass loss at 700, or engineering plastics matrixes. As an engineering
800 and 900uC was 0?9, 1?9 and 2?3% respectively
relative to the mass at 600uC. This mass loss is believed
to derive from evaporation of structural water; since
existing hydroxyl units in heated kaolin have a negative
effect on its activity in the alkaline medium, it was
concluded that an optimised calcination could be
determined by from an amorphous XRD pattern and
the maximum mass fall detected by TG tests.
XRD cannot provide useful information for micro-
structural changes in the alkali activation step: usually
there are no significant differences between XRD
patterns of reacted and unreacted clays59,60 because
most changes take place in amorphous phases of the
material and there is no crystalline phase in the reaction
products. However, FTIR and MAS-NMR analysis can
29
provide very useful data on molecular changes during 5 Si and 27Al MAS-NMR spectra for metakaolin based
geopolymerisation. One significant molecular change geopolymer cured at room temperature and 80uC63

Materials Technology 2009 VOL 24 NO 2 83

Majidi Geopolymer technology, from fundamentals to advanced applications
6 Residual flexural strength of cross-ply laminates after
fire exposure64
material for infrastructure applications, the residual
strength of composites after fire exposure is very
important. Figure 6 indicates residual flexural strength
of cross-ply laminated composites after fire exposure. It
can be seen that, even after exposure to more severe
thermal environment (800uC, 75 kW m22) than organic
composites the geopolymer matrix composite has higher
residual strength.
Lin et al.65 used short carbon fibres with different
lengths (2, 7 and 12 mm) to reinforce a geopolymer
matrix. Regardless of fibre length, carbon reinforced
geopolymer was found to exhibit pseudoplastic fracture,
as opposed to the sudden fracture mode of pure matrix.
Geopolymer matrix samples showed brittle failure mode
in three-point bending tests, while composites deformed
without complete fracture. The maximum flexural
strength and fracture work was obtained by using
7 mm fibres. Addition of 7 mm fibres increased the
flexural strength of the matrix from 16?8 to 91?3 MPa
and work of fracture from 54?2 to 6435?3 J m22.
Scanning electron micrographs of the tensile side and
fracture surface of composite deformed in three point
bending are shown in Fig. 7. Fibre pull-out appears to
be the main toughening mechanism in these composites.
The clean surface of the pulled-out fibres also indicates
that matrix/fibre bonding was weak.
More recently, similar results have been reported by
Li and Xu,66 who investigated the impact loading
response of basalt fibre reinforced geopolymers. The
addition of basalt fibres was shown to enhance the
deformation and energy absorption capacities of a
geopolymer matrix significantly.
Research67 on the application of a geopolymer matrix
for repair and rehabilitation of reinforced concrete
beams has indicated that the geopolymer performs
better than organic polymers in terms of adhesion of
carbon fibres to reinforced concrete beams.
The tribological behaviour of metakaolinite based
geopolymer composites has also been investigated. It
was found that addition of PTFE powder to the
geopolymer matrix changes the wear mode from severe
to mild owing to a composite soft layer formed during
the friction.68
Geopolymers and Portland cements
Availability of raw materials and its ease of production
and application have made Portland cement concrete the
most popular and widely used building material. The
application of concrete in infrastructure and transport
has unquestionably improved the development of
civilisation, economic progress and the quality of life.69
84 Materials Technology 2009 VOL 24 NO 2
7 Scanning electron micrographs a perpendicular and b
parallel to fracture surface of carbon fibre/geopolymer
composite65
However, some inherent disadvantages of Portland
cement remain difficult to overcome. Perhaps the
important of these is the high ‘carbon content’: 1 t
CO2 per tonne ordinary Portland cement (OPC) is
released to the atmosphere and y1?5 t per tonne of raw
materials. This makes production of OPC extremely
resource and energy intensive. Calculations70 indicate
that the total energy required to produce Portland
cement is y3630 MJ/t, compared with an energy
consumption for geopolymer cement production of
990 MJ/t. The difference is mainly due to the lower
calcination temperature for geopolymers (800 versus
1450uC). It has been estimated that total CO2 emission
for production of geopolymer cements is only 0?184 t
per tonne of cement, about one-sixth that of Portland
cement.71 Considering global warming and international
attempts to reduce greenhouse gas emissions, and
government commitments under the Kyoto protocol,
geopolymers as an alternative to Portland cements may
potentially have a remarkable impact on CO2 emission
reduction strategies.
