Minerals: Fly Ash-Based Geopolymer Binder: A Future Construction Material

minerals
Review
Fly Ash-Based Geopolymer Binder: A Future
Construction Material
Nakshatra B. Singh
Department of Chemistry, Sharda University, Greater Noida-201306, India; nbsingh43@gmal.com

Received: 15 May 2018; Accepted: 1 July 2018; Published: 12 July 2018
Abstract: A large amount of waste coming out from industries has posed a great challenge in its
disposal and effect on the environment. Particularly fly ash, coming out from thermal power plants,
which contains aluminosilicate minerals and creates a lot of environmental problems. In recent years,
it has been found that geopolymer may give solutions to waste problems and environmental issues.
Geopolymer is an inorganic polymer first introduced by Davidovits. Geopolymer concrete can be
considered as an innovative and alternative material to traditional Portland cement concrete. Use of
fly ash as a raw material minimizes the waste production of thermal power plants and protects
the environment. Geopolymer concretes have high early strength and resistant to an aggressive
atmosphere. Methods of preparation and characterization of fly ash-based geopolymers have been
presented in this paper. The properties of geopolymer cement/mortar/concrete under different
conditions have been highlighted. Fire resistance properties and 3D printing technology have also
been discussed.
Keywords: geopolymer; fly ash; compressive strength; microstructure; heat evolution; foam concrete
1. Introduction
Development of a country may be directly linked with the development of a cement industry.
Portland cement is the most widely produced man-made material on earth used for the manufacture of
concrete, the most prevalent building material on the planet. Demand for cement is increasing continuously
and in the next decades, cement and concrete production is expected to increase further. The production
of concrete is used by some economists as a measure of a country’s economic strength [1,2]. Cement
manufacture consumes huge amounts of raw materials and energy. Apart from this, a large amount of
solid waste and gaseous emissions particularly CO2 are produced [3]. Cement industry is considered to
be one of the greenhouse gas (GHG) emitters [4]; 0.83 kg CO2 is produced per kg cement production [5–7]
leading to 8% of total global anthropogenic CO2 emissions.
There are a number of drawbacks to Portland cement manufacture. Some of the major drawbacks
are: consumption of huge amounts of natural resources and energy, release of greenhouse gases, etc.
Apart from these, Portland cement is poor in immobilization of contaminants and the concretes made
from it are not durable in corrosive atmospheres. Atmospheric CO2 also reacts with the hydration
products and deteriorates the structure.
Above demerits of OPC compelled researchers to find new binders as an alternative to traditional
OPC so that a better, less energy and raw materials consuming with less emissions of greenhouse
gases can be obtained. Now, one of the most important new binding materials is geopolymer
cement [8–16]. Geopolymers are binding materials different from OPC and made by activating source
materials containing silica and alumina such as (fly ash) FA with alkali solutions and Na2 SiO3 .
A three-dimensional amorphous aluminosilicate network is formed due to geopolymerization.
Geopolymer binders are becoming important because of utilization of waste materials. One such
important source material is FA, which has extensively been used for synthesis of geopolymer concrete
Minerals 2018, 8, 299; doi:10.3390/min8070299 www.mdpi.com/journal/minerals

Minerals 2018, 8, 299 2 of 21
Minerals 2018, 8, x FOR PEER REVIEW 2 of 21
with better mechanical, chemical,

geopolymerization. Geopolymer thermal
bindersand
aredurability
becomingproperties
important as compared
because to OPC concrete
of utilization of waste [15].
However, there are many other source materials which have potentials to be used
materials. One such important source material is FA, which has extensively been used for synthesis as replacement
or addition to fly ash
of geopolymer in making
concrete with geopolymers.
better mechanical,Geopolymers made from
chemical, thermal different properties
and durability source materials
as
showcompared to OPC concrete
different properties. [15]. However,
Functionally gradedthere are manyspecimens
geopolymer other sourcehave materials
also beenwhich have by
fabricated
potentials
consecutive to be of
pouring used
twoasdifferent
replacement
pastesor with
addition to fly
fly ash ash in making
of different geopolymers.
particle Geopolymers
size and Si/Al weight ratios.
made from different source materials show different properties. Functionally graded geopolymer
These showed some interesting results [17]. New classes of geopolymers known as boroaluminosilicate
specimens have also been fabricated by consecutive pouring of two different pastes with fly ash of
geopolymers have also been synthesized from mixtures of fly ash and anhydrous borax [18,19].
different particle size and Si/Al weight ratios. These showed some interesting results [17]. New
Theseclasses
have entirely different microstructures.
of geopolymers known as boroaluminosilicate geopolymers have also been synthesized from
The increasing
mixtures of fly ashknowledge in understanding
and anhydrous the have
borax [18,19]. These science of geopolymerization
entirely is responsible
different microstructures.
for improving the properties of geopolymers particularly fly ash-based geopolymers.
The increasing knowledge in understanding the science of geopolymerization is responsible Because forof its
unique structure,the
improving geopolymer
properties is
ofageopolymers
better substitute for OPCfly
particularly in ash-based
different applications.
geopolymers. ABecause
literature survey
of its
unique
revealed thatstructure, geopolymer
geopolymers possessis aproperties
better substitute
superiorfor to
OPC OPCin different applications.
and because A literature
of various advantages,
survey revealed
geopolymer concretesthat
aregeopolymers
used in a numberpossessofproperties
areas. In superior to various
this article OPC andaspects
becauseofofflyvarious
ash-based
advantages, geopolymer concretes are used in a
geopolymer cement, mortars and concrete have been discussed.number of areas. In this article various aspects of fly
ash-based geopolymer cement, mortars and concrete have been discussed.
2. Geopolymer Cement
2. Geopolymer Cement
Geopolymer may be treated as one of the most promising and important alternative materials and
Geopolymer may be treated as one of the most promising and important alternative materials
it was first coined by the French scientist Joseph Davidovits [20]. When inorganic aluminosilicate-based
and it was first coined by the French scientist Joseph Davidovits [20]. When inorganic
materials react with alkaline
aluminosilicate-based solutions,
materials polycondensation
react with alkaline solutions,reaction forming reaction
polycondensation geopolymers
formingoccur.
Geopolymer
geopolymersstructure may be divided
occur. Geopolymer into
structure maythree basic into
be divided formsthreewhich depend
basic forms ondepend
which Si/Al onratios.
The three
Si/Al basic
ratios.units, polybasic
The three (sialate),
units, poly (sialate-siloxo)
poly (sialate), and poly (sialate-disiloxo)
poly (sialate-siloxo) as reported
and poly (sialate-disiloxo) as by
Yun-Ming et al.
reported by[13] are shown
Yun-Ming et al. in
[13]Figure 1. in Figure 1.
are shown
Figure 1. Structure of polysialates [13] (Reproduced with permission from Progress in Materials
Figure 1. Structure of polysialates [13] (Reproduced with permission from Progress in Materials Science;
Science; published by Elsevier, 2016).
published by Elsevier, 2016).
On activating aluminosilicate present in FA by alkalies, an inorganic polymer known as
geopolymer
On is formed.
activating The chemical
aluminosilicate structure
present inisFA
written as:
by alkalies, an inorganic polymer known as
geopolymer is formed. The chemicalM structure is written
n{—(SiO2)q—AlO2—}n as:
where M is an alkali cation, n the degree of polycondensation, and q is the Si/Al ratio. In general,
Mn {—(SiO2 )q —AlO2 —}n
geopolymer is a synthetic inorganic polymer and during the chemical reaction under alkaline
conditions, a three-dimensional polymeric chain structure is developed. Composition of raw
where M is an alkali cation, n the degree of polycondensation, and q is the Si/Al ratio. In general,
materials and the nature and concentrations of alkaline solutions control the microstructures and
geopolymer is a synthetic inorganic polymer and during the chemical reaction under alkaline
mechanical properties of the geopolymers.
conditions, a three-dimensional polymeric chain structure is developed. Composition of raw materials
and the nature and concentrations of alkaline solutions control the microstructures and mechanical
properties of the geopolymers.
Minerals 2018, 8, 299 3 of 21
The significance of geopolymer binders in replacing OPC binders is based on the fact that there are
huge amounts of waste materials containing aluminosilicates obtained from industries and agriculture
and result in
The
Minerals problems
8, x FOR of
significance
2018, their disposalbinders
of REVIEW
PEER geopolymer [21]. in replacing OPC binders is based on the fact that 3there
of 21
are huge amounts of waste materials containing aluminosilicates obtained from industries and
3. SynthesisThe
ofsignificance
and resultof
Geopolymer
agriculture ingeopolymer
Cementofbinders
problems in replacing
their disposal [21]. OPC binders is based on the fact that there
are huge amounts of waste materials containing aluminosilicates obtained from industries and
Geopolymers
3. Synthesisand
agriculture are
of normally
Geopolymer
result synthesized
Cement
in problems by mixing
of their disposal [21]. source materials having alumino-silicate and
the alkaline solutions. Source materials used are kaolinite, clays, zeolite, fly ash, silica fume, slag,
Geopolymers are normally synthesized by mixing source materials having alumino-silicate and
3. Synthesisash,
POFA, rice-husk of Geopolymer
red mud, Cement
etc. The most
the alkaline solutions. Source materials usedcommon alkaline
are kaolinite, clays,liquid
zeolite,used in geopolymerization
fly ash, silica fume, slag, is a
combination
POFA, of NaOH/KOH
Geopolymers
rice-husk arered
ash, and
mud,sodium
normally The silicate.
synthesized
etc. mostby Whenalkaline
mixing
common any ofmaterials
source the above
liquid source
having
used in materials (for
alumino-silicate
geopolymerization is aexample
and
the
fly ash (FA) alkaline
in solid
combination solutions.
ofform) Source
are
NaOH/KOH materials
mixed
and with
sodiumused
alkaliaresolutions
kaolinite,
silicate. When any clays,
of of zeolite,
appropriate
the abovefly concentration
ash, silica
source fume, and
materials slag,
(forsodium
silicate,POFA,
example rice-husk
geopolymers ash,formed.
fly ash (FA)
are redsolid
in mud, Itetc.
form)hasThe
are mostreported
mixed
been common alkaline
with alkali
by Xiaoliquid
solutions of used
et al. in geopolymerization
appropriate
[7] that concentration
during is a
and
the polymerization
combination
sodium silicate,of NaOH/KOH
geopolymers and sodium It
are formed. silicate.
has beenWhen any ofbythe
reported above
Xiao source
et al. materials
[7] that during (for
the
reaction of fly ash, the following processes may take place (Figure 2).
example fly ash reaction
polymerization (FA) in solid
of flyform) arefollowing
ash, the mixed with alkali solutions
processes may takeofplace
appropriate
(Figure concentration
2). and
sodium silicate, geopolymers are formed. It has been reported by Xiao et al. [7] that during the
polymerization reaction of fly ash, the following processes may take place (Figure 2).
Figure 2. Processes of geopolymerization from FA [7] (Reproduced with permission from Journal of
Figure 2. Processes of geopolymerization from FA [7] (Reproduced with permission from Journal of
Cleaner Production; published by Elsevier, 2016).
CleanerFigure
Production; published
2. Processes by Elsevier, from
of geopolymerization 2016).
FA [7] (Reproduced with permission from Journal of
Sometimes
Cleaner the alkali
Production; activator
published in solid 2016).
by Elsevier, form is milled together with source materials (e.g., FA)
with a certain composition, resulting
Sometimes the alkali activator in solid form in a fine grain similar to
is milled cement. with
together This issource
then mixed with an
materials (e.g., FA)
Sometimes
appropriate the alkali
amount activator
of water at theintime
solidofform is milled
its use together
[13,22]. with source
Diagrammatical materials (e.g.,
representation of FA)
the
with a certain
with composition,
a certain composition,resulting in a a fine3.grain similar to cement. This is then mixed with anwith an
fine grain similar to cement. This is then mixed
method as reported [13] can resulting
be seen ininFigure
appropriate amount of water at the time
appropriate amount of water at the time ofof its useits[13,22]. Diagrammatical
use [13,22]. Diagrammaticalrepresentation
representation of
of the
the method
as reported [13]
method ascan be seen
reported [13] in
canFigure
be seen3.in Figure 3.
Figure 3. Geopolymerization by dry mixing [13] (Reproduced with permission from Progress in
Materials Science; published by Elsevier, 2016).
Minerals 2018, 8,
Minerals 2998, x FOR PEER REVIEW
2018, 4 of 21 4 of 21
Figure 3. Geopolymerization by dry mixing [13] (Reproduced with permission from Progress in
4. Geopolymer Concrete
Materials Printing
Science; published by Elsevier, 2016).
Use of group of
4. Geopolymer techniques
Concrete in making 3D structures straightway from a digital model is known
Printing
as additive manufacturing (AM). This may (1) reduce the number of workers resulting into cost
Use of group of techniques in making 3D structures straightway from a digital model is known
reduction and safety; (2) reduce construction time; (3) reduce the chances of mistakes and (4) increase
as additive manufacturing (AM). This may (1) reduce the number of workers resulting into cost
architectural freedom [23,24]. Now, 3D printing of concrete is developed more in comparison to
reduction and safety; (2) reduce construction time; (3) reduce the chances of mistakes and (4)
conventional methods of casting
increase architectural freedomconcrete
[23,24].into
Now,formwork. Layering
3D printing processes
of concrete in geopolymers
is developed more inresult in
an increase in flexural
comparison strength [25].
to conventional methods of casting concrete into formwork. Layering processes in
Three-D printing
geopolymers resultprocesses increased
in an increase compressive
in flexural strength [25].strengths of geopolymer mortars made from
variety ofThree-D printing processes
aluminosilicate increased
materials compressive
including FA. It strengths
was found of geopolymer
that theremortars made from in the
was anisotropy
variety of aluminosilicate materials including FA. It was found that
compressive strengths due to layered deposition of the geopolymer mortars [26]. there was anisotropy in the
compressive strengths due to layered deposition of the geopolymer mortars [26].
5. Reactions during Geopolymerization
5. Reactions during Geopolymerization
The process of geopolymerization is a chemical reaction between an alkali solution and source
The process of geopolymerization is a chemical reaction between an alkali solution and source
material containing
material aluminosilicate
containing aluminosilicate(FA)
(FA) and givesaathree-dimensional
and gives three-dimensional polymeric
polymeric chainchain and ring
and ring
structure consisting of Si–O–Al–O bonds, as reported by Scheme 1 [27]. The reactions can
structure consisting of Si–O–Al–O bonds, as reported by Scheme 1 [27]. The reactions can occur at occur at
room room
temperature. Therefore,
temperature. it it
Therefore, cancanbe
beconsidered asenergy
considered as energyand
and source
source efficient
efficient and and
muchmuch cleaner.
cleaner.
Scheme1.1.Reactions
Scheme Reactions during
duringgeopolymerization
geopolymerization[27].[27].
The following steps may be involved during the geopolymerization reaction [28,29]:
The following steps may be involved during the geopolymerization reaction [28,29]:
 Si and Al atoms present in the fly ash may dissolve by the action of hydroxide ions.
•  and
Si Precursor
Al atomsions may bein
present converted intomay
the fly ash monomers.
dissolve by the action of hydroxide ions.
•  Polycondensation of monomers into polymeric
Precursor ions may be converted into monomers. structures.
• These three steps

