Journal of Cleaner Production 230 (2019) 557e579

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Journal of Cleaner Production

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Review

Geopolymer-zeolite composites: A review

_ *, Magdalena Kro
Piotr Rozek  l, Włodzimierz Mozgawa
AGH University of Science and Technology, Faculty of Materials Science and Ceramics, Al. Mickiewicza 30, 30-059, Krakow, Poland

a r t i c l e i n f o a b s t r a c t

Article history: Although the formation of zeolites in geopolymers have been mentioned in many works, a particular
Received 15 January 2019 interest in geopolymer-zeolite composites started to increase very recently. Such hybrid materials con-
Received in revised form nect the advantageous properties of both constituents: geopolymer serves as a strong and durable
13 May 2019
support for zeolites, when zeolites provide high surface area, porosity and adsorption capacity. The
Accepted 14 May 2019
Available online 16 May 2019
composites can be therefore used as bulk-type adsorbents as well as membranes in separation and
pervaporation processes. The possibility of the utilization of industrial wastes for their production is also
a sustainability benefit. This review article highlights advances in the field of geopolymer-zeolite com-
Keywords:
Geopolymer
posites manufacturing and applications. The resistance of zeolites in geopolymer matrices, methods of
Alkali-activation their detection and effect of their presence on the properties of hybrid materials are discussed as well.
Zeolite © 2019 Elsevier Ltd. All rights reserved.
Geopolymer-zeolite
Self-supporting
Membrane

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
1.1. Geopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 558
1.2. Zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 558
1.3. Geopolymer-zeolite composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 559
2. Synthesis of geopolymer-zeolite composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 560
2.1. Zeolites as raw materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 560
2.2. Direct zeolites formation in the matrix of geopolymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561
2.3. Hydrothermal treatment of geopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 567
2.4. Mechanism of zeolites formation in geopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
3. Resistance of zeolites in the geopolymeric matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
4. Methods used to detect zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 570
5. Applications of geopolymer-zeolite composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
6. Influence of zeolites on the properties of geopolymer-zeolite composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
7. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
Declarations of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575

1. Introduction

Geopolymers are generally understood as alkali-activated alu-

minosilicates. They may be considered as an inorganic two-
component system which consists of: (1) a reactive solid source
* Corresponding author. of SiO2 and Al2O3, and (2) an alkaline activation solution (Buchwald
_
E-mail address: prozek@agh.edu.pl (P. Rozek).

https://doi.org/10.1016/j.jclepro.2019.05.152
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
558 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579