In addition, the poor resistance of OPC concrete to
corrosion and chemical attacks is a concern for
designers, since OPC can deteriorate when exposed to
severe environments. In contrast, geopolymers have
shown superior resistance against chemical attacks.
Song et al.72 compared the durability of geopolymer
and Portland cement concretes against sulphuric acid
attack, concluding that the geopolymer concrete was
highly resistant to sulphuric acid with a very low mass
loss, ,3% (Fig. 8).
Therefore, owing to their outstanding mechanical
behaviour and environmentally friendly production,
geopolymers have potential to substitute ordinary
cements in construction applications or at least can
decrease demand for Portland cement production. As
discussed below, cost considerations also apply.
Nevertheless, geopolymers are an ideal material for
sustainable development, being characterised by:73
(i) abundant raw materials resources
(ii) energy saving and environment protection
(iii) simple preparation technique

8 Mass change in 10% sulphuric acid in ASTM C267 test
of geopolymeric and Portland cement concretes72
(iv) good volume stability
(v) short setting time
(vi) ultra-high durability
(vii) high fire resistance and low thermal
conductivity
(viii) ability to immobilise toxic atoms
(ix) superior resistance to chemical attack.
All these properties make geopolymers a good substitute
for ordinary materials in fields of industry such as civil
engineering, automotive and aerospace, non-ferrous
foundries, waste management and art and decoration.
Geopolymer industry
Portland cement is widely used around the world; with
an annual consumption well in excess of 1000 Mt, water
is the only material used in greater quantities by
mankind. Over the 180 or so years it has been in
widespread use, knowledge has built up about its
processing and long-term behaviour, and limestone,
from which it is derived, is one of the most abundant
materials on the earth. Considering these factors, the
market position of Portland cement is strong. For
construction applications in particular, new materials
must meet a set of highly prescriptive standards and
validation procedures which is extremely expensive and
time-consuming for manufacturers.
Although the lack of knowledge, especially on the
long term behaviour of geopolymers, cannot be
neglected, an important reason for the slow development
of markets for geopolymers is this conservative view of
new materials. Consequently, it is not anticipated that
geopolymers will supply a significant amount of the
global need for cements in a near future. However, a
geopolymer industry is forming and an increasing
number of geopolymer supplier companies are becoming
established based on research activities in universities
and research institutes. Although there is no firm data
on the market size, geopolymer concrete is now used in
the transport sector in the USA and more recently in
Australia. The short setting time of geopolymer cement
makes it an ideal solution for repairing highways and
airport runways.
It is estimated that geopolymer products as pre-cast
concretes are 10–15% more expensive than OPC
concretes which, although the properties and service
lives are not the same, limits demands for geopolymer
concretes. However, when it comes to concretes for
severe environmental conditions such as oil wells,
geopolymers are very cost effective choices.
Note, however, that the cost of geopolymer concretes
varies according to raw materials. Selecting an Al–Si
material allowing acceptable levels of mechanical
properties to be obtained using low concentrations of
alkali atoms and silicate units to is the key to produce
Majidi Geopolymer technology, from fundamentals to advanced applications
cheaper geopolymer concretes. The effect of carbon
taxes on the cement and concrete industry will also help
the geopolymer industry to enhance its competitiveness
with respect to Portland cements. For example, the
European Emissions Trading Scheme (ETS),74 which
determines taxes on carbon dioxide release in the range
of J23–38/t CO2,75,76 will ensure that the economic
advantage of ordinary cements does not continue at its
current level.