Polycondensation of can occur almost
monomers intosimultaneously and may also overlap.
polymeric structures.
Reaction (2) indicates that during polymerization, water is eliminated. On the other hand,
These
duringthree stepsofcan
hydration occur
OPC, almost
water simultaneously and may also overlap.
is consumed.
Furthermore,
Reaction due that
(2) indicates to different
during sizes and charge water
polymerization, densities, different alkali
is eliminated. On cations
the otheraffect theduring
hand,
nucleation and growth of aluminosilicate
hydration of OPC, water is consumed. chains in different ways and, as a result, the rate and the
extent of polymerization
Furthermore, change differently
due to different [12,30].
sizes and For example,
charge densities,K+ different
cation (1.33alkali
Å) having a larger
cations affect the
size and lower charge density than that of Na cation (0.97 Å) leads to a higher degree of
+
nucleation and growth of aluminosilicate chains in different ways and, as a result, the rate and
polymerization of geopolymer matrix [12,31]. The exact mechanism of setting and hardening of the
the extent of polymerization change differently [12,30]. For example, K+ cation (1.33 Å) having a
larger size and lower charge density than that of Na+ cation (0.97 Å) leads to a higher degree of
polymerization of geopolymer matrix [12,31]. The exact mechanism of setting and hardening of the
geopolymer material is not well understood. However, based on the findings of Marios et al. [32],
tentative mechanism of geopolymerization can be proposed by Scheme 2 [32].
geopolymer material is not well understood. However, based on the findings of Marios et al. [32],
geopolymer
tentative materialofisgeopolymerization
mechanism not well understood.
canHowever, based
be proposed byon the findings
Scheme 2 [32]. of Marios et al. [32],
tentative mechanism of geopolymerization can be proposed by Scheme 2 [32].
Minerals 2018, 8, 299 5 of 21
Scheme
Scheme2.2.Proposed
Proposed mechanism
Proposed ofgeopolymerization.
mechanismof
mechanism geopolymerization.
When
When
When flyfly
fly ash
ash ash reacts
reacts withwith
reacts with alkalies
alkalies
alkalies forming
forming
forming geopolymers,
geopolymers,
geopolymers, its surface
its
its surface surface
gets getscorroded
gets
corroded corroded
and andand
amorphous
amorphous
amorphous
reaction reaction
products are products
reaction are
productsRyu
formed. formed.
areet
formed. Ryu et aal.
al. proposed al.model
proposed
proposed aamodel
(Figure model
4) [33]. (Figure
(Figure 4)4) [33].
[33].
The reaction The
The reaction
reaction
products make
products
products makethe
make thestructure
structuredense.
dense.
the structure dense.
Figure 4. Interaction of fly ash with alkali activator [33] (Reproduced with permission from
Figure 4. Interaction
Interaction
Construction ofof fly
and Building fly ash
ash with
with
Materials; alkali
alkali activator
published activator [33]
[33]
by Elsevier, (Reproduced
(Reproduced with
2013). with permission
permission from
Construction and Building Materials; published by Elsevier,
Elsevier, 2013).
2013).
6. The Structure of Geopolymers
6. The
The Structure
Structure of Geopolymers
In spite of large number of studies, a definite structural model could not be proposed for
geopolymers.
In spite ofItlarge
may be due to of
number its amorphous nature. Small
studies, a definite molecules
structural
structural (oligomers)
model
model could
could not
notcombine togetherfor
be proposed
forming 3D network
geopolymers. It
It may beduring
may be due togeopolymerization.
due its
its amorphous nature.Spectroscopic
Small methods(oligomers)
Small molecules
molecules have been used
(oligomers) to propose
combine together
structure
forming
forming 3D to polymers.
network Theoretical
during models have
geopolymerization. been proposed and ab initio DFT calculations
geopolymerization. Spectroscopic methods have been used propose
Spectroscopic methods have been used to were
made
structure by Koleżyński et al. [14];
structure to polymers. Theoretical the proposed
Theoretical models
models havestructural
have been model
been proposed for
proposed and geopolymer is given in Figure
and ab initio DFT calculations were 5.
Using
made solid state MAS NMR, a new model was also proposed for N–A–S–H gel [15].
made by Koleżyński
Koleżyński et
et al.
al. [14];
[14]; the
the proposed
proposed structural
structural model
model for
for geopolymer
geopolymer isis given
given in
in Figure
Figure 5.
5.
Using solid state MAS NMR, a new model was also proposed for N–A–S–H gel [15]. [15].
Minerals 2018, 8, 299 6 of 21
Figure 5. Structural model of geopolymer with 800 (Si:Al = 2.81) [14] (Reproduced with permission
Figure 5. Structural model of geopolymer with 800 (Si:Al = 2.81) [14] (Reproduced with permission
from Journal of Molecular Structure; published by Elsevier, 2018).
from Journal of Molecular Structure; published by Elsevier, 2018).
7. Casting and Curing of Test Specimens
7. Casting and Curing of Test Specimens
Although there is no standard method prescribed, geopolymer concrete is made in a similar
way as conventional
Although there is noPortland
standardcementmethod concrete. First of
prescribed, all, activator
geopolymer solutions
concrete as given
is made in ahere are way
similar
prepared. The required quantity of NaOH pellets is dissolved in water to have
as conventional Portland cement concrete. First of all, activator solutions as given here are prepared. to the required
concentration. For example, to prepare an 8 M NaOH solution, 320 g of NaOH pellets are dissolved
The required quantity of NaOH pellets is dissolved in water to have to the required concentration.
in one liter of solution since the molecular weight of NaOH is 40. This solution is then mixed with
For example, to prepare an 8 M NaOH solution, 320 g of NaOH pellets are dissolved in one liter of
the required quantity of Na2SiO3 solution to fix the ratio of alkaline activator solution as 1.5, 2.0 and
solution
2.5. since thesand
Fly ash, molecular
and theweight
aggregatesof NaOH
are firstismixed
40. This solution
together in dryis then mixed
state and thenwith
mixed thewith
required
quantity of Na
alkaline 2 SiOand
liquid 3 solution
a small to fix of
dose the ratio
the superof plasticizer.
alkaline activator
Extra water solution
may beasadded
1.5, 2.0 and 2.5.The
if needed. Fly ash,
sand and
freshthe aggregates
concrete was castareand
first mixed together
compacted in dry
in the molds of state andsize.
standard thenGenerally,
mixed with alkaline(60–90
heat-curing liquid and
°C)dose
a small of geopolymer
of the super concrete is done.Extra
plasticizer. It assists
waterthe may
chemical reactionifthat
be added occursThe
needed. in the geopolymer
fresh concrete was
paste. Microwave heating can also be used for curing [34].
cast and compacted in the molds of standard size. Generally, heat-curing (60–90 C) of geopolymer ◦
concrete is done. It assists the chemical reaction that occurs in the geopolymer paste. Microwave
8. Factors Affecting Geopolymerization
heating can also be used for curing [34].
Some of the important factors which affect the process of geopolymerization are given below.
8. Factors Affecting Geopolymerization
I. Type of raw materials containing aluminosilicate
II. of the
Some Surface area of solid
important rawwhich
factors materials
affect the process of geopolymerization are given below.
III. Glassy phase content in the raw material
I. IV.
Type ofAmount
raw materials
of aluminumcontaining aluminosilicate
and reactive silicon
V.
II. Surface Presence
area of of iron,raw
solid calcium, and inert particles in FA
materials
III. VI.
Glassy Curing
phase temperature
content in the and pressure
raw material
VII. Duration of curing
IV. VIII.
Amount of aluminum and reactive silicon
Type of curing (conventional heating or microwave heating)
V. Presence
IX. of and
Type iron,concentration
calcium, and of inert particles in FA
alkalies
VI. Curing
X. temperature
Alkaline and pressure
liquid-to-raw material ratio
XI.
VII. Duration H2Ooftocuring
Na2O molar ratio
XII. Water to Geopolymer solids ratio
VIII. Type of curing (conventional heating or microwave heating)
XIII. Na2O to SiO2 ratio
IX. XIV.
Type and
SiOconcentration
2 to Al2O3 ratio
of alkalies
X. Alkaline liquid-to-raw material ratio
XI. H2 O to Na2 O molar ratio
XII. Water to Geopolymer solids ratio
XIII. Na2 O to SiO2 ratio
XIV. SiO2 to Al2 O3 ratio
Minerals 2018, 8, 299 7 of 21
In general, geopolymerization increase with curing time and curing temperature (up to 90 ◦ C).
In general, geopolymerization increase with curing time and curing temperature (up to 90 °C).
Higher
Higher concentrations
concentrationsofofalkalies
alkaliesenhance
enhance thethe geopolymerization,
geopolymerization, whereaswhereasthe thetype
type
ofof alkalies
alkalies also
also
affect thethe
affect process. With
process. Withthethe
increase
increaseofof
HH 2 O-to-Na
2O-to-Na 2 O, Water/Geopolymer Solids, Na2 O/SiO
2O, Water/Geopolymer Solids, Na2O/SiO 2 ratios,
2 ratios,
compressive strength decreases indicated lesser geopolymerization.
compressive strength decreases indicated lesser geopolymerization.
TheThevariation
variationofofcompressive
compressivestrength
strengthwith
with SiO /Na2O
SiO22/Na 2 O/Al
/Al O3 /Na
2O23/Na 2 O ratio
2O ratio as reported
as reported by et
by Ryu Ryu
et al. [33] is
is shown
shownin inFigure
Figure6.6.As
Asthe
theratio
ratio increased,
increased, thethe compressive
compressive strength
strength decreased.
decreased.
Figure 6. 6.Compressive
Figure CompressiveStrength
Strength vsvsSiO2 /Na
SiO O and
2/Na22O and Al22OO3/Na
3 /Na
2O2 O ratio[33]
ratio [33](Reproduced
(Reproduced with
with
permission
permissionfrom Construction
from Constructionand
andBuilding
BuildingMaterials;
Materials; published byElsevier,
published by Elsevier,2013).
2013).
Barbosa et al. [35] found that the optimum Na2O/SiO2, H2O/Na2O and SiO2/Al2O3 ratios were
Barbosa et al. [35] found that the optimum Na2 O/SiO2 , H2 O/Na2 O and SiO2 /Al2 O3 ratios
found to be 0.25, 10.0, and 3.3 for better performance [36]. In order to have an idea about the effect of
were found to be 0.25, 10.0, and 3.3 for better performance [36]. In order to have an idea about the
different parameters on geopolymerization, setting times were determined. Experiments were
effect of different parameters on geopolymerization, setting times were determined. Experiments
designed using the Taguchi model [37]. Furthermore, when geopolymers are subjected to high
were designed using the Taguchi model [37]. Furthermore, when geopolymers are subjected to
temperature (350 °C)◦ and high pressure known as hot pressing the mechanical properties are
high temperature (350 C) and high pressure known as hot pressing the mechanical properties are
enhanced [38].
enhanced [38].
9. Characterization of Geopolymers
9. Characterization of Geopolymers
There are a large number of techniques which have been used for the characterization of
There arecements.
geopolymer a large Some
number of techniques
of the techniqueshave
which
beenhave beenbelow.
discussed used for the characterization of
geopolymer cements. Some of the techniques have been discussed below.
9.1. X-ray Diffraction Technique
9.1. X-ray Diffraction Technique
XRD patterns of fly ash and geopolymer as recorded by Hanjitsuwan et al. [39] are shown in
XRD7.patterns
Figure The fly of
ashfly ash and
consists of geopolymer
an amorphous asphase
recorded
withby Hanjitsuwan
broad et al.2θ
hump around [39] are shown
= 20–38°. The in
Figure 7. The fly ash consists of an amorphous phase with broad hump around 2θ = 20–38 ◦ . The other
other peaks are due to some crystalline phases present. In geopolymer the hump is not changed.
peaks are due to some crystalline phases present. In geopolymer the hump is not changed.
Minerals 2018, 8, 299 8 of 21
Figure 7.Figure
XRD 7. XRD pattern
pattern of flyand
of fly ash ashgeopolymer
and geopolymer
[39][39] (Reproducedwith
(Reproduced with permission
permission from
fromCement
Cement and
and Concrete Composites; published by Elsevier, 2014).
Concrete Composites; published by Elsevier, 2014).
9.2. Figure 7. XRD pattern of fly ash and geopolymer [39] (Reproduced with permission from Cement
FTIR Spectra of Geopolymers
and Concrete
9.2. FTIR Spectra Composites; published by Elsevier, 2014).
of Geopolymers
FTIR spectra of geopolymer prepared in the presence of different concentrations of NaOH and
FTIRcured
9.2. at Spectra
spectra
FTIR 60 of
°C geopolymer
asofreported by prepared
Geopolymers Nath et al. [40] arepresence
in the shown in Figure 8. Bands
of different at 460 cm−1 and 550
concentrations cm−1
of NaOH and
◦
respectively
cured at 60 FTIR are
C asspectra
reportedassigned to in plane
by Nath etpreparedand bending
al. [40] in
are vibrations of Al–O/Si–O [39]. −
Geopolymer
1 550 cm−1
with
of geopolymer theshown in of
presence Figure 8. Bands
different at 460 cm
concentrations of NaOHandand
8M NaOH showed a much broader peak, may be due to the presence of large amount of structural
respectively
cured are
at 60assigned to inby
°C as reported plane
Nath and
et al. bending vibrations
[40] are shown of8.Al–O/Si–O
in Figure Bands at 460[39]. Geopolymer
cm−1 and 550 cm−1 with
water. Appearance of a band at ~1456 cm−1 may be due to C=O vibrations, confirming the presence
8M NaOHrespectively
showed are
a assigned
much to in plane
broader peak,andmaybending
be vibrations
due to the of Al–O/Si–O
presence of [39].
largeGeopolymer
amount ofwith
structural
of carbonate groups [40].
8M NaOH showed a much broader peak,
− 1 may be due to the presence of large
water. Appearance of a band at ~1456 cm may be due to C=O vibrations, confirming the presence of amount of structural
water. Appearance of a band at ~1456 cm−1 may be due to C=O vibrations, confirming the presence
carbonate groups [40].
of carbonate groups [40].
Figure 8. FTIR spectra of geopolymer [40] (Reproduced with permission from Construction and
Building Materials; published by Elsevier, 2016).
Figure 8. FTIR spectra of geopolymer [40] (Reproduced with permission from Construction and
9.3. NMR Spectroscopic Technique
Figure 8. FTIRMaterials;
Building spectra published
of geopolymer [40]2016).
by Elsevier, (Reproduced with permission from Construction and
BuildingNMR is a technique
Materials; to derive
published structural
by Elsevier, and compositional features (or changes) of most of the
2016).
compact
9.3. or porous Technique
NMR Spectroscopic (zeolitic) natural and synthetic aluminosilicates [41]. 29 Si-NMR allows
9.3. NMR Spectroscopic Technique
NMR is a technique to derive structural and compositional features (or changes) of most of the
compact or porous (zeolitic) natural and synthetic aluminosilicates [41]. Si-NMR allows
29
NMR is a technique to derive structural and compositional features (or changes) of most
of the compact or porous (zeolitic) natural and synthetic aluminosilicates [41]. 29 Si-NMR allows
straightforward determination of the framework Si/Al ratios and the resolution of crystallographically
non-equivalent sites. The distribution of Al atoms on the various sites can either be random or
Minerals
Minerals 2018,
2018, 8, 2998, x FOR PEER REVIEW 9 of 219 of 21
straightforward determination of the framework Si/Al ratios and the resolution of