to fully amorphous (Provis et al., 2005). It exhibits high chemical

List of abbreviations: and fire resistance as well as relatively high mechanical strength
(Zhang et al., 2018). Therefore, geopolymers can be used as con-
BA bottom ash struction and building materials, with a prospect of being an
BET Brunauer-Emmett-Teller environmentally-friendly Portland cement replacement.
C-A-S-H calcium aluminosilicate hydrate Geopolymer-stabilized aggregate bases, in turn, can be used as
CFB circulating fluidized bed stabilizing agents in flexible pavement applications (Hu et al.,
FA fly ash 2018b). Another important application of geopolymers is the
FS fumed silica adsorption of heavy metals and dyes, which is the result of their
FT-IR Fourier-transform infrared spectroscopy porous structure and the presence of negative charges, located on
BFS blast furnace slag aluminum tetrahedra, as well as their mechanical stability, cost-
HT hydrothermal treatment effectiveness, eco-friendliness and high efficiency (Siyal et al.,
MK metakaolin 2018).
MAS NMR magic angle spinning nuclear magnetic resonance The product of geopolymerization is amorphous N-A-S-H gel
N-A-S-H sodium aluminosilicate hydrate (sodium aluminosilicate hydrate). In the initial stage of the acti-
RHA rice hull (husk) ash vation it forms in as Al-rich gel, gradually becoming richer in Si
RT room temperature with the reaction progress, when more SieO groups dissolve and
SEM scanning electron microscope the concentration of silicon in the reaction medium rises (Granizo
SA sodium aluminate et al., 2014). The 3D network structure of geopolymers consists of
SH sodium hydroxide SieOeAl framework (spatially connected chains of [SiO4] and
WG water glass (sodium silicate solution) [AlO4] tetrahedra, sharing oxygen corners) and charge-balancing
XRD X-ray diffraction metal cations. When a raw material with some content of CaO is
used for the synthesis of geopolymers, two types of gels coexist,
i.e. N-A-S-H and CeSeH (calcium silicate hydrate) or its Al-
substituted C-A-S-H form (Khalid et al., 2018). It was also sug-
et al., 2011). The mechanism responsible for geopolymer formation gested that at low alkalinities both N-A-S-H and CeSeH gels form,
e geopolymerization e involves the dissolution of silicon and while at high alkalinities N-A-S-H is a predominant phase with
aluminum atoms from the source material, reorientation of pre- some precipitates of calcium compounds within (Zhang et al.,
cursor ions, and their condensation to form a final solid product. In 2010). The mechanism of geopolymerization involves three steps
addition to an amorphous gel, geopolymers may contain some (Krol et al., 2018): (1) dissolution of aluminosilicate raw material;
amounts of unreacted material as well as newly formed crystalline (2) decrease in the content of polymeric aluminosilicate species
phases, especially zeolites. Such products can be more properly with increase in orthosilicate phases; (3) condensation of tetra-
termed as geopolymer-zeolite composites. These hybrid materials hedra and disappearance of polarized forms. Depending on the
connect the properties of both constituents, exhibiting synergistic alkali-activator used in the synthesis, the speed of the first step
effect. increases in order Li < Na < K (Kro l et al., 2018). The geopolymeric
gel is often considered as zeolite-like phase, zeolite precursors, or
1.1. Geopolymers metastable amorphous zeolites, unable to crystallize due to un-
favorable conditions (Sturm et al., 2016). The Ostwald Law of
In the synthesis of geopolymers, two most commonly used Successive Transformations states that a phase does not always
aluminosilicate precursors are metakaolin and coal fly ash. Meta- transform directly into the most stable state, but often changes
kaolin is an anhydrous aluminosilicate obtained by the thermal into a metastable state of greater likeness to itself (Rees et al.,
decomposition of kaolin, a naturally occurring clay containing 2008).
kaolinite mineral [Al2Si2O5(OH)4] and trace amounts of quartz and
other minerals. Hydroxyl ions are strongly bonded to the alumi- 1.2. Zeolites
nosilicate framework of kaolinite and can be eliminated at tem-
peratures above 550
C; dehydroxylation causes a considerable Zeolites are crystalline, hydrated tectoaluminosilicates with a
atomic rearrangement (Ferna ndez-Jimenez et al., 2008). The utili- specific framework structure, consisting of silica and alumina
zation of industrial by-products and wastes for the synthesis of tetrahedra linked by shared oxygen atoms, and containing well-
materials that can be applied for different purposes is particularly defined channels and chambers, filled with ions and water mole-
important. For instance, the global production of coal combustion cules. Such structure makes their physical and chemical properties
products, including fly ash, was 780 million tonnes in 2010, and its unique, which results with a very wide range of their practical
utilization rate was around 50% (Heidrich et al., 2013). Therefore, applications (Krol et al., 2012). Zeolites are based on TO4 tetrahedra
the preparation of coal fly ash-based geopolymers provides a sus- (T is an aluminum or silicon atom), which can be regarded as pri-
tainable way for the disposal of this by-product, which remains a mary building units (PBU). Linkages between larger number of
worldwide challenge. Another industrial by-products used for tetrahedra are called secondary building units (SBU) (Baerlocher
geopolymer synthesis are, for instance, red mud (Hu et al., 2018a; and McCusker, 2018).
Nie et al., 2019), slag (Sun and Vollpracht, 2018), and biomass fly As mentioned above, zeolites can be obtained in the matrix of
ash (De Rossi et al., 2018). An aluminosilicate precursor has to be geopolymer as a direct product, forming parallel to geo-
alkali-activated. For this purpose alkaline hydroxides, silicates, polymerization. Such an approach manifests sustainability benefits
aluminates, carbonates, sulphates, or their combinations are used since the synthesis of geopolymers is more energy- and time-
(Buchwald et al., 2011). Another important factor for the activation efficient compared to the conventional zeolite synthesis, which in
is heat providing, due to the activation barrier that has to be sur- most cases requires autoclave hydrothermal reactor. Moreover,
passed for the reaction to take place (Bakharev, 2005a). A final solid standard hydrothermal synthesis of zeolites from fly ash fail to
product possesses regions varying in degrees of crystallinity, produce zeolites with the desired structural crystallinity (Alzeer
ranging from highly crystalline, nanocrystalline, or polycrystalline and MacKenzie, 2018). The differences in the synthesis of
 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
geopolymers and zeolites are also in reaction mixtures, i.e. the
liquid/solid ratios and alkalinities used. Zeolites generally form in
systems with H2O/SiO2 molar ratios of 10e100 and OH/SiO2 of
2e20, in comparison to geopolymers, which employ H2O/SiO2 of
2e10 and OH/SiO2 of 0.1e0.5 (Rees et al., 2008). Table 1 presents
the structures codes, SBUs and chemical formulas of zeolites
commonly appearing in geopolymeric matrices.
As shown in Fig. 1 hydroxysodalite, faujasite, and zeolite A are
built of sodalite cages (SOD-cage) formed by connected single four-
and six-membered rings (SBU: S4R, S6R) (Buchwald et al., 2011).
Zeolite A (LTA framework) possesses the so-called a-cage
comprised of 8 cuboctahedra linked by 12 cuboids. Due to its
microstructure, it has excellent ion-exchange capacities, satisfac-
tory hydrophilic properties, and is environmentally neutral, so it is
widely used in household detergents and ion-exchange mem-
branes (Duan et al., 2015; Yan et al., 2012). In LTA, each SOD-cage is
connected with six nearest neighboring SOD-cages by double T4-
rings (D4R) (Buchwald et al., 2011).
Faujasite-structure zeolites (zeolite X, Y, and natural faujasite)
are also interesting zeolites with their three-dimensional pores
structure, consisting of sodalite cages, which are connected into
double six-membered rings (D6R). Faujasite shows an open
framework and high cation exchange capacity. Thus, faujasite has
many different applications in the adsorption of heavy metals,
separation of small gas or liquid molecules, and as a catalyst in fluid
catalysis cracking (Liu et al., 2016a). In faujasite structures, a SOD-
cage is connected with four nearest neighboring SOD-cages by
double T6-rings (D6R) (Buchwald et al., 2011).
In sodalite each SOD-cage is connected with six nearest neigh-
boring SOD-cages by common T4-rings (Buchwald et al., 2011).
Sodalite b-cage frame is indicated by [AlSiO4]66, a basic unit
Table 1
Zeolite structures commonly appearing in geopolymeric matrices (Baerlocher and McCusker, 2018; Mozgawa, 2001).
Zeolite structure Zeolite
ANA analcime
CAN hydroxycancrinite
CHA chabazite (herschelite)
FAU zeolite X
zeolite Y