The ability of geopolymer matrixes to immobilise
toxic materials and form an isolating coating for
radioactive materials has been widely tested and appears
to be accepted. In 1998 a pilot-scale experiment was
successfully carried out in the Wismut mine water
treatment facility at Schlema-Alberoda, Germany.77
This study showed geopolymer matrixes to be a mature
and cost-efficient solution to many problems where
hazardous residues must be treated and stored under
critical environmental requirements. In another success-
ful application, a geopolymeric shelter has been applied
to encapsulate high level waste from the failed
Chernobyl reactor 4.
Another promising application of geopolymers is
advanced fire resistant geopolymer composites.
Geopolymers reinforced with carbon or glass fibres
exhibit extraordinary mechanical properties at elevated
temperatures (Fig. 6) and are ideal materials for aero-
space applications. In 1994, a geopolymer matrix
composite was successfully used in a Formula 1 racing
car, replacing titanium parts in exhaust system, and
subsequently these composites have been widely adopted
in racing cars where their thermal properties are
effective.78 Carbon fibre reinforced geopolymer compo-
sites do not ignite, burn or release any smoke after
exposure to severe heat flux, which makes them
appropriate materials for aircraft cabin fire protection,
substituting for ordinary polymer matrix composites.
The US Air Force is now uses bombers equipped with
geopolymer composites as fire resistant materials.
Future research
Geopolymer technology is gaining interest because of
the successful application of products in various fields,
driven by the superior properties of geopolymers relative
to currently used materials. In addition, the environ-
mental impact of the production process of Portland
cement will drive active consideration of alternatives,
including geopolymers. However, the research commu-
nity first needs to address existing gaps in knowledge in
geopolymerisation and the properties of geopolymers. It
is possible to outline some key areas for future research.
First, improved characterisation of raw materials
appropriate for geopolymerisation is necessary.
Balancing mixture composition to meet ‘key para-
meters’, as suggested by Davidovits, usually leads to
contradictory results. It seems that XRF analysis of a
material and knowledge of the different oxide contents
alone cannot be used to predict precisely the response of
the material in alkali activation. The relationship
between XRD pattern and behaviour of the alumino-
silicate phases present in clays and wastes during
geopolymerisation should be considered and studied.
Second, the effects of the physical properties of the
Al–Si source on dissolution of the material in the alkali
solution and the kinetics of geopolymerisation deserve
Materials Technology 2009 VOL 24 NO 2 85
Majidi Geopolymer technology, from fundamentals to advanced applications
further investigation. For example, the effects of particle
size, morphology and zeta-potential on setting time,
microstructure and mechanical properties of geopoly-
mers needs to be clarified.
Third, little has been published on the effects of curing
conditions on the mechanical behaviour of geopolymers.
Optimised curing condition and the effects of atmo-
sphere humidity and heating of the paste on the
properties of the final geopolymer should be elucidated.
Fourth, the behaviour of geopolymer concretes with
different reinforcements is not fully understood. For
example, the corrosion mechanisms of steel embedded in
geopolymer matrixes would benefit from further
research.
Finally, the lack of knowledge on the long term
behaviour of geopolymers appears to be an important
barrier to further uptake. Data on the response of geo-
polymeric products to severe environments and under
creep and fatigue loading will be beneficial.
Conclusion
A brief history of geopolymers and highlights of
research activities in this area have been presented.
Geopolymer technology has a history of a little more
than half a century. Desirable properties, abundant raw
materials and successful applications of geopolymers
promise considerable progress in large scale production
of geopolymers in the near future.
In the past two decades, considerable research has
been carried out throughout the world, providing a large
volume of useful data and important findings on
geopolymerisation and the properties of geopolymers.
Various types of natural alumino-silicates and industrial
by-products have been examined as raw materials for
geopolymers and appropriate activation processes have
been proposed.
However, a lack of information on some aspects of
geopolymerisation has become apparent and the
research community should focus on these gaps.
Despite the current status and wide acceptance of
Portland cement, the desirable properties of geopoly-
mers, their environmental benefits and the strong
academic and commercial R&D activity suggest that
geopolymer technology is poised for significant progress
in the near future.
References
1. V. D. Glukhovsky: ‘Soil silicates’; 1959, Kiev, Gosstroyizdat
Ukrainy Publishing (in Russian).