specific. 27 Al-NMR characterizes
crystallographically non-equivalent sites. Theindistribution
Al species of Al atoms on the
different coordination. MAS various
NMR sites can either is
spectroscopy
be random
an important or for
tool specific. 27Al-NMR characterizes Al species in different coordination. MAS NMR
the study of inorganic solids such as minerals, zeolites, clays, ceramics and
spectroscopy is an important tool27for the study of inorganic solids such as minerals, zeolites, clays,
cementitious systems with 29 Si and Al representing some of the most important nuclei. In 29 Si MAS
ceramics and cementitious systems with 29Si and 27Al representing some of the most important
NMR, the chemical shift (δ( Si)) depends on the local environments of the 29 Si nucleus.
29
nuclei. In 29Si MAS NMR, the chemical shift (δ(29Si)) depends on the local environments of the 29Si 29
The exploratory investigations on silicates with known molecular structure showed that Si
nucleus.
chemical The shiftexploratory
mainly depends on theondegree
investigations ofwith
silicates condensation
known molecularof SiO4structure
tetrahedra showedwiththat
increasing
29Si
condensation corresponding to a high-field shift, i.e., more negative δ( 29 Si). Furthermore, it was shown
chemical shift mainly depends on the degree of condensation of SiO4 tetrahedra with increasing
that each AlO4 tetrahedron
condensation corresponding connected to a SiO
to a high-field 4 group
shift, increases
i.e., more δ(29δ(
negative Si) byFurthermore,
29Si). approximately 5 ppm.
it was
shown that
In addition, the each
NMRAlO 4 tetrahedron
intensity connected
is directly to a SiO4 group
proportional to the increases
number δ( of2929
Si)Sibynuclei
approximately 5
present which
allowsppm. In addition,
quantitative the NMR intensity
determination of Si iscomponents. Thus, 29toSithe
directly proportional MASnumber
NMR of represents
29Si nuclei present
a valuable
whichforallows
technique studyingquantitative
amorphous determination
systems, and of in
Si the
components. Thus, 29Si MAS
area of cementitious systemsNMR represents
to obtain a
structural
valuable technique for studying amorphous systems, and in the area of cementitious systems to
and kinetic information. NMR was used for the first time in the 1980s to investigate the structure of
obtain structural and kinetic information. NMR was used for the first time in the 1980s to investigate
metakaolin-based geopolymer by Davidovits.
the structure of metakaolin-based geopolymer by Davidovits.
29 Si MAS NMR results showed that fraction of aluminum-rich structural units were found more
29Si MAS NMR results showed that fraction of aluminum-rich structural units were found
compared
more to silicon-rich
compared units with
to silicon-rich increasing
units reactionreaction
with increasing times. The increase
times. in strength
The increase was due
in strength was to (i)
more due
aluminum
to (i) morerich structural
aluminum units;
rich (ii) higher
structural units; cross linking
(ii) higher and
cross (iii) higher
linking and (iii)compactness
higher compactness[42].
[42].
9.4. Thermal Methods of Characterization of Geopolymer
9.4. Thermal Methods of Characterization of Geopolymer
With heat treatments, shrinkage and weight loss of Na-geopolymers at 1.15 ≤ Si/Al ≤ 2.15
With heat
occurred [40,41]. treatments,
The shrinkage shrinkage and weight by
can be influenced lossthe
of Si/Al
Na-geopolymers
ratio. TGA at of
1.15
the≤ geopolymers
Si/Al ≤ 2.15 as
reported by Nath et al. [40] are shown in Figure 9. Loss in weight between 100 C and 700 ◦ Cascould
occurred [40,41]. The shrinkage can be influenced by the Si/Al ratio. TGA of the◦ geopolymers
be duereported by Nath etbonded
to structurally al. [40] are shown
water in in Figure
the 9. Loss gel.
N–A–S–H in weight
Thisbetween 100gave
indirectly °C andan700 °C about
idea could the
be due to structurally bonded water in the N–A–S–H gel. This indirectly gave an idea about the
reaction product.
reaction product.
Figure 9. TGA of geopolymer [40] (Reproduced with permission from Construction and Building
Figure 9. TGApublished
Materials; of geopolymer [40]2016).
by Elsevier, (Reproduced with permission from Construction and Building
Materials; published by Elsevier, 2016).
9.5. Heat Evolution during Geopolymerization
9.5. Heat Evolution during Geopolymerization
Sun and Vollpracht [43] studied in detail the heat evolution of FA geopolymerization in the
presence
Sun and of NaOH (Figures
Vollpracht 10–12). Sample
[43] studied designation
in detail the heatwith differentof
evolution parameters is given in Table 1.
FA geopolymerization in the
presence of NaOH (Figures 10–12). Sample designation with different parameters is in
Effect of NaOH concentration on heat evolution and cumulative heat at 20 °C is given Figure
given in 10.
Table 1.
As soon as the activator solution is mixed with fly ash, an exothermic peak due to wetting appeared
Effect of NaOH concentration on heat evolution and cumulative heat at 20 ◦ C is given in Figure 10.
[44].
As soon as the activator solution is mixed with fly ash, an exothermic peak due to wetting appeared [44].
Minerals 2018, 8, 299 10 of 21