GIS zeolite NaeP1
LTA zeolite A
NAT natrolite
SOD hydroxysodalite (sodalite hydrate)
Fig. 1. Structure of zeolites.
559
forming the sodalite framework. Other non-framework compo-
nents, such as Naþ, OH, and H2O, are contained in the b-cages of
the structure (Oh et al., 2011a). Although hydroxysodalite is a
feldspathoid, it is closely related to zeolites. In this review
hydroxysodalite refers to sodalite hydrate.
Hydroxycancrinite, Na8[AlSiO4]6(OH)2$2H2O, represents the
cancrinite framework in ABC-6 family (Oh et al., 2011b). 19 mem-
bers of zeolite framework types can be described as ABC-6 family.
Other zeolites belonging to the ABC-6 family are sodalite, chabazite,
levyne, and offretite. This family is characterized by a basic struc-
tural layer consisting of six-membered rings of Si- and Al-
tetrahedra. The difference between zeolites representing the ABC-
6 family is in the stacking sequence of this layer. If the position of
one six-membered ring on one layer is called ‘A’ and the two
possible positions of the next layer above ‘A’ are called ‘B’ and ‘C’, all
the stacking sequences of the basic layers can be described as ‘AB’,
‘ABC’ or ‘AABB’, etc. Hydroxycancrinite is in ‘ABAB’ arrangement
and chabazite in ‘AABBCC’ arrangement (Oh et al., 2010).
1.3. Geopolymer-zeolite composites
Geopolymer-zeolite composites may merge interesting proper-
ties of both aluminosilicate materials. While geopolymeric gel
serves as a strong and durable support for zeolites, zeolites provide
higher surface area, porosity and cation exchange capacity (Provis
et al., 2005). Such zeolite-geopolymer bulk materials provide
inter-connected and multiscale distributed pores as a combination
of zeolite microporosity and geopolymer meso- and macropores
(Takeda et al., 2013; Papa et al., 2018). A synergistic effect of zeolite
crystals formation in the matrix of geopolymer, which serves as a
strong support, results in the potential for applications, e.g. as
SBU Chemical formula (sodium form)
S4R Na[AlSi2O6]$H2O
S6R Na8[AlSiO4]6(OH)2$2H2O
D6R Na[AlSi2O6]$3H2O
D6R Na2[Al2Si2.4O8.8]$6.7H2O
D6R Na1.88[Al2Si4.8O13.54]$9H2O
S4R Na3.6[Al3.6Si12.4O32]$12H2O
D4R Na2[Al2Si1.85O7.7]$5H2O
4e1 Na2[Al2Si3O8]$2H2O
S6R Na6[AlSiO4]6$8H2O
560 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
monolithic membranes (De Rossi et al., 2018). Studies on the syn-
thesis of these hybrid materials are still limited.
A significant hydrolysis of amorphous phase is necessary to form
zeolitic crystals from raw materials, which usually requires an
alkaline reaction system, high solution to solid ratio, and elevated
temperature (above 50
) (Van Deventer et al., 2006). Although the
alkaline activation of metakaolin and fly ash results in aluminosil-
icate gel as a main reaction product, differences in the composition
and microstructure of a raw material affect the microstructure of
the final product. The utilization of metakaolin results in a very
homogeneous matrix, a low Si/Al ratio of a gel, and a high degree of
zeolitization. Fly ash, in turn, induces the formation of heteroge-
neous matrices with a higher content of unreacted material, a
higher Si/Al ratio of a gel, and a smaller percentage of zeolites
(Ferna ndez-Jime nez et al., 2008).
Provis et al. (2005) reexamined the results concerning the na-
ture of geopolymer gel. This phase should be considered as nano-
particulate with nanometer-scale crystal particles (5 nm in
diameter) surrounded by a secondary continuous phase and/or
regions of nanoporosity. Oh et al., 2010, 2011a, 2011b stated that the
product of geopolymerization (N-A-S-H gel) may be regarded as a
zeolite precursor, namely a disordered form of the ABC-6 family
group of zeolites (or a single layer of the ABC-6 family structure,
Fig. 2), with hydroxysodalite and hydroxycancrinite as the best
candidates representing this type of a structure due to their
simplest atomic arrangement (AB). The similarity level is as com-
parable as tobermorite and jennite are to C-(A)-S-H in the cement
science. The amorphous precursor gel from which zeolites crys-
tallizes contains many quasi-crystalline regions, acting as sites for
zeolite nucleation, and their growth begins with the formation of
nanosized crystallites within the amorphous gel particles (Provis
et al., 2005).
Although the formation of zeolites in geopolymers have been
mentioned in many papers, there are only several papers that
directly deal with the production, characterization, application and
development of geopolymer-zeolite composites (De Rossi et al.,
2018; Khalid et al., 2018; Sturm et al., 2016, 2018; Papa et al.,
2018; Lee et al., 2016a, 2017; Greiser et al., 2017; Minelli et al.,
2018). Therefore, the papers only mentioning the appearance of
zeolites in geopolymers are also referred to in this article. In this
Fig. 2. Schematic drawing of basic layer of the ABC-6 family consisting of 6-membered
rings (dark gray indicates Al-tetrahedra; light gray indicates Si-based tetrahedra).
Reproduced with permission from Ref. (Oh et al., 2010). Copyright 2010 Elsevier.
review the manufacturing approaches of these hybrid materials are
presented (Section 2), the resistance of zeolites in composites
(Section 3) is discussed as well as their characterization methods
(Section 4), the applications (Section 5) and the influence of zeolites
on the properties of hybrid materials (Section 6).
2. Synthesis of geopolymer-zeolite composites
In this section, a comprehensive review of geopolymer-zeolite
composites manufacturing is presented, including three main ap-
proaches made for this purpose: (1) using zeolites as geo-
polymerization precursors, (2) zeolites formation as a result of the
reaction parallel to geopolymerization, and (3) hydrothermal
treatment of geopolymers. The role of several factors is discussed,
for instance raw materials, activator, additives, and curing regime.
2.1. Zeolites as raw materials
A simple way to obtain zeolitic phases in geopolymers is the
utilization of zeolites as raw materials. It is possible due to their
aluminosilicate nature. Such an approach has been applied with
both natural and synthetic zeolites, using them not only as addi-
tives or fillers with conventional materials such as fly ash or met-
akaolin, but also as geopolymerization precursors, contributing to
the formation of N-A-S-H gel. In some studies, however, zeolitic
phases dissolved completely during the process of alkali-activation,
which resulted in the absence of diffraction peaks corresponding to
zeolites in the diffraction patterns of final materials (Auqui et al.,
2017; Lynch et al., 2018; Hu et al., 2009; Yousef et al., 2009, 2012;
Ulloa et al., 2018). Therefore, the utilization of zeolite as a raw
material does not guarantee that a final product will be a
geopolymer-zeolite composite.
Since zeolites utilized for the synthesis of geopolymers usually
dissolve to a greater or lesser extent, the intensities of diffraction
peaks corresponding to zeolites decrease after alkali-activation,
which was observed, e.g. in the case of Mexican zeolite (mainly
clinoptilolite with minor heulandite part) (Villa et al., 2010), Jor-
danian zeolitic tuff (mainly phillipsite) (El-Eswed et al., 2015;
Alshaaer et al., 2016), and Ecuadorian zeolite-rich tuff (mordenite
e 70%) (Baykara et al., 2017). The degree of zeolite dissolution can
vary significantly, e.g. the amount of mordenite in the study
(Baykara et al., 2017) varied from 30 to 60 wt% depending on acti-
vator concentration. The type of activator also affects the degree of
zeolite dissolution during geopolymerization. Nikolov et al. (2017)
used clinoptilolite-rich (75%) natural zeolite as aluminosilicate
precursor. Zeolite phase was detected in the obtained materials
when sodium carbonate and water glass were used as activator,
while the activation with sodium hydroxide caused the disap-
pearance of clinoptilolite peaks. The compressive strength was
measured for mortars and was relatively low (1e4 MPa) due to the
fact that geopolymers were cured at ambient temperature. Never-
theless, the authors stated that natural zeolite-based geopolymers
can be used as coatings and plasters due to relatively high adhesion
strength (over 2 MPa).
It can be stated that the part of zeolite transforms into geo-
polymeric gel and contributes to the development of compressive
strength (Villa et al., 2010), while unreacted zeolitic phase is still
present in a newly-formed geopolymeric matrix and enhances
other properties, such as heavy metals immobilization capacity, like
in the study (El-Eswed et al., 2015): heavy metals cations could
replace exchangeable sodium cations in the framework of zeolite
phillipsite. The positive effect of natural zeolite on the compressive
strength was also observed in the case of geopolymers on the basis
of metakaolin with the addition of clinoptilolite as a filler
(Andrejkovi  et al., 2016). The diffraction peaks corresponding
cova
 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579 561