2. V. D. Glukhovsky: ‘Oil silicates: their properties, technology and
manufacturing and fields of application’, DTech.Sc. Thesis, Civil
Engineering Institute, Kiev, Ukraine, 1965.
3. M. L. Granizo: ‘Activation alcalina de metacaolin: desarrolllo de
nuevos materials cementantes’, PhD thesis, University Autonoma
of Madrid, 1998 (in Spanish).
4. D. H. Campbell and R. L. Folk: ‘The ancient Egyptian pyramids –
concrete or rock’, Concrete Int., 1991, 29–44.
5. D. M. Roy and C. A. Langton: ‘Studies of ancient concretes as
analogs of cementituos sealing materials for repository in Tuff’,
Report LA-11527-MS, Los Alamos National Laboratory, USA,
1989.
6. J. Davidovits: ‘Soft mineralurgy and geopolymers’, Proc. 1st Int.
Conf. on Geopolymers, Compiegne, France, June 1988, Vol. 1, 19–
23.
7. A. Palomo, M. W. Grutzeck and M. T. Blanco: Cement Concrete
Res., 1999, 29, 1323.
86 Materials Technology 2009 VOL 24 NO 2
8. V. D. Glukhovsky, G. S. Rostovskaja and G. V. Rumyna: ‘High
strength slag-alkaline cements’, Proc. 7th Int. Conf. on Chemical
Cement, Paris, France, 1980, Vol. 3, 164–168.
9. P. V. Krivenko: ‘Alkaline cements’, Proc Int. Conf. on Alkaline
Cement and Concrete, 1994, Vol. 1, 11–130.
10. Hongling Wang, Haihong Li and Fengyuan Yan: ‘Synthesis and
mechanical properties of metakaolinite-based geopolymer’,
Colloids Surf. A: Physiocochem. Eng. Aspects, 2005, 268, 1–6.
11. J. Davidovits: ‘Geopolymers: man-made rocks, geosynthesis and
the resulting development of very early high strength cements’, J.
Mater. Educ., 1994, 16, 91–139.
12. Hua Xu and J. S. J. van Deventer: ‘The effect of alkali metals on
the formation of geopolymeric gels from alkali-feldspars’, Colloids
Surf. A: Physiocochem. Eng. Aspects, 2003, 216, 27–44.
13. F. Pacheco-Torgal, J. Castro-Gomes and S. Jalali: ‘Tungsten mine
waste geopolymeric binder: preliminary hydration products inves-
tigations’, Constr. Building Mater., 2009, 23, 200–209.
14. J. Davidovits: J. Therm. Anal., 1991, 37, (8), 1633.
15. J. Davidovits: J. Mater. Educ., 1994, 16, (2–3), 91.
16. H. Xu and J. S. J. Van Deventer: Int. J. Miner. Process., 2000, 59,
(3), 247.
17. H. Xu, J. S. J. Van Deventer and G. C. Lukey: Ind. Eng. Chem.
Res., 2001, 40, (17), 3749.
18. J. W. Phair, J. S. J. Van Deventer and J. D. Smith: Ind. Eng. Chem.
Res., 2000, 39, (8), 2925.
19. J. W. Phair and J. S. J. Van Deventer: Miner. Eng., 2001, 14, (3),
289.
20. J. G. S. Van Jaarsveld, J. S. J. Van Deventer and L. Lorenzen:
Miner. Eng., 1997, 10, (7), 659.
21. J. G. S. Van Jaarsveld and J. S. J. Van Deventer: Ind. Eng. Chem.
Res., 38, (10), 3932.
22. J. G. S. Van Jaarsveld and J. S. J. Van Deventer: Chem. Concr.
Res., 1999, 29, (8), 1189.
23. J. G. S. Van Jaarsveld, J. S. J. Van Deventer and A. Schwartzman:
Miner. Eng., 1999, 12, (1), 75.
24. P. S. Singh, T. Bastow and M. Trigg: ‘Outstanding problems posed
by nonpolymeric particulates in the synthesis of a well-structured
geopolymeric material’, Cement Concrete Res., 2004, 34, 1943–
1947.