Table 1. Oxide molar ratio of NaOH activated Fly Ash with SiO2 /Al2 O3 = 4.6 [43].
Table 1. Oxide molar ratio of NaOH activated Fly Ash with SiO2/Al2O3 = 4.6 [43].
Table 1. Oxide molar ratio of NaOH activated Fly Ash with SiO2/Al2O3 = 4.6 [43].
Sample ID SampleSiO
ID 2 /Na
SiO
2O2/Na2O SiO
SiO 2/(Na
2 /(Na 2O 2O+ +CaO)
CaO) HH
2O/Na
2 O/Na2O O H2O/(Na
2 2O + CaO)
H2 O/(Na 2 O + CaO)
Sample ID SiO2/Na
FA-6-0.45 4.3 2O SiO2/(Na22.8 O + CaO) H2O/Na13.1 2O H2O/(Na28.8
O + CaO)
FA-6-0.45 4.3 2.8 13.1 8.8
FA-6-0.45 4.3 2.8 13.1 8.8
FA-9-0.45FA-9-0.45 3.5 3.5 2.52.5 10.0
10.0 7.1 7.1
FA-9-0.45
FA-12-0.45FA-12-0.45 3.2 3.53.2 2.5
2.32.3 10.0
8.88.8 7.1
6.4 6.4
FA-12-0.45 3.2
FA-9-0.4 FA-9-0.4 3.8 3.8 2.3
2.62.6 8.8
9.79.7 6.4
6.7 6.7
FA-9-0.5FA-9-0.4
FA-9-0.5 3.2 3.8 3.2 2.6
2.42.4 9.7
10.2
10.2 6.7
7.4 7.4
FA-9-0.6FA-9-0.5
FA-9-0.6 2.8 3.2 2.8 2.4
2.12.1 10.2 10.6
10.6 7.4
8.0 8.0
FA-9-0.7FA-9-0.6
FA-9-0.7 2.5 2.8 2.5 1.9
2.11.9 10.6 10.9
10.9 8.5 8.5
8.0
FA-9-0.7 2.5 1.9 10.9 8.5
FigureFigure 10. of
10. Effect Effect
NaOH of NaOH concentration
concentration on heaton heat evolution.
evolution. (a) Heat(a)flow
Heat flow inFA,
in mW/g mW/g FA, (b)
(b) Cumulative
heat Figure 10. [43]
inCumulative
J/g FA Effect
heat of J/g
in NaOH
(Reproduced concentration
FA [43] (Reproduced
with onwith
permission heat evolution.
permission
from Cementfrom (a) Cement
and Heat flow
Concrete andin mW/g published
Concrete
Research; FA, (b) by
Research;
Cumulative
published heat in J/g FA [43] (Reproduced with permission from Cement and Concrete Research;
Elsevier, 2018). by Elsevier, 2018).
Figure 11 gives the effect of liquid/solid ratio on heat of reaction during activation of FA by
Figure
NaOH. 11
Figure gives thethe
11 gives
A low effect ofofliquid/solid
effect
liquid/solid ratio liquid/solid
retards ratioon
ratio
the process ongeopolymerization
of heatofofreaction
heat reaction during
during
[45]. activation
activation of FAofbyFA by
NaOH.
NaOH. A low
A low liquid/solid
liquid/solid ratioretards
ratio retards the
the process
process of
ofgeopolymerization
geopolymerization [45].
[45].
Figure 11. Heat evolution in the presence of varying liquid/solid ratio. (a) Heat flow in mW/g FA, (b)
Figure 11. Heat
Figure evolution
11. Heat
Cumulative in J/gin
evolution
heat inthe
FA [43]presence
the presence ofvarying
of
(Reproduced varying liquid/solid
liquid/solid
with permission ratio.ratio.
from (a)and
(a) Heat
Cement Heat
flow inflow
mW/g
ConcreteinResearch;
mW/g
FA, (b) FA;
(b) Cumulative
published heat
Cumulative heat
by in
in J/g FA[43]
J/g FA
Elsevier, [43](Reproduced
2018). (Reproduced with
with permission
permission fromfrom Cement
Cement and and Concrete
Concrete Research;
Research;
published
published by Elsevier,
by Elsevier, 2018).
2018).
Temperature affects the heat evolution strongly. The increase of curing temperature converts a
Temperature
single peak into affects
a number the heat evolution
of peaks strongly.
(Figure 12). ThisThe indicates
increase ofthatcuring temperature
multiple chemicalconverts a
steps are
Temperature
single peak into
affects
a
the heat
number of
evolution
peaks
strongly.
(Figure 12). This
The increase
indicates that
of multiple
curing temperature
chemical
converts
steps are
a
involved during geopolymerization.
singleinvolved
peak into a number
during of peaks (Figure 12). This indicates that multiple chemical steps are involved
geopolymerization.
during geopolymerization.
Minerals 2018, 8, 299 11 of 21
12. Heat
FigureFigure evolution
12. Heat at different
evolution temperatures.
at different (a)(a)Heat
temperatures. Heatflow
flowininmW/g FA, (b)
mW/g FA, (b)Cumulative
Cumulativeheatheat in
in J/g FA [43] (Reproduced with permission from Cement and Concrete
J/g FA [43] (Reproduced with permission from Cement and Concrete Research; published Research; published by
by Elsevier,
2018).Elsevier,
Figure 2018).
12. Heat evolution at different temperatures. (a) Heat flow in mW/g FA, (b) Cumulative heat
in J/g FA [43] (Reproduced with permission from Cement and Concrete Research; published by
9.6. SEM of Fly2018).
Elsevier, Ash-Based Geopolymer
9.6. SEM of Fly Ash-Based Geopolymer
9.6.Nath
SEM et al. Ash-Based
of Fly [40] performed detailed microscopic studies. Figure 13a–i shows SEM pictures of
Geopolymer
Nath et al. [40]
geopolymers. performed
With change indetailed microscopic and
alkali concentrations studies.
curingFigure 13a–i shows
temperature, SEM pictures of
the microstructures
Nath
geopolymers. et al.change
With [40] performed detailed
in alkali microscopic and
concentrations studies. Figuretemperature,
curing 13a–i shows SEM
the pictures of
microstructures
changed [40].
geopolymers. With change in alkali concentrations and curing temperature, the microstructures
changed [40].
changed [40].
Figure 13.
Figure 13.SEM
SEMpictures
picturesof
ofFA-based geopolymers(a)
FA-based geopolymers (a)6M27;
6M27;(b)
(b)6M45;
6M45;(c)(c) 6M60;
6M60; (d)(d) 8M27;
8M27; (e) (e) 8M45;
8M45;
Figure(f)13.
(f)
SEM (g)
8M60; pictures
8M60;(g) 10M27; of
10M27;(h)
FA-based
(h)10M45;
10M45; (i)
geopolymers
(i) 10M60
(a) 6M27;
[40] (Reproduced
10M60 [40] (Reproduced (b)permission
with
with
6M45; (c)from
permission 6M60;
from (d) 8M27;and
Construction
Construction
(e) 8M45;
and
(f) 8M60; (g) 10M27; (h)
BuildingMaterials;
Building 10M45;
Materials;published(i)
published by10M60 [40]
by Elsevier, (Reproduced
Elsevier, 2016).
2016). with permission from Construction and
Building Materials; published by Elsevier, 2016).
Minerals 2018, 8, 299 12 of 21
10. Properties of Geopolymer
10.1. Compressive
Minerals 2018,Strength
8, x FOR PEER REVIEW 12 of 21
Compressive strength
10. Properties of geopolymer mortars and concretes is an important property. The strength
of Geopolymer
change in FA geopolymer concrete is due to shape, size distribution, calcium content and high
10.1. Compressive Strength
amorphous microstructure of raw material [46]. The silicon and aluminum components of FA are
activated by Compressive
alkali solution strength
whichofpolymerizes
geopolymer intomortars and concretes
molecular chains isand
an becomes
importanta property. The binds
binder which
strength change in FA geopolymer concrete is due to shape, size distribution, calcium content and
the coarse and fine aggregates into a homogeneous mass and attains optimum strength at elevated
high amorphous microstructure of raw material [46]. The silicon and aluminum components of FA
temperatures. Calcium content of FA contributes very significantly in the strength development of
are activated by alkali solution which polymerizes into molecular chains and becomes a binder
geopolymer concrete. However,
which binds the coarse and fine low-calcium FAa homogeneous
aggregates into is preferablemass for and
highattains
binding properties
optimum strengthsince a
geopolymer bindertemperatures.
at elevated depends more on high
Calcium content
content of FAof aluminosilicate
contributes very minerals forin
significantly performance.
the strength Alkali
development
concentrations also of geopolymer
affect concrete.
the strength However, low-calcium
of geopolymer concrete.FAAs is the
preferable for high binding
concentration of alkali was
properties since a geopolymer binder depends more on high content
increased, the strength also increased. Blending FA, kaolin and SF in geopolymer concrete of aluminosilicate minerals for
increase the
performance. Alkali concentrations also affect the strength of geopolymer concrete. As the
compressive strength up to a certain limit. With the increase of kaolin, compressive strength decreased.
concentration of alkali was increased, the strength also increased. Blending FA, kaolin and SF in
Furthermore, the addition
geopolymer of slag the
concrete increase increased the strength
compressive compressive
up to astrength. This
certain limit. is as
With theaincrease
result ofof closer
packing kaolin,
of finecompressive
particles ofstrength
slag which fills the pore spaces in the composite mixture.
decreased. Furthermore, the addition of slag increased the compressive This resulted in
fine surface texture and increase in compressive strength [46].
strength. This is as a result of closer packing of fine particles of slag which fills the pore spaces in the
composite
Okoye et al.mixture. This resulted
[47] reported thatinstrength
fine surface texture and
increases upincrease in compressive
to certain temperatures strength [46].after that,
but
Okoye et al. [47] reported that strength increases up to certain temperatures but after that, it
it decreases (Figure 14).
decreases (Figure 14).
Figure 14. Change in compressive strength of FA-based geopolymer concrete in presence of kaoline
at Change
Figure 14. different in compressive
temperatures [47]strength of FA-based
(Reproduced geopolymer
with permission fromconcrete in presence
Construction of kaoline at
and Building
differentMaterials;
temperatures [47] (Reproduced with
published by Elsevier, 2015). permission from Construction and Building Materials;
Silica fume addition decreases the compressive strength of the paste whereas in case of mortar,
strength is increased. In the case of paste, porosity is increased, whereas in the case of mortars,
Silica fumeisaddition
porosity decreaseddecreases the compressive
in the presence of silica fume. strength
In the caseof
ofthe paste whereasinin
mortars/concretes, case oftomortar,
addition
strengthreaction
is increased. In the case of paste, porosity is increased, whereas in the case of
of silica fume with alkalies, fine particles also enter into the pores and increase the mortars, porosity
compactness. According to Okoye et al. [48] in mortars and concretes, increase in
is decreased in the presence of silica fume. In the case of mortars/concretes, in addition to reaction strength was found
of silica even
fume upwith
to 40%alkalies,
silica fume addition
fine (Figure
particles 15).enter into the pores and increase the compactness.
also
According to Okoye et al. [48] in mortars and concretes, increase in strength was found even up to 40%
silica fume addition (Figure 15).
Minerals 2018, 8, 299 13 of 21
Figure 15. Effect of silica fume on compressive strength [48] (Reproduced with permission from
Figure 15. Effect of silica fume on compressive strength [48] (Reproduced with permission from
Ceramics International; published by Elsevier, 2016).
Ceramics International; published by Elsevier, 2016).
Saxena et al. [49] reported that similar to silica fume, Alccofine powder also increased the
compressive strength. Curing can alternatively be done by microwave heating, where
Saxena et al. [49] reported that similar to silica fume, Alccofine powder also increased the
electromagnetic energy is converted to thermal energy and heat uniformly. This rapidly accelerates
compressive strength. Curing can alternatively be done by microwave heating, where electromagnetic
the strength gain [50]. Compressive strength of geopolymer mortars cured by conventional and
energy microwave
is converted to thermal
heating energy
are given in Table 2and heatdata
[34]. The uniformly.
show that 30This
minrapidly
heating inaccelerates
a microwavethe
ovenstrength
gain [50]. Compressive
gives strength
higher strength than 12ofh geopolymer
of conventionalmortars
heating cured by conventional and microwave heating
at 80 °C.
are given in Table 2 [34]. The data show that 30 min heating in a microwave oven gives higher strength
Table 2. Mix design with sodium hydroxide (14 M), sodium silicate and lithium silicate and
than 12 h of conventional heating at 80 ◦ C.
compressive strength by conventional and microwave heating [34].
Pond Natural
Table 2. Mix design with sodiumNaOH
hydroxideSodium
(14 M), sodiumLithiumsilicate Compr.Str.
and lithium(MPa)
silicateCompr.Str. (MPa)
and compressive
MIX Fly Ash Sand Solution Conventional Curing MW Curing (30
strength by conventional Silicate (g) [34].
Silicate (g)
(g) (g)and microwave
(g) heating 80 °C (12 h) min)
Mix-4 200 600 40 80 0 39.0 40.0
Mix-8 200
Pond 600
Natural NaOH40 0 80 32.6
Compr.Str. (MPa) 39.0
Compr.Str.
Mix-12 200 600 40 Sodium
80 Lithium
0 40.6 42.0 MW
MIX Fly Ash Sand Solution Conventional (MPa)
Mix-16 200 600 Silicate
0 (g) Silicate (g)
(g) (g) (g)40 80 32.0
Curing 80 ◦ C (12 h) 39.9(30 min)
Curing
Mix-4 200 600 40 80 0 39.0 40.0
10.2. Flexural
Mix-8 200and Splitting
600 Tensile
40 Strength 0 80 32.6 39.0
Mix-12Normally,
200 a fly600ash-based40 geopolymer
80 has low tensile
0 strength.40.6
It also has low 42.0
fracture
Mix-16 200 600 40 0 80 32.0 39.9
toughness. Because of these properties, fly ash-based geopolymers suffer from brittle failure. These
properties can be enhanced if the geopolymer is embedded with chitosan or fibers of steel (ST),
10.2. Flexural andalcohol
polyvinyl Splitting Tensile
(PVA), Strength
sweet sorghum and cotton.
Normally, a fly Properties