to clinoptilolite were registered for the geopolymers regardless the
content of zeolite (25, 50 and 70 wt%). The similar effect was
observed when additionally cork waste residue was added (20 wt%)
to metakaolin-zeolite geopolymers (Sudagar et al., 2018).
Synthetic zeolites are also subjected to alkali-activation or uti-
lized as additives to conventional metakaolin- or fly ash-based
geopolymers. Papa et al. (2018) used commercially available pow-
der of zeolite Na13X as a filler for metakaolin-based geopolymers in
order to merge the microporosity of zeolite with the mesoporosity
of the geopolymer matrix. Prior to mixing, zeolite form was
changed from dehydrated to hydrated to avoid the influence on
geopolymerization process. The hydration of zeolite in geopolymer
slurry could affect an established water/solid ratio of geopolymer
due to water evaporation (as hydration is an exothermic reaction),
and its entrapment in zeolite pores and channels. Zeolite addition
(22e27 wt%) caused a decrease in compressive strength in com-
parison with reference geopolymers (without zeolite) e e.g. from
27 to 17 MPa (samples activated with potassium hydroxide and
silicate solution) or from 7.5 to 3 MPa (samples activated with
NaOH). Such mechanical strengths are sufficient for the application
as self-supporting monoliths. Mineralogical characterization
revealed that zeolite Na13X was present in geopolymer-zeolite
composites. Moreover, in the case of samples activated with
NaOH two zeolitic phases were detected e zeolite Na13X used as a
filler and zeolite A as a result of a partial transformation of geo-
polymeric gel. This sample had the highest total pore volume and
specific surface area, and thus was most promising for CO2
adsorption which had a value of 3.1%. The comprehensive study on
carbon dioxide adsorption of these geopolymers (22e36 wt% of
zeolite Na13X) were also conducted (Minelli et al., 2018). The CO2
capacity of Na-activated geopolymer-zeolite composite was close to
the values obtained for pure zeolite Na13X. In the study of Huang
et al. (2012) zeolite 5 A was used as a filler in fly ash-based
geopolymers. The diffraction peaks corresponding to zeolite A
were recorded for the prepared materials, so this zeolite was pre-
sent in geopolymer matrix in unreacted form, positively affecting
formaldehyde adsorption capacity.
Zeolitic wastes were used for the synthesis of geopolymers as
well. Rodríguez et al. (2013a) investigated a spent fluid catalytic
cracking catalyst as the precursor of geopolymerization. It con-
tained quartz, mullite as well as zeolitic phases: mordenite, zeolite
ZSM-5 and dehydrated dealuminated zeolite US-Y (FAU type). As a
result of alkali-activation, zeolite US-Y dissolved regardless alka-
linity, while high alkalinity caused also the dissolution of mor-
denite. A high dissolution degree (reactivity) of zeolite Y is related
to the fact that it possesses a high number of acid sites as a result of
dealuminated framework. Mordenite, in turn, can be partially dis-
solved in high-alkaline systems as it has wider pores and, in
consequence, fewer reactive sites. Having much higher SiO2/Al2O3
ratio than mordenite, zeolite ZSM-5 is more stable at high pH.
Alkali-activation of waste fluid cracking catalysts was performed by
Silva et al. (2016) as well. Xu et al. (2016) prepared metakaolin-
based geopolymers with the addition of strontium-loaded zeolite
A. In comparison to Portland cement-based products, the geo-
polymer solidification materials exhibited higher compressive
strength, thermal stability as well as Sr leaching resistance.
2.2. Direct zeolites formation in the matrix of geopolymer
The utilization of zeolites as raw materials for the production of
geopolymer-zeolite composites is, however, cost generating since
zeolites can form in geopolymer matrix by themselves. Their for-
mation is often an accompanying reaction to geopolymerization,
and the type and amount of zeolite depend on the chemical
composition of raw materials, the type of alkaline activator as well
as curing conditions (Table 2).