25. J. Davidovits: ‘Chemistry of geopolymeric systems, terminology’,
Proc. Int. Conf. Geopolymer ’99, France, pp. 9–40.
26. J. Davidovits: ‘Properties of geopolymer cements’, Proc. 1st Int.
Conf. on Alkaline Cements and Concretes, Scientific Research
Institute on Binders and Materials, Kiev State Technical
University, Kiev, Ukraine, 1994, pp. 131–149.
27. R. Cioffi, L. Maffucci and L. Santoro: ‘Optimisation of geopoly-
mer synthesis by calcination and polycondensation of a kaolinitic
residue’, Resources, Conservation Recycling, 2003, 40, 27–38.
28. H. Xu and J. S. J Van Deventer: ‘The geopolymerisation of
alumino-silicate minerals’, Int. J. Miner. Process., 2000, 59, 247–
266.
29. J. Davidovits: ‘Geopolymers: inorganic polymeric new materials’,
J. Therm. Anal., 1991, 37, 1633–1656.
30. Ch. Kaps and A. Buchwald: ‘Property controlling influences on the
generation of geopolymeric binders based on clay’, Proc. Int. Conf.
Geopolymer 2002, Melbourne, Australia, October 2002.
31. H. Rahier, B. Wullart and B. Van Mele: ‘Influence of the degree of
dehydroxylation on the properties of aluminosilicate glasses’, J.
Therm. Anal. Calorimetry, 2000, 62, (2), 417–427.
32. M. L. Granizo, M. T. Blanco-Varela and A. Palomo: ‘Influence of
the starting kaolin on alkali-activated materials based on meta-
kaolin. Study of the reaction parameters by isothermal conduction
calorimetry’, J. Mater. Sci., 2000, 35, 6309–6315.
33. J. L. Provis, P. Duxson, J. S. J. Van Deventer and G. C. Lukey:
‘The role of mathematical modelling and gel chemistry in
advancing geopolymer technology’, Chem. Eng. Res. Design,
2005, 83, 853–860.
34. J. L. Provis and D. G. Vlachos: ‘Silica nanoparticle formation in
the system TPAOH–TEOS–H2O: a population balance model’, J.
Phys. Chem. B, 2006, 110, 3098–3108.
35. M. L. Granizo, M. T. Blanco-Varela and A. Palomo: ‘Influence of
the starting kaolin on alkali-activated materials based on meta-
kaolin. Study of the reaction parameters by isothermal conduction
calorimetry’, J. Mater. Sci., 2000, 35, 6309–6315.
36. S. Alonso and A. Palomo: ‘Alkaline activation of metakaolin and
calcium hydroxide mixtures: influence of temperature, activator
concentration and solids ratio’, Mater. Lett., 2001, 47, 55–62.
37. S. Alonso, A. Palomo: ‘Calorimetric study of alkaline activation of
calcium hydroxide–metakaolin solid mixtures’, Cement Concrete
Res., 2001, 31, 25–30.

38. H. Rahier, B. Van Mele, M. Biesemans, J. Wastiels and X. Wu:
‘Low-temperature synthesised aluminosilicate glasses. 1. Low-
temperature reaction stoichiometry and structure of a model
compound’, J. Mater. Sci., 1996, 31, 71–79.
39. H. Rahier, B. Van Mele and J. Wastiels: ‘Low-temperature
synthesised aluminosilicate glasses. 2. Rheological transformations
during low temperature cure and high-temperature properties of a
model compound’, J. Mater. Sci., 1996, 31, 80–85.
40. H. Rahier, J. F. Denayer and B. Van Mele: ‘Low-temperature
synthesised aluminosilicate glasses. Part IV, Modulated DSC study
on the effect of particle sise of metakaolinite on the production of
inorganic polymer glasses’, J. Mater. Sci., 2003, 38, 3131–3136.
41. L. Weng, K. Sagoe-Crentsil and T. Brow: ‘Speciation and
hydrolysis kinetics of aluminates in inorganic polymer systems’,
Proc. Int. Conf. Geopolymer 2002, October 2002, Melbourne,
Australia.