10.3. Electrical ash-based geopolymer
of Geopolymer has low tensile strength. It also has low fracture toughness.
Pastes
Because of these properties, fly ash-based geopolymers suffer from brittle failure. These properties can
Electrical properties of FA-based geopolymer pastes at different NaOH concentrations and
be enhanced if thewere
frequencies geopolymer
measured by is embedded
Hanjitsuwanwith
et al. chitosan or shown
[39] and are fibers of steel (ST),
in Figure polyvinyl
16. The dielectric alcohol
(PVA), sweet sorghum and cotton.
constant (16a) decreased and electrical conductivity increased with frequency (16b).
10.3. Electrical Properties of Geopolymer Pastes

Electrical properties of FA-based geopolymer pastes at different NaOH concentrations and
frequencies were measured by Hanjitsuwan et al. [39] and are shown in Figure 16. The dielectric
constant (16a) decreased and electrical conductivity increased with frequency (16b).
Minerals 2018, 8, 299 14 of 21
Minerals2018,
Minerals 2018,8,8,xxFOR
FORPEER
PEERREVIEW
REVIEW 14of
14 of21
21
Figure
Figure 16.(a)
16.16.
Figure (a)Dielectric
(a) Dielectricconstant
Dielectric constant and
constant and (b)
and (b) AC
(b) AC conductivity
AC conductivity (σ
conductivity (σ
(σ )) of
acac
ac )ofofFAGP
FAGP [39]
FAGP[39] (Reproduced
[39](Reproduced
(Reproducedwith
with
with
permission
permission
permission from
from
from Cementand
Cement
Cement andConcrete
and ConcreteComposites;
Concrete Composites;published
Composites; publishedby
published by Elsevier,
byElsevier, 2014).
Elsevier,2014).
2014).
10.4.
10.4.
10.4. Fire
Fire
Fire RetardantProperties
Retardant
Retardant Properties
Properties
Geopolymers have
Geopolymers have low
low thermal
thermal conductivity and and they dodo not emit
emit toxic
toxic fumes
fumes when
when heated.
heated.
Geopolymers have low thermal conductivity
conductivity andthey they donotnot emit toxic fumes when heated.
Geopolymer concretes
Geopolymer concretes areare one
one ofof the
the most
most important
important building
building materials
materials which
which can can withstand
withstand high
high
Geopolymer concretes are one of the most important building materials which can withstand high
temperature. Geopolymer
temperature.Geopolymer concrete
Geopolymer concrete
concrete is is more
is more porous and favors the escape of internal steam pressure
temperature. more porous
porousandandfavors
favorsthe
theescape
escapeofof internal
internalsteam
steam pressure
pressure
duringheating
during heatingandandas asaaresult
resultbecomes
becomesaagood goodfire-resistant
fire-resistantmaterial.
material.
during heating and as a result becomes a good fire-resistant material.
Saxena et
Saxena et al.
al. [51]
[51] measured
measured compressive
compressive strength
strength ofof FA-based
FA-based geopolymer
geopolymer mortarsmortars in in the
the
Saxena
absenceand
et al. [51]
andpresence
presenceof
measured
ofsilica
compressive
silicafume
fumeat atdifferent
strength
differentcuring
of FA-based
curingtemperatures.
geopolymer
temperatures.Results
mortars
Results(Figure
(Figure17)
in
17)[51]
the absence
[51]showed
showed
absence
and presence
that in the of silica and
the presence
presence fume at different
absence of SF
SF in curing
in temperatures.
geopolymer mortars,Results (Figure 17)
the compressive
compressive [51] showed
strength increased that
that in and absence of geopolymer mortars, the strength increased
in up
thetopresence
600°C°Cbutand
butafterabsence
afterthat, of
that,thereSF
therewasin geopolymer
wasaacontinuous mortars,
continuousdecrease.
decrease. the compressive strength increased up to
up◦ to 600
600 C but after that, there was a continuous decrease.
Figure Compressive
17.17.
Figure Compressivestrength
strengthat
atdifferent temperatures
different temperatures [51] (Reproduced
temperatures [51]
[51] (Reproducedwith
withpermission
permission from
from
Figure 17. Compressive strength at different (Reproduced with permission from
Materials Today:
Materials Proceedings;
Today: Proceedings;published
publishedbybyElsevier, 2017).
Elsevier,2017).
2017).
Materials Today: Proceedings; published by Elsevier,
Minerals 2018, 8, 299