Table 2
Zeolites formed in geopolymers depending on synthesis and curing conditions.

Synthesis conditions Curing conditions Obtained zeolitic structure types Ref.

Precursor Activator Si/Al Na/Al LTA FAU CHA SOD other

MK SH 1.0 1.0 60
C, 6h þ Wan et al. (2017b)

MK SH 1.0 e 50
C, 24 h þ Zibouche et al. (2009)
MK SH 1.0 0.88 80
C, 24 h þ Krol et al. (2016)
MK SH 1.0 1.0 95
C, 24 h þ Krol et al. (2016)
MK SH 1.0 1.0 95
C, 24 h þ þ Krol et al. (2017a)
MK SH 1.0 1.0 80
C, 24 h þ Krol et al. (2017a)
MK SH 1.0 1.10 40
C, 54 h þ Zhang et al. (2012)
MK SH 1.0 1.47 30
C, 72 h þ Zhang et al. (2012)
MK SH 1.03 0.85 60
C, 24 h þ Li et al. (2017)
MK SH, WG 1.13 1.0 95
C, 24 h þ Krol et al. (2017a)
MK SH 1.12 1.492 60
C, 24 h þ þ Ozer and Soyer-Uzun (2015)
MK SH 1.12 1.492 60
C, 7d þ Ozer and Soyer-Uzun (2015)
MK SH, WG 1.25 1.0 90
C, 48 h þ Rasouli et al. (2015)
MK SH, WG 1.11 1.0 95
C, 24 h þ þ Krol et al. (2016)
MK SH 1.12 1.0 90
C, 48 h þ Rasouli et al. (2015)
MK SH, WG 1.13 1.0 80
C, 24 h þ Krol et al. (2017a)
MK SH, WG 1.24 1.0 95
C, 24 h þ Krol et al. (2016)
MK SH, WG 1.25 1.0 95
C, 24 h þ Krol et al. (2017a)
MK SH 0.25 0.66 40
C, 1 h; 90
C, night þ Fletcher et al. (2005)
MK SH 0.5 0.66 þ Fletcher et al. (2005)
MK SH, WG 2.50 1.67 40
C, 53 d þ De Silva and Sagoe-Crenstil (2008)
MK SH, WG 1.9 0.99 110
C, 1 m ANA Lancellotti et al. (2013)
RHA SA 1.5 1.27 40
C, 21 d þ þ Hajimohammadi and van Deventer (2017)
GSb SA 1.5 1.3 40
C, 21 d þ þ ANA Hajimohammadi et al. (2011a)
FA SH 2.78 1.02 80
C, 6 h CAN Oh et al. (2010)
FA SH 2.3 1.31 20
C, 0.5 h CAN Sun and Vollpracht (2018)
FA SH, SA 1.0 1.0 70
C, 24 h þ þ Temuujin et al. (2010)
MSa SA 1.0 0.98 80
C, 3 d þ þ þ Sturm et al. (2016)
MSa SA 3.0 0.98 80
C, 3 d þ þ Sturm et al. (2016)
a
Microsilica.
b
geothermal silica.
562 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
The role of Si/Al ratio. One of the most important factor affecting
the possibility of zeolites appearing during geopolymerization is
the molar ratio of silicon to aluminum (Si/Al) in a reaction system e
the elements which also form zeolitic frameworks. The composi-
tion of zeolites is generally close to the composition of the gel from
which they crystallize (Panagiotopoulou et al., 2015). Metakaolin is
often treated as a model geopolymeric system due to its relatively
simple chemistry (van Deventer et al., 2007). Moreover, zeolite
formation is commonly observed in metakaolin-based geopolymer
matrix. Wan et al. (2017a) identified zeolite A only at Si/Al ratio of 1
in such geopolymers. At extended Si/Al ratios, with silica fume as
additional silica source, zeolites did not appeared, suggesting that
higher ratios (from 1.5 to 4) prevent zeolites from crystallization.
Similar observations at Si/Al close to 1 was presented in the studies
(Zibouche et al., 2009; Kro l et al., 2016). Zeolites were more likely to
arise when the content of aluminum is higher, so at the lower Si/Al
ratio, confirming the optimal value of 1.0 for the formation of
zeolite A. Zeolite X appeared at Si/Al ratio higher than 1.1 and H2O/
Na2O ratio seemed not to have any significant effect on the type and
quantity of zeolitic products (Kro l et al., 2016). The suggestion that
Si/Al ratio a little higher than one favors the formation of faujasite
structure is consistent with works (Buchwald et al., 2011; Kro l et al.,
2017a). In contrast, Rasouli et al. (2015) observed zeolite A at
slightly higher Si/Al of 1.25, while zeolite X at 1.12. In fact the
reacting gel could have a lower or higher Si/Al ratio at least locally
where the particular zeolites were forming. When the content of
aluminum is too high, the formation of zeolite A is hampered,
though. In high-alumina metakaolin-based geopolymers with SiO2/
Al2O3 ratios of 0.5 and 1.0 only hydroxysodalite was identified
(Fletcher et al., 2005). This phase was also observed at high Si/Al
ratio of 2.46 (Kro l et al., 2016).
In the case of fly ash-based geopolymers zeolite chabazite has
been observed in several studies (Temuujin et al., 2010; Azevedo
and Strecker, 2017; Ferna ndez-Jime nez et al., 2006; Ye and
Radlin ska, 2016; Provis et al., 2009; Bhagath Singh and
Subramaniam, 2017; Criado et al., 2007; Oh et al., 2014). It was
stated that higher contents of silica favors the early formation of
chabazite (Criado et al., 2007). Oh et al. (2014) obtained Al-rich Na-
chabazite and Na-chabazite (herschelite) at Si/Al ¼ 2.6 and Ca/
Si ¼ 0.4 in geopolymer based on fly ash activated with NaOH at
60
C. Zeolite A formed at Si/Al of 3.0, which is relatively high
compared to metakaolin-based geopolymers, and Ca/Si of 0.1.
Chabazite zeolites possess double 6-membered rings and belong to
ABC-6 family and the geopolymer consisting of these zeolites
achieved higher compressive strength since geopolymeric gel is
structurally related to this particular type of zeolite framework
(ABC-6).
Rees et al. (2007) investigated the effect of different silicate
concentrations on fly ash-based geopolymers (Si/Na ¼ 0.75) cured
at 30
C for 100 days. Hydroxysodalite appeared at low silicate
concentrations (0e0.6 M SiO2), faujasite at moderate concentra-
tions (0.8e1.2 M) and no zeolites at high concentrations (>3.5 M).
Irfan Khan et al. (2015) also found that the formation of hydrox-
ysodalite is favored by low Si/Al ratio (1.78) and Na/Al ratio higher
than 0.8. Generally, hydroxysodalite is an easily-forming phase in
the case of fly ash-based geopolymers (Azevedo and Strecker, 2017;
Fernandez-Jime nez et al., 2006; Provis et al., 2009; Criado et al.,
2007; Bo €ke et al., 2015; Temuujin et al., 2014). Komljenovi c et al.
(2010) activated different fly ashes with various activators and
showed that the obtained products were mainly amorphous and
the formation of zeolite faujasite was rather the exception than the
rule. The increase in silicon ions content in the solution resulted in
the decrease in the probability of zeolite formation. Similar obser-
vations were presented by Buchwald et al. (2011) in the case of
aluminosilicate geopolymeric gel prepared from pure alkali silicate
and alkali aluminate solutions. At constant activator concentrations
hydroxysodalite was eager to form at low Si/Al ratio of 1, faujasite at
2 and 3, while higher ratios resulted in completely amorphous
products. Hajimohammadi and van Deventer (2017), in turn,
identified zeolite X and zeolite A in geopolymers prepared from rice
hull ash and sodium aluminate at Si/Al of 1.5 and H2O/Na2O of 14,
while at higher Si/Al (2.5) and lower H2O/Na2O (12) no zeolites
were observed. Rice husk (or hull) ash (RHA) is an industrial waste
generated as a by-product of burning rice husks, an abundantly
available by-product of rice milling. The worldwide production of
rise husks is about 70 million tons per year (Hwang and Huynh,
2015). The zeolitic phases were observed after 21 days of curing
(no peaks were registered after 2, 6 and 14 days) (Hajimohammadi
and van Deventer, 2017), which is related to the fact that the growth
of zeolite crystals is relatively slow (Komljenovi c et al., 2010) and
depends for example on silica availability. The influence of silica
availability on geopolymerization was examined with the use of
geothermal silica (Hajimohammadi et al., 2011a). The sample with
the lowest Si availability needed the longest time to develop the
zeolitic phases: after 4 days of curing zeolite A was present in all
samples, while faujasite in samples with higher silica availability. In
the sample with the lowest Si availability faujasite was observed
after 21 days of curing, so similar chemical changes were taking
place regardless silica availability, but with different rates.
Sturm et al. (2016) obtained geopolymer-zeolite composites
using different sources of silica (microsilica and residue from the
chlorosilane production) and sodium aluminate. For microsilica-
based samples zeolite A and hydroxysodalite were dominant pha-
ses. However, the higher the silica content, the higher the relative
amount of zeolite A and lower of hydroxysodalite. Moreover, in the
low-silica systems also chabazite was present. For chlorosilane
residue-based specimens zeolite A was a major phase, but in low-
silica samples hydroxysodalite, faujasite and zeolite EMT (hexago-
nal zeolite Y) were detected as well. It was assumed that the direct
formation of hydroxysodalite and early transformation of zeolite A
into hydroxysodalite structures were caused by a higher pH.
The role of an activator. The role of an alkali-activator in the
process of zeolites formation is rather complex. Sodium hydroxide
is a commonly used alkali-activator, while potassium hydroxide is
used quite rarely. They induce the appearance of different zeolitic
phases in a geopolymeric matrix. The concentration is an important
factor as well. When sodium silicate solution (water glass) is used at
the same time as hydroxides, the effect of introduced silicon should
be also considered since Si/Al ratio is, as mentioned above, a crucial
factor. For instance, Li et al. (2017) observed the formation of zeolite
A in metakaolin-based geopolymer activated with NaOH solution,
but no zeolites with water glass. It can be then supposed that Si/Al
raised to too high level, hampering the possibility of zeolite A
crystallization. Similar observations were noticed in the case of fly
ash-based geopolymers: sodium chabazite formed in fly ash acti-
vated with NaOH (10 M), while no zeolites when sodium silicate
was used as an activator (Zhang et al., 2008). The formation of
cancrinite and hydroxysodalite in fly ash/waste glass geopolymers
activated with sodium hydroxide was showed in the study
(Bobirica et al., 2015). In the case of activation with sodium silicate
no zeolites crystallized. The presence of sodium silicate can affect
not only the possibility, but also the type of zeolites forming in
geopolymeric matrix. Moon et al. (2014) activated basaltic-type
natural pozzolanic material in order to obtain geopolymers:
zeolite Y and hydroxysodalite were formed in samples activated
with sodium hydroxide, while phillipsite and small amount of
zeolite Y in the case of sodium hydroxide/water glass activation.
Panagiotopoulou et al. (2015) stated that the increase in silicon
content in the activator solution leads to the formation of more
disordered phases. At the lowest Si/Al ratio (1.0) hydroxysodalite
 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
was identified, at Si/Al ¼ 2.4 faujasite, while at the highest ratio no
zeolites were detected. The use of activation solutions with low
silicon and high alkali content favors the formation of zeolitic
phases. Ma et al. (2016) observed the transition of geopolymeric gel
into zeolite (analcime) in fly ash-based geopolymers activated with
sodium hydroxide already at 25
C, while with sodium silicate only
at 80
C, which was related to the mechanism that soluble silicates
hamper the crystallization of zeolites in geopolymers. Torres-
Carrasco and Puertas (2015) examined glass waste as a potential
activator (accompanied by NaOH solution) in fly ash geopolymer
systems. Hydroxysodalite and Na-chabazite as well as N-A-S-H gel
were detected in the obtained materials. The same was observed in
conventional systems, activated with NaOH and NaOH/water glass.
In the case of the concentration of alkalis, it was observed that
the formation of zeolite A in metakaolin-based geopolymers is
preferred at lower alkali content (10 M vs. 12 M NaOH) and at
higher temperature, since zeolites prefer to form at slightly lower
alkalinity and higher reaction temperature (high alkali concentra-
tions favor hydroxysodalite formation rather than zeolite A) (Zhang
et al., 2012). The similar observation was presented in the study
(Boonjaeng et al., 2014), where zeolite A formed at extremely low
concentrations of activator (0.01 and 0.1 M NaOH) in the matrices of
alkali-activated metakaolin with Ca(OH)2 (metakaolin/calcium hy-
droxide mass ratio of 0.4). The dependence of zeolite type on sys-
tem alkalinity is related to the fact that some building units of
zeolites remain stable under different alkalinities. At higher con-
centrations (3 and 5 M), chabazite and zeolite ZK-14 were identi-
fied. The fact that increasing system alkalinity (NaOH
concentration) favors the formation of zeolite ZK-14 was also re-
ported in activated calcined kaolinitic-illitic clay (El Hafid et al.,