42. M. R. Anseau, J. P. Leung, N. Sahai and T. W. Swaddle:
‘Interactions of silicate ions with zinc (II) and aluminium (III) in
alkali aqueous solution’, Inorg. Chem., 2005, 44, (22), 8023–8032.
43. M. R. North and T. W. Swaddle: ‘Kinetics of silicate exchange in
alkaline aluminosilicate solutions’, Inorg. Chem., 2000, 39, (12),
2661–2665.
44. P. De Silva, K. Sagoe-Crenstil and V. Sirivivatnanon: ‘Kinetics of
geopolymerisation: role of Al2O3 and SiO2’, Cement Concrete Res.,
2007, 37, 512–518.
45. J. L. Provis and J. S. J. van Deventer: ‘Geopolymerisation kinetics.
1. In situ energy-dispersive X-ray diffractometry’, Chem. Eng. Sci.,
2007, 62, 2309–2317.
46. L. Weng, K. Sagoe-Crentsil, T. Brown and S. Song: ‘Effects of
aluminates on the formation of geopolymers’, Mater. Sci. Eng. B,
2005, 117, 163–168.
47. J. L. Provis and J. S. J. van Deventer: ‘Geopolymerisation kinetics.
2. Reaction kinetic modelling’, Chem. Eng. Sci., 2007, 62, 2318–
2329.
48. J. Faimon: ‘Oscillatory silicon and aluminum aqueous concentra-
tions during experimental aluminosilicate weathering’, Geochim.
Cosmochim. Acta, 1996, 60, 2901–2907.
49. H. Xu: ‘Geopolymerisation of aluminosilicate minerals’, PhD
thesis, Department of Chemical Engineering, University of
Melbourne, Australia.
50. J. G. S. Van Jaarsveld, J. S. J. Van Deventer and G. C. Lukey: ‘The
characterisation of source materials in fly ash-based geopolymers’,
Mater. Lett., 2003, 57, (7), 1272–1280.
51. J. Davidovits: ‘Gopolymers: inorganic polymeric new materials’, J.
Mater. Education, 1994, 16, 91–139.
52. Z. Zuhua, Y. Xiao, Z. Huajun, C. Yue: ‘Role of water in the
synthesis of calcined kaolin based-geopolymer’, Appl. Clay Sci., in
press
53. H. Wang, H. Li, F. Yan: ‘Synthesis and mechanical properties of
metakaolinite-based geopolymer’, Colloids Surf. A: Physicochem.
Eng. Aspects, 2005, 268, 1–6.
54. M. Luz Granizo, M. T. Blanco-Varela and S. Martınez-Ramırez:
‘Alkali activation of metakaolins: parameters affecting mechanical,
structural and microstructural properties’, J. Mater. Sci., 2007, 42,
2934–2943.
55. K. Komnitsas, D. Zaharaki and V. Perdikatsis: ‘Effect of synthesis
parameters on the compressive strength of low-calcium ferronickel
slag inorganic polymers’, J. Haz. Mater., 2009, 161, 760–768.
56. P. Duxson, J. L. Provis, G. C. Lukey, S. W. Mallicoat, W. M.
Kriven and J. S. J. Van Deventer: ‘Understanding the relationship
between geopolymer composition, microstructure and mechanical
properties’, Colloids Surf. A: Physicochem. Eng. Aspects, 2005, 269,
(1–3), 47–58.
57. J. Temuujin, A. van Riessen and R. Williams: ‘Influence of calcium
compounds on the mechanical properties of fly ash geopolymer
pastes’, J. Haz. Mater., in press.
Majidi Geopolymer technology, from fundamentals to advanced applications
58. C. K. Yip, J. L. Provis, G. C. Lukey and J. S. J. van Deventer:
‘Carbonate mineral addition to metakaolin-based geopolymers’,
Cement Concrete Compos., in press.
59. W. K. W. Lee and J. S. J. Van Deventer: ‘Use of infrared
spectroscopy to study geopolymerisation of heterogeneous amor-
phous aluminosilicates’, Langmuir, 2003, 19, 8726–8734.