10.5. Properties in Presence of Nanomaterials 15 of 21
In the presence of nano-silica, the compressive strength of high volume fly ash mortars at room
10.5. Properties
temperature in Presence
curing
Minerals 2018, of REVIEW
is PEER
8, x FOR Nanomaterials
reported to be improved significantly. The nano-silica enhances 15 of 21 the
polymerization
In 10.5.
the presenceprocess because of itsthe
high specific areastrength
and amorphous
of high nature
volume[52].
Properties inof nano-silica,
Presence of Nanomaterials compressive fly ash mortars at
When graphene (GR) was incorporated into the matrix
room temperature curing is reported to be improved significantly. The nano-silica of fly ash-based geopolymer
enhances (FAG),
the
In the presence
electroconductive GR/FAG of nano-silica,
composite the compressive
was obtained. strength of high volume
Photocatalytic fly ash mortars
degradation of at roomcarmine
indigo
polymerization
temperature processcuringbecause of its to
is reported highbe specific
improved area and amorphous
significantly. nature [52].
The nano-silica enhances the
over When
1.0GR/FAG
graphene composite
(GR) was studied by Zhang
incorporated et al.the
into [53] is shown
matrix in Figure
of fly ash-based18. Fe 2O3 present in FA
polymerization process because of its high specific area and amorphous nature [52]. geopolymer (FAG),
and in turn in
electroconductive geopolymer
GR/FAG
When graphene
is
(GR)
wrapped
composite inside and
was obtained.
was incorporated
1.0GR/FAG composite
into the Photocatalytic
in presence
degradation
matrix of fly ash-based
of(FAG),
sunlight
of indigo
geopolymer
acts
carmine
as a photocatalyst
over electroconductive
1.0GR/FAG and degrades
GR/FAG
composite the dye.
composite
studied was obtained.
by Zhang Photocatalytic
et al. [53] is shown degradation
in Figure 18.of indigo
Fe O carmine
present in FA
2 3
over in
and in turn 1.0GR/FAG
geopolymercomposite studied inside
is wrapped by Zhang et 1.0GR/FAG
and al. [53] is shown in Figure 18.
composite Fe2O3 present
in presence in FA
of sunlight acts
and in turn in geopolymer is wrapped inside and 1.0GR/FAG composite in presence of sunlight acts
as a photocatalyst and degrades the dye.
as a photocatalyst and degrades the dye.
Figure
Figure 18. 18. Photocatalytic
Photocatalytic degradation
degradation ofofindigo
indigo carmine
carmine over
overGR/FAG
GR/FAG composite [53] (Reproduced
composite [53] (Reproduced
withPhotocatalytic
Figure 18. permission
with permission from from
degradation
Chemical
Chemical
of indigo
Engineering
Engineering
carmine
Journal;
Journal;
over GR/FAG
published
published byby
Elsevier,composite
2018).
Elsevier, 2018).
[53] (Reproduced
with permission from Chemical Engineering Journal; published by Elsevier, 2018).
11. Durability
11. Durability
11. Durability
Durability of geopolymers (resistance to chloride, sulfate, acid, freeze-thaw, thermal and
Durability of geopolymers
efflorescence) depends on the (resistance
microstructuretoand chloride, sulfate,
the movement acid,
of ions freeze-thaw,
within the structurethermal
[54]. and
Durability of geopolymers (resistance to chloride, sulfate, acid, freeze-thaw, thermal and
efflorescence) depends
Geopolymer madeon by the
NaOHmicrostructure
is found to beand thecrystalline
more movement andofhence
ionsmore
within the whereas
stable, structure [54].
efflorescence) depends on
geopolymers withthe
themicrostructure and the movement ofless
ions within themedium.
structure [54].
Geopolymer mademade by NaOH sodium
is found silicate activator
to be moreis crystalline
amorphous and
and stable
hence in acidic
more stable, whereas
Geopolymer made
Active sites by NaOH
present is found
on the surface to be more
of alumnosilcate gel crystalline and hence
are also responsible morestability.
for chemical stable, Kwhereas
+
geopolymers made with the sodium silicate activator is amorphous and less stable in acidic medium.
geopolymers made
ions also affectwith
it. If the sodiumdeteriorates
geopolymer silicate activator
in acidicismedium,
amorphousit mayand lesstostable
be due in acidic medium.+
depolymerization
Active sites present on
and liberation
the surface ofcations
alumnosilcate gel arebyalso responsible for chemical stability. K
Active sites present of onsilicic
the acid. Na+ of
surface may be replaced
alumnosilcate gel arehydrogen ion as given
also responsible forbelow (Figurestability.
chemical
ions also affect it. If geopolymer deteriorates in acidic medium, it may be due to depolymerization
K+ ions 19).
also affect it. If geopolymer deteriorates in acidic medium, it may be due to depolymerization
and liberation of silicic acid. Na+ cations may be replaced by hydrogen ion as given below (Figure
and liberation of silicic acid. Na+ cations may be replaced by hydrogen ion as given below (Figure 19).
19).
Figure 19. Replacement of Na+ ions by H+ ions during depolymerization in acidic medium.
When geopolymer is attacked by acids, Si–O–Al bonds are broken and as a result Si–OH and
Al–OH groups get increased in the structure. As a result, the amount of silicic acid and dimmers get
Figure 19. Replacement of Na+ ions by H+ ions during depolymerization in acidic medium.
increased in the
Figure 19. solution leading
Replacement of Na+toions
massbyloss.
H+Because of this,
ions during mechanical properties
depolymerization are decreased.
in acidic medium.
Acid resistance of geopolymer increases with curing temperature. FA-based geopolymer cured
When
at 80geopolymer is attacked
°C for 10 h when immersedby in acids, Si–O–Al
HCl solution bonds
did not are broken
deteriorate much and as a resultcured
[55]. Microwave Si–OH and
Al–OHWhen geopolymer
groups is attacked
get increased by acids, As
in the structure. Si–O–Al bonds
a result, are broken
the amount and as
of silicic a result
acid Si–OH and
and dimmers get
Al–OH
increasedgroups
in theget increased
solution in the
leading to structure.
mass loss.As a result,
Because the amount
of this, of silicic
mechanical acid and
properties aredimmers get
decreased.
increased
Acid in the solution
resistance leading to mass
of geopolymer loss. with
increases Because of this,
curing mechanical
temperature. properties
FA-based are decreased.
geopolymer cured
at 80 °C for 10 h when immersed in HCl solution did not deteriorate much [55]. Microwave cured
Acid resistance of geopolymer increases with curing temperature. FA-based geopolymer cured
at 80 ◦ C for 10 h when immersed in HCl solution did not deteriorate much [55]. Microwave cured
Minerals 2018, 8, 299 16 of 21
FA-based geopolymer gave enhanced densification comparable to the conventional curing and as a
result more durable in acidic environment [56].
Chloride diffusion into the concretes promotes the corrosion of steel bars in the structure. Chloride
diffusion can be minimized by using higher concentrations of NaOH. This refines the pore structure
due to polycondensation reactions.
Geopolymer when exposed to fire has the tendency for shrinkage and cracking. However,
fly ash-based geopolymer has much less effect of fire as compared to OPC-based concretes [57].
There occurs expansion, cracking and scaling mass loss due to freeze-thaw attack [58].
In geopolymers excess of hydroxide solution remain in the pores and excess sodium oxide in pore
network. This in contact to atmospheric CO2 degrade the geopolymer [59,60]. Efflorescence depends
on alkali activator, curing temperature and calcium content. KOH instead of NaOH as activator
reduces the efflorescence of geopolymer [61].
It is reported that heat curing with surface sealing can prevent the early carbonation of FA-based
geopolymer paste by increasing polycondensation reaction [62].
12. Foamed Geopolymer Concrete

Geopolymer foams (GFs) show a large number of properties and are eco-building materials [63].
Foamed geopolymer concretes are formed by adding foaming agents to a geopolymer and have a
porous structure. Because of the foaming agents, gases are evolved and entrapped in the structure
before the gel hardens. The gel contains different sizes and types of pores [64]. Chemical and mechanical
foaming methods are generally used. In chemical methods, density can be reduced but large voids are
generated [65].
When foaming agents are added to FA slurry in alkali activator solutions, geopolymer foam is
formed. The number of compounds is known which produce gases on addition to geopolymers and
are then entrapped to produce a foamed microstructure in the hardened material [66]. When foaming
agents are mixed, chemical reactions liberate different gases which are entrapped in the structure.
Because it is highly reactive, when aluminum metal is kept in alkaline solution, H2 gas is evolved
and aluminum hydroxide is formed. Following reactions (Equations (1)–(3)) occur [67].
2Al + 6H2 O + 2NaOH Õ 2NaAl(OH)4 + 3H2 (1)
2NaAl(OH)4 Õ NaOH + Al(OH)3 (2)
2Al + 6H2 O Õ 2Al(OH)3 + 3H2 (3)
Hydrogen peroxide reacts, evolving oxygen gas, which is entrapped in the paste, giving foamed
structure. Equations (4) and (5) represent the reactions [66].
H2 O2 + OH− Õ HO2 − + H2 O (4)
HO2 − + H2 O2 Õ H2 O + O2 + OH− (5)
NaOCl also liberates gases as per Equations (6) and (7) and makes foamed geopolymer
concrete [68].
NaOCl Õ NaCl + 1/2 O2 (6)
2NaOCl + C Õ 2NaCl + CO2 (7)
Silica fume when added, during geopolymerization, silicon of silica fume is oxidized by water
(Equation (8)) liberating H2 gas [64].
4H2 O + Si Õ 2H2 + Si(OH)4 (8)