2017). Alvarez-Ayuso et al. (2008) prepared fly ash-based geo-
polymers and observed that chabazite and hydroxysodalite were
present in most cases, zeolite X and zeolite 4 A in geopolymers
obtained at low alkaline solution (5 M NaOH), while zeolite NaeP1
at higher alkalinity (8 and 12 M). In the case of aluminosilicate
geopolymeric gel prepared from pure alkali silicate and alkali
aluminate solutions, at Si/Al ratio of 1.0, the pH was a crucial factor
in terms of zeolites crystallization (Buchwald et al., 2011). The
lower the concentration of NaOH, the higher the formation ability
of zeolite A and zeolite X. A high NaOH concentration favored
hydroxysodalite crystallization. A similar conclusion was drawn in
the studies (Rozek_ et al., 2018; Krol et al., 2017b), where the in-
tensity of diffraction peaks corresponding to hydroxysodalite was
growing with the increasing content of NaOH in the reaction me-
dium of fly ash-based geopolymers. Moreover, the addition of so-
dium aluminate promoted the formation of hydroxysodalite (Kro l
et al., 2017b).
The type of zeolite that forms parallel to geopolymerization de-
pends on the dominant cation in an activator solution. Shearer et al.
(2016) prepared geopolymers based on fly ash from co-combustion
of coal and biomass and detected in their matrices Na-chabazite,
faujasite and analcime (activation with 7% Na2O). An increase in
activator content reduced the formation of zeolites, especially fau-
jasite. Also, an increase in soluble silica slowed their crystallization.
For ashes activated with potassium no zeolites formed, suggesting
that the formation of potassium zeolites is not so favored as the
formation of sodium ones. The kind of alkali ion affects not only the
dissolution of the aluminosilicate material, but also the poly-
condensation of a geopolymeric gel (Kro l et al., 2018). Bakharev
(2005b) observed zeolite NaeP1 and hydroxysodalite in fly ash-
based geopolymers. These phases were observed to be more or-
dered in the case of the sample activated with NaOH than in the
sample activated with NaOH together with KOH. The activation of
meta-illite-smectite clay with NaOH at 75
C resulted in the for-
mation of phillipsite, while the use of KOH gave only traces of zeolite
563
L, confirming that the activation with KOH is less related to zeolite
formation (Hu et al., 2017). However, it positively affects the for-
mation of an amorphous geopolymeric network (Panagiotopoulou
et al., 2015). The presence of zeolite KeI (K2Al2Si2O8$3.8H2O) in
blast furnace slag activated with KOH (4 and 8 M) as well as potas-
sium gismondine (in the case of 4 M KOH) was observed in the study
(de Moraes Pinheiro et al., 2018). The effect of olive-stone biomass
ash was also investigated: it hampered the formation of zeolitic
phases since zeolite KeI was not detected. In geopolymers based on
metakaolin faujasite and zeolite V (Na3K3Al3Si3O24$12H2O) were
found (Duxson et al., 2007). Analcime, zeolite NaeP1 and two zeo-
lites with natrolite type structure: gonnardite ((Na,Ca)2(Si,A-
l)5O10$2H2O) and mesolite (Na2Ca2Al5Si9O30$8H2O) were detected
in fly ash-based geopolymers activated with sodium silicate
(Rodríguez et al., 2013b). The activation with nanosilica resulted in
the formation of faujasite with no other zeolitic phases. The acti-
vation with potassium silicate, in turn, caused the crystallization of
K-chabazite. Elert et al. (2015) treated clay with 5 M solution of NaOH
and KOH and investigated phase composition after 1 week,1, 2.5, 4, 6
months and one year of treatment. In the case of NaOH treatment,
faujasite was observed after 6 months and hydroxysodalite after a
year. The KOH environment induced the formation of zeolite KeI and
chabazite after 4 months and 1 year, respectively. The formation of F-
type zeolite (KAlSiO4$1.5 H2O) in metakaolin foams activated with
potassium silicate was observed in the works (Prud’Homme et al.,
2011; Prud’Homme et al., 2012; Delair et al., 2012).
The formation of natrolite was proposed to improve the strength
of BFS-FA geopolymeric binders (Huang et al., 2017). It was also
detected in the same system also with the addition of metakaolin
(Huang et al., 2018), while in geopolymers based on heated
kaolinitic-illitic clay also chabazite was present (El Hafid and
Hajjaji, 2015). In fly ash-based geopolymers natrolite was detec-
ted together with zeolite NaeP1 (Bhagath Singh and Subramaniam,
2016). At higher SiO2/Na2O ratio (2.16) natrolite and zeolite NaeP1
were identified, but the latter disappeared after 7 days. At lower
ratio (1.51) the same zeolites were detected, however, the amount
of zeolite NaeP1 was increasing with time. Natrolite has been also
found in circulating fluidized bed (CFB) combustion fly ash geo-
polymers (Eiamwijit et al., 2015), also when silica fume was added
(Chindaprasirt et al., 2014), which was attributed to a high con-
centration of activator (15 M NaOH). Also zeolite Y formed in such
geopolymers with increasing peaks intensity with decreasing SiO2/
Na2O molar ratio (increasing alkalinity). Tyni et al. (2014), in turn,
identified faujasite and Na-chabazite in geopolymers based on CFB
bottom ash. In the case of samples prepared with 10 M NaOH
activator solution, both zeolitic phases were observed, while in
geopolymers prepared with 5 M NaOH only chabazite was detected.
The role of curing. It should be noted that curing of geopolymers
is directly related, e.g. with alkalinity and silica to alumina ratio. It
was observed that different temperatures of activation result in the
formation of various zeolitic phases. Cwirzen et al. (2014) activated
metakaolin and limestone blends with NaOH (3 M), which resulted
in the formation of zeolite A, both at low (20
C) and high (80
C)
temperature of curing. However, the activation with 5 M NaOH
showed a significant temperature effect, i.e. no zeolites at a low-
temperature activation, and faujasite formation at a higher tem-
perature. In the case of Si/Al different zeolitic phases were obtained
in the matrix of metakaolin-based geopolymers depending on
curing temperatures as well: at Si/Al of 1.12 zeolite A at 95
C and
zeolite X at 80
C, while at 1.25 zeolite X at 95
C and no zeolites at
80
C (Kro
l et al., 2017a). Granizo et al. (2014) evaluated time and
temperature of metakaolin-based geopolymers curing (Fig. 3). Ze-
olites started to form after 10 h of curing. Zeolite A and zeolite X
formed at 25
C after 9 days and hydroxysodalite was detected in
36-day sample. At 85
C reactions were much faster, namely after
564 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
Fig. 3. Zeolites present in the solid phase at (a) 25 and (b) 85
C (N5 e activation with 5 M NaOH, N8 e 8 M NaOH). Reproduced with permission from Ref. (Granizo et al., 2014).
Copyright 2014 Elsevier.
8 h zeolite A began to transform into hydroxysodalite and to
disappear totally after 14 days. Zeolites are metastable and may
successively transform into one or several more stable phases
(Criado et al., 2007). Also, an increase in the crystallinity of zeolite
A, faujasite and hydroxysodalite in geopolymers based on meta-
kaolin and rise husk ash was observed with increasing curing
temperature (Sore et al., 2016). In geopolymers based on water
treatment sludge and fly ash chabazite formed at 65, 75 and 85
C,
while gismondine only at higher temperatures (75 and 85
C)
(Suksiripattanapong et al., 2015). In the case of geopolymers pre-
pared with using of sewage sludge ash as a partial replace of
metakaolin, zeolite (faujasite) crystallized in the samples cured at
65
C in a thermal bath, while no peaks were observed in case of
25
C (Istuque et al., 2016). The effect of curing regime on the type
of zeolites formed in fly-ash based geopolymers activated with
NaOH was shown in the study (Bakharev, 2005a). Zeolite A and
chabazite were present in the samples precured in room temper-
ature for 2 h and then cured at elevated temperature (75
C) for one
month, while chabazite, zeolite NaeP1 and hydroxysodalite in the
samples with precuring time of 24 h and 6 or 24 h of heat curing.
Duan et al. (2015) used metakaolin as a precursor e zeolite A
occurred in the matrix of geopolymers cured for 16 h at 70
C and
higher temperatures, however, at 110 and 130
C peaks corre-
sponding to zeolite A were significantly weaker. The highest
amount of zeolite A was observed in geopolymer synthesized with
Na/Al ratio of 1.0, water/binder ratio of 0.7, cured at 70
C for 16 h.
Bernal et al. (2011) observed the formation of gismondine in