60. W. K. W. Lee and, J. S. J. Van Deventer: ‘Structural reorganisation
of class F fly ash in alkaline silicate solutions’, Colloids Surf. A:
Physicochem. Eng. Aspects, 2002, 211, 49–66.
61. D. M. Zirl and S. H. Garofalini: ‘Structure of sodium alumino-
silicate glass surfaces’, J. Am. Ceram. Soc., 1992, 75, 2353–
2362.
62. P. I. K. Onorato, M. N. Alexander, C. W. Struck, G. W. Tasker
and D. R. Uhlmann: Bridging and nonbridging oxygen atoms in
alkali aluminosilicate glasses, J. Am. Ceram. Soc., 1985, 68, C148–
C150.
63. P. S. Singh, M. Trigg, I. Burgar and T. Bastow: ‘Geopolymer
formation processes at room temperature studied by 29Si and 27Al
MAS-NMR’, Mater. Sci. Eng. A, 2005, 396, 392–402.
64. R. E. Lyon, U. Sorathia, P. N. Balaguru, A. Foden, J. Davidovits
and M. Davidovics: Proc. 1st Int. Conf. on Fibre Composites in
Infrastructure (ICCI ’96), Tucson, AZ, USA, January 1996,
University of Arizona, pp. 972–981.
65. T. Lin, D. Jia, P. He, M. Wang and D. Liang: ‘Effects of fibre
length on mechanical properties and fracture behavior of short
carbon fibre reinforced geopolymer matrix composites’, Mater. Sci.
Eng. A, 2008, 497, 181–185.
66. W. Li and J. Xu: ‘Mechanical properties of basalt fibre reinforced
geopolymeric concrete under impact loading’, Mater. Sci. Eng. A,
in press.
67. P. N. Balaguru, S. Kurtz and J. Rudolph: ‘Geopolymer for repair
and rehabilitation of reinforced concrete beams’, Cement Concrete
Compos., 1997, 30, 431–443.
68. H. Wang, H. Li and F. Yan: ‘Reduction in wear of metakaolinite-
based geopolymer composite through filling of PTFE’, Wear, 2005,
258,1562–1566.
69. P. K Mehta: ‘Advanced cements in concrete technology’, Concrete
Int., 1999, 21, 67–76.
70. J. Davidovits: ‘Geopolymer chemistry and applications’, 505; 2005,
Saint Quentin, Institut Géopolymère.
71. J. Davidovits: ‘Environmentally driven geopolymer cement appli-
cations’, Proc. Int. Conf. Geopolymer 2002, Melbourne, Australia,
October 2002.
72. X. J. Song, M. Marosszeky, M. Brungs and R. Munn: Proc.
10DBMC Int. Conf. on Durability of Building Materials and
Components, Lyon, France, April 2005.
73. Z. Li, Z. Ding, Y. Zhang: ‘Development of sustainable cementi-
tious materials’, Proc. Int. Workshop on ‘Sustainable development
and concrete technology’, Beijing, China, 2004, 55–76.
74. Directive 203/87/Ec, European Union CO2 emissions trading
scheme.
75. C. Bohringer and A. Lange: ‘Efficiency, compensation and
discrimination: what is at stake when implementing the EU
emissions trading scheme?’, Centre for European Economic
Research, University of Heidelberg, Germany.
76. Z. Zhang: ‘Greenhouse gas emission trading and the world trading
system’, J. World Trade, 1998, 32, 219–239.
77. E. Hermann, C. Kunze, R. Gatzweiler, G. Kiebig and J.
Davidovits: ‘Solidification of various radioactive residues by
geopolymer with special emphasis on long-term stability’, Proc.
Conf. Géopolymère ’99, June–July 1999, Saint-Quentin, France,
Institut Géopolymère, 211–228.
78. J. Davidovits: ‘30 years of successes and failures in geopolymer
applications. Market trends and potential breakthroughs, Proc.
Int. Conf. Geopolymer 2002, Melbourne, Australia, October 2002.
Materials Technology 2009 VOL 24 NO 2 87