Minerals 2018, 8, 299 17 of 21
Sodium dodecyl benzene sulfonate and gluten have also been used as foaming agent using fly
ash and sheet glass powder as solid materials. The appearance and pore structure of the sintered
geopolymer foam studied by Zuhua et al. [64] are shown in Figure 20.
Figure 20. (a) Sintered geopolymer foam and (b) SEM image [64] (Reproduced with permission from
Figure 20. (a) Sintered geopolymer foam and (b) SEM image [64] (Reproduced with permission from
Construction and Building Materials; published by Elsevier, 2014).
Construction and Building Materials; published by Elsevier, 2014).
13. Carbon Foot Print in Production and Construction of Portland Cement and Geopolymer
Concretes
13. Carbon Foot Print in Production and Construction of Portland Cement and
Geopolymer Concretes
CO2 emissions from all the processes involved in the manufacture of 1 m3 of geopolymer and
COPortland cement concrete were evaluated by Turner and Collins [69] and are shown
3 in Figure 21.
2 emissions from all the processes involved in the manufacture of 1 m of geopolymer and
The total emissions from the OPC and geopolymer concrete mixes were estimated as 354 kg CO2
Portland cement concrete were evaluated by Turner and Collins [69] and are shown in Figure 21.
e/m3and 320 kg CO2 e/m3 respectively, showing 9% difference.
The total emissions from the OPC and geopolymer concrete mixes were estimated as 354 kg CO2
e/m3 and 320 kg CO2 e/m3 respectively, showing 9% difference.
Minerals 2018, 8, 299 18 of 21
Figure 21. CO
21. CO 2-e for concrete mixtures with OPC and geopolymer [69] (Reproduced with permission
Figure 2 -e for concrete mixtures with OPC and geopolymer [69] (Reproduced with permission
from Construction and Building Materials; published by Elsevier, 2013).
from Construction and Building Materials; published by Elsevier, 2013).
14. Economic Benefits of Geopolymer Concrete
14. Economic Benefits of Geopolymer Concrete
There are a number of economic benefits of Fly ash-based geopolymer concrete over Portland
There
cementare a number
concrete. of economic
An approximate costbenefits of Fly concrete
of geopolymer ash-based geopolymer
of one cubic meterconcrete over
is reported Portland
to be 45
cementUSD concrete.
whereas An
thatapproximate cost of geopolymer
for Portland cements concrete, it is concrete of one cubic
60 USD. Additional meter benefits
economic is reported
mayto be
45 USDalsowhereas
be due that
to low
for drying shrinkage
Portland cementsand creep, excellent
concrete, resistance
it is 60 USD. to sulfate
Additional attack benefits
economic and fire may
resistance offered by geopolymer concrete when it is used in infrastructure applications [46].
also be due to low drying shrinkage and creep, excellent resistance to sulfate attack and fire resistance
offered by geopolymer concrete when it is used in infrastructure applications [46].
15. Conclusions and Future Prospects
15. Conclusions andof
Production Future Prospects
geopolymer cement and concretes using fly ash is a better alternative to
conventional OPC concrete because it gives high early strength, is durable, economical and emits
Production of geopolymer cement and concretes using fly ash is a better alternative to conventional
less carbon. At the same time it minimizes waste generation. The properties of geopolymer cement
OPC concrete
concrete depend
because onit gives highfactors.
various early strength,
However,is the durable,
most economical
important oneandisemits lessconditions,
curing carbon. At the
sametemperature
time it minimizes waste generation. The properties of geopolymer cement concrete
and duration. It can be used as a fire resistant material in the construction industry. depend on
various factors.
Because of However,
variations the most important
of composition of flyone is itcuring
ash, conditions,
is difficult to havetemperature
standards forand duration.
this concrete.It can
be used as a fire
Attempts resistant
should material
be made in the
to have construction
solid geopolymers industry.
which canBecause of variations
be easily mixed on of thecomposition
site of
of fly ash, it is difficult to have standards for this concrete. Attempts should be made to haveatsolid
construction. Further systems/additives should be found out which can give high strength even
room temperature
geopolymers which cancuring in a mixed
be easily shorteron period of time.
the site Detailed investigations
of construction. are required so that
Further systems/additives should
geopolymer can become an alternative to Portland cement concrete.
be found out which can give high strength even at room temperature curing in a shorter period of
time. Detailed investigations are required so that geopolymer can become an alternative to Portland
Funding: This research received no external funding.
cement concrete.
Conflicts of Interest: The author declares no conflict of interest.
Funding: This research received no external funding.
References
Conflicts of Interest: The author declares no conflict of interest.
1. Mikulčić, H.; Klemeš, J.J.; Vujanović, M.; Urbaniec, K.; Duić, N. Reducing greenhouse gasses emissions by
Referencesfostering the deployment of alternative raw materials and energy sources in the cleaner cement
manufacturing process. J. Clean. Prod. 2016, 136, 119–132.
1. Mikulčić,
2. H.;Jiménez,
Shi, C.; Klemeš,A.F.;
J.J.; Palomo,
Vujanović, M.; Urbaniec,
A. New cements forK.;
theDuić, N. Reducing
21st century: greenhouse
The pursuit gasses emissions
of an alternative to
by fostering the deployment
Portland cement. Cem. Concr.of Res.alternative raw materials and energy sources in the cleaner cement
2011, 41, 750–763.
3. The European
manufacturing Cement
process. Industry
J. Clean. Association
Prod. 2016, 136, (CEMBUERAU). The Role of Cement in the 2050 Low Carbon
119–132. [CrossRef]
2. Shi, C.; Jiménez, A.F.; Palomo, A. New cements for the 21st century:Available
Economy—Full Report; CEMBUERAU: Brussels, Belgium, 2014. online:
The pursuit www.cembureau.be
of an alternative to Portland
(accessed on 3 February 2016).
cement. Cem. Concr. Res. 2011, 41, 750–763. [CrossRef]
4. Valderrama, C.; Granados, R.; Cortina, J.L.; Gasol, C.M.; Guillem, M.; Josa, A. Implementation of best
3. The European Cement Industry Association (CEMBUERAU). The Role of Cement in the 2050 Low Carbon
available techniques in cement manufacturing: A lifecycle assessment study. J. Clean. Prod. 2012, 25, 60–67.
Economy—Full Report; CEMBUERAU: Brussels, Belgium, 2014; Available online: www.cembureau.be
(accessed on 3 February 2016).
4. Valderrama, C.; Granados, R.; Cortina, J.L.; Gasol, C.M.; Guillem, M.; Josa, A. Implementation of best
available techniques in cement manufacturing: A lifecycle assessment study. J. Clean. Prod. 2012, 25, 60–67.
[CrossRef]
Minerals 2018, 8, 299 19 of 21
5. Teklay, A.; Yin, C.; Rosendahl, L. Flash calcination of kaolinite rich clay and impact of process conditions
on the quality of the calcines: A way to reduce CO2 footprint from cement industry. Appl. Energy 2015.
[CrossRef]
6. Oh, D.Y.; Noguchi, T.; Kitagaki, R.; Park, W.J. CO2 emission reduction by reuse of building material waste in
the Japanese cement industry. Renew. Sustain. Energy Rev. 2014, 38, 796–810. [CrossRef]
7. Zhuang, X.Y.; Chen, L.; Komarneni, S.; Zhou, C.H.; Tong, D.S.; Yang, H.M.; Yu, W.H.; Wang, H. Fly ash-based
geopolymer: Clean production, properties and applications. J. Clean. Prod. 2016, 125, 253–267. [CrossRef]
8. Fan, F.; Liu, Z.; Xu, G.; Peng, H.; Cai, C.S. Mechanical and thermal properties of fly ash based geopolymers.
Constr. Build. Mater. 2018, 160, 66–81. [CrossRef]
9. Wu, Y.G.; Xie, S.S.; Zhang, Y.F.; Du, F.P.; Cheng, C. Superhigh strength of geopolymer with the addition of
polyphosphate. Ceram. Int. 2018, 44, 2578–2583. [CrossRef]
10. Colangelo, F.; Roviello, G.; Ricciotti, L.; Ferrandiz-Mas, V.; Messina, F.; Ferone, C.; Tarallo, O.; Cioffi, R.;
Cheeseman, C.R. Mechanical and thermal properties of lightweight geopolymer composites. Cem. Concr. Compos.
2018, 86, 266–272. [CrossRef]
11. Singh, B.; Ishwarya, G.; Gupta, M.; Bhattacharyya, S.K. Geopolymer concrete: A review of some recent
developments. Constr. Build. Mater. 2015, 85, 78–90. [CrossRef]
12. Mehta, A.; Siddique, R. An overview of geopolymers derived from industrial by-products. Constr. Build. Mater.
2016, 127, 183–198. [CrossRef]
13. Liew, Y.M.; Heah, C.Y.; Kamarudin, H. Structure and properties of clay-based geopolymer cements: A review.
Prog. Mater. Sci. 2016, 83, 595–629. [CrossRef]
14. Koleżyński, A.; Król, M.; Żychowicz, M. The structure of geopolymers—Theoretical studies. J. Mol. Struct.
2018, 1163, 465–471. [CrossRef]
15. Walkley, B.; Rees, G.J.; San Nicolas, R.; van Deventer, J.S.; Hanna, J.V.; Provis, J.L. New structural model of
sodium aluminosilicate gels and the role of charge balancing extra-framework Al. J. Phys. Chem. C 2018, 122,
5673–5685. [CrossRef]
16. Huseien, G.F.; Mirza, J.; Ismail, M.; Ghoshal, S.K.; Hussein, A.A. Geopolymer mortars as sustainable repair
material: A comprehensive. Renew. Sustain. Energy Rev. 2017, 80, 54–74. [CrossRef]
17. Nazari, A.; Sanjayan, J.G. Stress intensity factor against fracture toughness in functionally graded
geopolymers. Arch. Civ. Mech. Eng. 2015, 15, 1007–1016. [CrossRef]
18. Nazari, A.; Maghsoudpour, A.; Sanjayan, J.G. Characteristics of boroaluminosilicate geopolymers.
Constr. Build. Mater. 2014, 70, 262–268. [CrossRef]
19. Bagheri, A.; Nazari, A.; Hajimohammadi, A.; Sanjayan, J.G.; Rajeev, P.; Nikzad, M.; Ngo, T.; Mendis, P.
Microstructural study of environmentally friendly boroaluminosilicate geopolymers. J. Clean. Prod. 2018, 18,
20. Davidovits, J. Geopolymers and geopolymeric new materials. J. Therm. Anal. Calorim. 1989, 35, 429–441.
[CrossRef]
21. Part, W.K.; Ramli, M.; Cheah, C.B. An overview on the influence of various factors on the properties of
geopolymer concrete derived from industrial by-products. Constr. Build. Mater. 2015, 77, 370–395. [CrossRef]
22. PT Semen Gresik. Brochure of Standart Spesification of Cement Products; PT Semen Gresik: Gresik, Indonesia,
2012.
23. Xia, M.; Sanjayan, J. Method of formulating geopolymer for 3D printing for construction applications.
Mater. Des. 2016, 110, 382–390. [CrossRef]
24. Ngo, T.D.; Kashani, A.; Imbalzano, G.; Nguyen, K.T.; Hui, D. Additive manufacturing (3D printing): A review
of materials, methods, applications and challenges. Compos. Part B 2018, 143, 172–196. [CrossRef]
25. Al-Qutaifi, S.; Nazari, A.; Bagheri, A. Mechanical properties of layered geopolymer structures applicable in
concrete 3D-printing. Constr. Build. Mater. 2018, 176, 690–699. [CrossRef]
26. Panda, B.; Mohamed, N.A.; Tan, M.J. Effect of 3D Printing on Mechanical Properties of Fly Ash-Based
Inorganic Geopolymer. In Proceedings of the International Congress on Polymers in Concrete, Washington,
DC, USA, 29 April–1 May 2018; pp. 509–515.
27. Abdullah, M.M.; Hussin, K.; Bnhussain, M.; Ismail, K.N.; Ibrahim, W.M. mechanism and chemical reaction
of fly ash geopolymer cement—A Review. Int. J. Pure Appl. Sci. Technol. 2011, 6, 35–44.
28. Xu, H.; van Deventer, J.S.J. The geopolymerisation of natural alumino-silicates. In Proceedings of the 2nd
International Conference on Geopolymer, Saint-Quentin, France, 30 June–2 July 1999; pp. 43–63.
Minerals 2018, 8, 299 20 of 21
29. Lizcano, M.; Hyunsoo, K.; Basu, S.; Radovic, M. Mechanical properties of sodium and potassium activated
metakaolin-based geopolymers. J. Mater. Sci. 2011, 47, 2607–2616. [CrossRef]
30. Duxson, P.; Lukey, G.C.; Separovic, F.; van Deventer, J.S.J. Effect of alkali cations on aluminum incorporation
in geopolymeric gels. Ind. Eng. Chem. Res. 2005, 44, 832–839. [CrossRef]
31. Van Jaarsveld, J.G.S.; van Deventer, J.S.J. Effect of the alkali metal activator on the properties of fly ash-based
geopolymer. Ind. Eng. Chem. Res. 1999, 38, 3932–3941. [CrossRef]
32. Soutsos, M.; Boyle, A.P.; Vinai, R.; Hadjierakleous, A.; Barnett, S.J. Factors influencing the compressive
strength of fly ash based geopolymers. Constr. Build. Mater. 2016, 110, 355–368. [CrossRef]
33. Ryu, G.S.; Lee, Y.B.; Koh, K.T.; Chung, Y.S. The mechanical properties of fly ash-based geopolymer concrete
with alkaline activators. Constr. Build. Mater. 2013, 47, 409–418. [CrossRef]
34. Saxena, S.K.; Kumar, M.; Singh, N.B. The influence of different alkali solutions on the properties of the pond fly
ash-based geopolymer mortar cured at different temperatures and under different conditions. Adv. Cem. Res.
2018, 30, 1–7. [CrossRef]
35. Barbosa, V.F.; MacKenzie, K.J.; Thaumaturgo, C. Synthesis and characterization of materials based on
inorganic polymers of alumina and silica: Sodium polysialate polymers. Int. J. Inorg. Mater. 2000, 2, 309–317.
[CrossRef]
36. Hardjito, D.; Rangan, B.V. Development and Properties of Low Calcium Fly Ash Based Geopolymer Concrete;
Research Report GC 1; Curtin University of Technology: Perth, Australia, 2005.
37. Siyal, A.A.; Azizli, K.A.; Man, Z.; Ullah, H. Effects of parameters on the setting time of fly ash based
geopolymers using taguchi method. Procedia Eng. 2016, 148, 302–307. [CrossRef]
38. Ranjbar, N.; Mehrali, M.; Maheri, M.R.; Mehrali, M. Hot-pressed geopolymer. Cem. Concr. Res. 2017, 100,
14–22. [CrossRef]
39. Hanjitsuwan, S.; Hunpratub, S.; Thongbai, P.; Maensiri, S.; Sata, V.; Chindaprasirt, P. Effects of NaOH concentrations
on physical and electrical properties of high calcium fly ash geopolymer paste. Cem. Concr. Compos. 2014, 45, 9–14.
[CrossRef]
40. Nath, S.K.; Maitra, S.; Mukherjee, S.; Kumar, S. Microstructural and morphological evolution of fly ash based
geopolymers. Constr. Build. Mater. 2016, 111, 758–765. [CrossRef]
41. Duxson, P. The Structure and Thermal Evolution of Metakaolin Geopolymers. Ph.D. Thesis, The University
of Melbourne, Melbourne, Australia, 2006.
42. Nikolić, V.; Komljenović, M.; Baščarević, Z.; Marjanović, N.; Miladinović, Z.; Petrović, R. The influence of fly
ash characteristics and reaction conditions on strength and structure of geopolymers. Constr. Build. Mater.
2015, 94, 361–370. [CrossRef]
43. Sun, Z.; Vollpracht, A. Isothermal calorimetry and in-situ XRD study of the NaOH activated fly ash,
metakaolin and slag. Cem. Concr. Res. 2018, 103, 110–122. [CrossRef]
44. Yao, X.; Zhang, Z.; Zhu, H.; Chen, Y. Geopolymerization process of alkali–metakaolinite characterized by
isothermal calorimetry. Thermochim. Acta 2009, 493, 49–54. [CrossRef]
45. Khale, D.; Chaudhary, R. Mechanism of geopolymerization and factors influencing its development: A review.
J. Mater. Sci. 2007, 42, 729–746. [CrossRef]
46. Okoye, F.N. Strength Characteristics of Green Concrete. Ph.D. Thesis, Sharda University, Greater Noida,
India, 2016.
47. Okoye, F.N.; Durgaprasad, J.; Singh, N.B. Mechanical properties of alkali activated flyash/Kaolin based
geopolymer concrete. Constr. Build. Mater. 2015, 98, 685–691. [CrossRef]
48. Okoye, F.N.; Durgaprasad, J.; Singh, N.B. Effect of silica fume on the mechanical properties of fly ash
based-geopolymer concrete. Ceram. Int. 2016, 42, 3000–3006. [CrossRef]
49. Saxena, S.K.; Kumar, M.; Singh, N.B. Effect of Alccofine powder on the properties of Pond fly ash based
Geopolymer mortar under different conditions. Environ. Technol. Innov. 2018, 9, 232–242. [CrossRef]
50. Graytee, A.; Sanjayan, J.G.; Nazari, A. Development of a high strength fly ash-based geopolymer in short
time by using microwave curing. Ceram. Int. 2018. [CrossRef]
51. Saxena, S.K.; Kumar, M.; Singh, N.B. Fire resistant properties of alumino Silicate geopolymer cement mortars.
Mater. Today Proc. 2017, 4, 5605–5612. [CrossRef]
52. Adak, D.; Sarkar, M.; Mandal, S. Structural performance of nano-silica modified fly-ash based geopolymer
concrete. Constr. Build. Mater. 2017, 135, 430–439. [CrossRef]
Minerals 2018, 8, 299 21 of 21
53. Zhang, Y.J.; He, P.Y.; Zhang, Y.X.; Chen, H. A novel electroconductive graphene/fly ash-based geopolymer
composite and its photocatalytic performance. Chem. Eng. J. 2018, 334, 2459–2466. [CrossRef]
54. Bakharev, T. Resistance of geopolymer materials to acid attack. Cem. Concr. Res. 2005, 35, 658–670. [CrossRef]
55. Nguyen, K.T.; Lee, Y.H.; Lee, J.; Ahn, N. Acid resistance and curing properties for green fly ash-geopolymer
concrete. J. Asian Archit. Build. 2013, 12, 317–322. [CrossRef]
56. Chindaprasirt, P.; Rattanasak, U.; Taebuanhuad, S. Resistance to acid and sulfate solutions of
microwave-assisted high calcium fly ash geopolymer. Mater. Struct. 2013, 46, 375–381. [CrossRef]
57. Sarker, P.K.; Kelly, S.; Yao, Z. Effect of fire exposure on cracking, spalling and residual strength of fly ash
geopolymer concrete. Mater. Des. 2014, 63, 584–592. [CrossRef]
58. Hobbs, D.W. Concrete deterioration: Causes, diagnosis, and minimising risk. Int. Mater. Rev. 2001, 46,
59. Najafi, K.E.; Allahverdi, A. Effects of chemical composition on basic engineering properties of inorganic
polymeric binders based on natural pozzolan. Ceram. Silik. 2009, 53, 195–204.
60. Pacheco-Torgal, F.; Jalali, S. Influence of sodium carbonate addition on the thermal reactivity of tungsten
mine waste mud based binders. Constr. Build. Mater. 2010, 24, 56–60. [CrossRef]
61. Duxson, P.; Provis, J.L.; Lukey, G.C.; van Deventer, J.S.J. 39 K NMR of free potassium in geopolymers.
Ind. Eng. Chem. Res. 2006, 45, 9208–9210. [CrossRef]
62. Criado, M.; Palomo, A.; Fernández-Jiménez, A. Alkali activation of fly ashes. Part 1: Effect of curing
conditions on the carbonation of the reaction products. Fuel 2005, 84, 2048–2054. [CrossRef]
63. Bai, C.; Ni, T.; Wang, Q.; Li, H.; Colombo, P. Porosity, mechanical and insulating properties of geopolymer
foams using vegetable oil as the stabilizing agent. J. Eur. Ceram. Soc. 2018, 38, 799–805. [CrossRef]
64. Zhang, Z.; Provis, J.L.; Reid, A.; Wang, H. Geopolymer foam concrete: An emerging material for sustainable
construction. Constr. Build. Mater. 2014, 56, 113–127. [CrossRef]
65. Hajimohammadi, A.; Ngo, T.; Mendis, P.; Sanjayan, J. Regulating the chemical foaming reaction to control
the porosity of geopolymer foams. Mater. Des. 2017, 120, 255–265. [CrossRef]
66. Masi, G.; Rickard, W.D.; Vickers, L.; Bignozzi, M.C.; Van Riessen, A. A comparison between different foaming
methods for the synthesis of light weight geopolymers. Ceram. Int. 2014, 40, 13891–13902. [CrossRef]
67. Hajimohammadi, A.; Ngo, T.; Mendis, P. How does aluminium foaming agent impact the geopolymer
formation mechanism? Cem. Concr. Compos. 2017, 80, 277–286. [CrossRef]
68. Böke, N.; Birch, G.D.; Nyale, S.M.; Petrik, L.F. New synthesis method for the production of coal fly ash-based
foamed geopolymers. Constr. Build. Mater. 2015, 75, 189–199. [CrossRef]
69. Turner, L.K.; Collins, F.G. Carbon dioxide equivalent (CO2 -e) emissions: A comparison between geopolymer
and OPC cement concrete. Constr. Build. Mater. 2013, 43, 125–130. [CrossRef]
© 2018 by the author. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Minerals: Fly Ash-Based Geopolymer Binder: A Future Construction Material