alkali-activated granulated blast furnace slag and its blends with
metakaolin. An increase in curing times contributed to the forma-
tion of zeolitic phases. The presence of gismondine was not stated
at early ages of curing, suggesting that longer time of curing is
required for the development of full crystallinity in this phase as a
consequence of its complex structure. Ozer and Soyer-Uzun (2015)
observed that the time of thermal curing (at 60
C) influenced the
formation of zeolite phases in metakaolin-based geopolymers
(with Si/Al ratio of 1.12): mainly zeolite A and small amount of
hydroxysodalite were present after 1-day, while mainly the latter
after 7-day curing. The phase evolution in geopolymers based on
geothermal silica and sodium aluminate, seeded with 0.5 wt% of
oxide (Al2O3, ZnO and ZrO2) nanoparticles, was observed in the
work (Hajimohammadi et al., 2011b). Zeolite A was present in the
samples after 4 days at 40
C, while after 3 weeks zeolite A as well
as faujasite and analcime. After 8 months faujasite peaks became
stronger in XRD patterns of seeded samples, while disappeared in
the case of unseeded sample since seeding reduces the nucleation
time required for zeolite synthesis. Criado et al. (2007) concluded
that the formation of well-crystallized zeolites requires a long
period of time, while amorphous zeolite precursor gel is expected
to form at ambient conditions in a short reaction time. The trans-
formation of amorphous phase into chabazite or zeolite X into ze-
olites A and P in metakaolin-based geopolymers was observed
between 53 and 210 days of curing at 40
C and corresponding
strength reduction (De Silva and Sagoe-Crenstil, 2008). Such phe-
nomenon was also observed in the case of commercial X-type
zeolite that transformed into the more stable P-type zeolite and
hydroxysodalite (Takeda et al., 2013). Analcime was observed in
metakaolin-based geopolymer cured at a relatively high tempera-
ture of 110
C for 1 month (Lancellotti et al., 2013). It is the most
stable and densest common zeolitic phase (Criado et al., 2007). The
extended curing time enhanced the formation of chabazite and
gismondine in silty clay-fly ash geopolymers (Sukmak et al., 2013).
In the study (Criado et al., 2010), the quantity of zeolites (chabazite,
hydroxysodalite) was increasing with time as follows: 4.9% (8 h),
24.8 (7 d), 28.1 (28 d), 36.5 (180 d).
The role of raw materials, additives and other factors. Slaty et al.
(2013) observed the formation of Na-zeolites (phillipsite and
natrolite) and hydroxysodalite in kaolinitic clay activated with
NaOH at 80
C for 24 h. The use of raw kaolinitic clay, however,
results in the presence of unreacted phases such as kaolinite,
muscovite and illite in the matrix of geopolymer. Heah et al. (2012)
activated kaolin with NaOH and WG and observed the formation of
zeolite X after curing at 80
C for 24 h. In the case of metakaolin-
based geopolymers, the temperature of kaolinite calcination may
be an additional factor affecting the formation of zeolites. Glid et al.
 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
(2017) showed that zeolite A formed in shorter times in the case of
kaolinite heated in 550 than in 800
C, namely 20 min versus
120 min. It was observed that the quantity of zeolite increased with
increasing specific surface area of metakaolin (Fig. 4) e the higher
the specific surface area, the higher the solubility of Al and Si ions,
resulting in an increase in zeolite formation (Takeda et al., 2013).
The activation (9 M NaOH at 70
C) of metakaolin obtained by
kaolinite calcination at 700
C resulted in the formation of zeolite A,
while from metakaolin calcined at 800
C only amorphous matrix
was obtained (Kro l and Rozek,
_ 2019). Belviso et al. (2015) prepared
geopolymers on the basis on fly ash/kaolinite mixtures. The tem-
perature of activation was relatively low, 45
C, and time differed
from 1 to 216 h. Zeolites X and ZK-5 were detected in the geo-
polymer based only on fly ash. The increasing part of kaolinite
resulted in a decrease in zeolite X amount, an increase in zeolite A
and a total elimination of zeolite ZK-5. FAU-type zeolites have been
also detected in geopolymers based on fly ash (Ye and Radlin  ska,
2016) and rice husk ash (Hwang and Huynh, 2015), in low-silica
fly ash-based geopolymers (Provis et al., 2009), and metakaolin-
based geopolymers (Takeda et al., 2013; Liew et al., 2012).
Peng et al. (2017a) observed zeolite NaeP1 and hydroxysodalite
in a one-part geopolymer obtained by alkali-fusion of bentonite
with 20% NaOH at 700
C. Faujasite and hydroxysodalite, in turn,
appeared when Na2CO3 was used as an activator at 850
C and also
zeolite NaeP1 at 1000
C. This zeolite was also found in a one-part
geopolymer obtained by hydration of bentonite calcined together
with dolomite and Na2CO3 (Peng et al., 2017b). Naghsh and Shams
(2017) applied a two-step method of geopolymer preparation,
including a fusion of kaolin with sodium hydroxide (400e800
C)
and hydration/dealkalization (washing with distilled water), so
kaolin may be used directly, without the necessity of its trans-
formation into metakaolin. Zeolite ZSM-5 was detected in geo-
polymer obtained from fusion at 800
C for 14 h with NaOH/kaolin
ratio of 2.2, while at 600
C geopolymer was completely amor-
phous. The presence of zeolite Y in one-part-mixing geopolymers
based on metakaolin geopolymer powder was confirmed as well
(Yun-Ming et al., 2017).
Ye et al. (2014) prepared geopolymers based on Bayer red mud
(waste residue from caustic soda digestion of alumina from bauxite
ore in the Bayer process). Cancrinite zeolite crystallized in the
samples containing only red mud as well as containing red mud
and granulated blast furnace slag (RM/GBFS 1:1 wt/wt). Its forma-
tion was related to adsorption of carbon dioxide from air in a highly
basic environment according to the equation:
2CO2 þ 6Naþ þ 2Ca2þ þ 6H3 SiO
4 þ 6AlðOHÞ4 /Na6 Ca2 Al6 Si6 O24 ðCO3 Þ2 , 2H2 O þ 18H2 O þ 2OH
Cancrinite was also observed in one-part geopolymer binders
prepared from red mud with the addition of silica fume (Ye et al.,
2016), geopolymers based on pumice-type natural pozzolanic
material (together with chabazite) (Najafi Kani et al., 2012), NaOH-
activated fly ash (Sun and Vollpracht, 2018; Oh et al., 2010), BFS/FA-
based geopolymers (Xu et al., 2014), and geopolymers based on
waste sandstone sludge (zeolite A and sodalite formed instead
when sludge was replaced by 50 wt% of metakaolin) (Clausi et al.,
2018). Zeolite vishnevite (Na8Al6Si6O24(SO4)$2H2O, CAN structure)
was observed in geopolymers based on bottom and fly ash from
pulverized coal combustion (Boonserm et al., 2012).
Komnitsas et al. (2009) observed the formation of hydrox-
ysodalite in geopolymers based on electric arc ferronickel slag and
565
Fig. 4. Relationship between the specific surface area of metakaolin and the amount of
zeolite in final materials (Takeda et al., 2013).
kaolin blends activated with sodium silicate and sodium or potas-
sium hydroxides. Hydroxysodalite was not detected when meta-
kaolin was used instead of kaolin, as kaolin provides OH ions
which accelerates the reaction of kaolin with NaOH, while meta-
kaolin does not contribute to the formation of hydroxysodalite
because it is the product of dehydroxylation. Zeolite ZK and
hydroxysodalite were observed in fly ash-based geopolymers
activated with 8 M solution of NaOH (zeolite ZK is similar to so-
dalite) (Nath et al., 2016). Hydroxysodalite has been also identified
in geopolymers based on, e.g. FA with BFS (Bobirica  et al., 2015;
Gordon et al., 2014; Muhammad et al., 2018), coal bottom ash
(Geetha and Ramamurthy, 2013), bagasse bottom ash (waste of
sugar industry) and natural clay (together with chabazite) (Noor-
Ul-Amin et al., 2016) as well as in alkali-activated aluminosilicate
glass with various CaO content (Garcia-Lodeiro et al., 2016). In
geopolymers based on heated clay with milled waste glass also
chabazite was found (El Hafid and Hajjaji, 2018). Also, zeolites of
gismondine-type structure (GIS) have been mentioned in several
works concerning geopolymers: garronite and zeolite NaeP1 were
detected in geopolymers based on slag/fly ash (25 wt%/75 wt%) and
fly ash (Ismail et al., 2014), thomsonite and garronite in MK/BFS-
based geopolymers (Zhang et al., 2010), gismondine in Ca-rich fly
ash-based geopolymer activated with mixed sodium hydroxide and
sodium silicate (Guo et al., 2010a) and in complex geopolymers
based on coal fly ash and other Ca-containing materials (Portland