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Minerals: Fly Ash-Based Geopolymer Binder: A Future Construction Material

Uploaded by

Copyright:

Available Formats

minerals

Minerals 2018, 8, 299; doi:10.3390/min8070299 www.mdpi.com/journal/minerals

with better mechanical, chemical,

• These three steps

Minerals 2018, 8, x FOR PEER REVIEW 7 of 21

Minerals 2018, 8, x FOR PEER REVIEW 8 of 21

straightforward determination of the framework Si/Al ratios and the resolution of

Minerals 2018, 8, x FOR PEER REVIEW 10 of 21

Minerals 2018, 8, x FOR PEER REVIEW 11 of 21

10. Properties of Geopolymer

Normally, a fly Properties

10.3. Electrical Properties of Geopolymer Pastes

Minerals 2018, 8, 299

12. Foamed Geopolymer Concrete

2Al + 6H2 O + 2NaOH Õ 2NaAl(OH)4 + 3H2 (1)

2NaAl(OH)4 Õ NaOH + Al(OH)3 (2)

2Al + 6H2 O Õ 2Al(OH)3 + 3H2 (3)

H2 O2 + OH− Õ HO2 − + H2 O (4)

HO2 − + H2 O2 Õ H2 O + O2 + OH− (5)

NaOCl Õ NaCl + 1/2 O2 (6)

2NaOCl + C Õ 2NaCl + CO2 (7)

4H2 O + Si Õ 2H2 + Si(OH)4 (8)

You might also like