cement, flue gas desulfurization gypsum, and water treatment re-
sidual) (Guo et al., 2010b), zeolite NaeP1 in the samples of meta-
kaolin activated with sodium silicate solution and cured at 80
C in
water bath (Zhu et al., 2013) as well as in halloysite-based geo-
polymer (Takeda et al., 2013).
The presence of limestone in the system of alkali-activated
metakaolin enhanced the formation of zeolites (in comparison to
samples based only on metakaolin) (Cwirzen et al., 2014). More-
over, the higher content of limestone favored the formation of
hydroxysodalite, while the lower content favors zeolite A. Jun and
Oh (2014) observed Al-rich chabazite, zeolite A and zeolite X in
fly ash-based geopolymers e chabazite was found only in geo-
polymer based on fly ash containing 10 wt% CaO, and was absent
566 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
when CaO content was lower than 5 wt%. The samples with cha-
bazite showed higher compressive strength than the samples with
zeolite A, although it can be related to the formation of CeSeH
phase due to the higher content of CaO. Tzanakos et al. (2014)
prepared geopolymer based on metakaolin and medical waste
incineration ash (fly ash and bottom ash) and obtained faujasite in
its matrix. The addition of calcium carbonate caused the formation
of phillipsite. It was however stated that sodium aluminosilicate
hydrate containing calcium (Ne(C)eAeSeH) is more stable, and
with the increase in the content of calcium and other elements, the
transition from amorphous gel to crystalline zeolite becomes more
and more difficult (Ma et al., 2016).
Fernandez-Jime nez et al. (2017) alkali-activated fly ash and glass
powder with cleaning solution from aluminum casting industry. In
both cases herschelite, zeolite NaeP1 and hydroxysodalite
appeared in a geopolymeric matrix. These zeolites did not form
when NaOH (8 M) was used as an activator, which suggests that the
character of cleaning solution induced zeolites crystallization,
namely its lower alkalinity and soluble Al presence. When high
surface area Al2O3 nanoparticles were introduced to a fly ash geo-
polymeric mix, zeolite NaeF (Na2Al2Si2O8$xH2O) formed e a syn-
thetic zeolite with the edingtonite structure type (EDI), observed in
geopolymers for the first time (Rees et al., 2008). In the seeded
geopolymer system the formation of zeolite F is favored in the re-
gions of Al-rich gel located close to the original nuclei, which
provides the proper stoichiometry. The presence of this Al-rich gel,
which did not occur in the unseeded system, explains the formation
of zeolite F at a lower Si/Al ratio than zeolite X that formed in the
absence of seeding. In the case of alkali-activated Ca-rich clay with
the addition of AlF3 production waste (a by-product silica with a
high AlF3 content, i.e. 60.15% and 35.52%, respectively), only
hydroxysodalite was present in the samples with 0, 10 and 25%
addition of the AlF3 production waste (Vai ciukyniene_ et al., 2018).
Zeolite A formed as a product of hydroxysodalite recrystallization in
the geopolymer with 50% addition, which caused a slight decrease
in compressive strength. Liu et al. (2017a) prepared foamed
geopolymer-zeolite blocks from fly ash with oleic acid and Al
powder, cured at 80
C for 36 h. Faujasite was a dominant phase in
geopolymer with the addition of 0.05 wt% of Al powder, while in
the case of 0.10 wt% zeolite NaeP1 was also present as a trace. It is
therefore possible to design the type of zeolite by controlling
aluminum content in the mixture.
Liu et al. (2017b) prepared Al2O3eSiO2 powder by the sol-gel
method, activated it with sodium silicate, and cured at 60
C for
6 h. It was shown that only the samples with H2O/Na2O molar ratio
higher than 8 can transform a geopolymeric gel into zeolite A. The
limitations on zeolites formation in systems with low amount of
free water are related to the fact that nutrients needed for the
crystallization cannot be provided due to transportation difficulties.
Additionally, the suspension solidification method was used to
prepare spheres e the geopolymeric slurry with H2O/Na2O ¼ 10
was dosed in droplets into silicon oil or polyethylene glycol (PEG-
6000). The geopolymer spheres formed in silicone oil transformed
into zeolite A, while in polyethylene glycol did not transform into
zeolites. When water diffuses from the inside to the surface of a
sphere, it is sealed due to the fact that is insoluble in silicon oil.
Tetrahedra of [SiO4] and [AlO4] rearrange around free sodium ions
because of the transport of water molecules and transform into
zeolites around the formed nanocrystalline core. Since water is
highly soluble in polyethylene glycol, water molecules with sodium
ions can diffuse outside a sphere, so there is no medium that can
transport and rearrange silicate and aluminate groups in the geo-
polymer gel which can transform into zeolite. The mechanism is
also discussed in Section 2.4.
Alkali-activation of metakaolin at 85
C resulted in the
formation of hydroxysodalite and traces of zeolite A (Ferna ndez-
Jimenez et al., 2008). Then the samples were treated at 150
C
and faujasite and greater amount of zeolite A were detected. That
thermal treatment caused the increase in the compressive strength
of alkali-activated matrices. The similar situation was observed for
metakaolin/fly ash geopolymer. After the exposure of fly ash/slag
geopolymer to 800
C dehydrated Ca-substituted zeolite A
appeared (Zhang et al., 2015). The formation of zeolite NaeP1 was
observed after thermal shock of fly ash-based geopolymers (Nazari
et al., 2017).
The factor which can induce the formation of zeolites in geo-
polymers is pH. Nguyen and Skv   ara (2016) provided evidence for
the appearance of zeolitic phase (minor amounts of zeolite NaeP1)
in the sample of fly ash-based geopolymer immersed in the solu-
tion of NaOH (pH of 14) for 360 days. Shi et al. (2018) observed the
formation of zeolites (zeolite A, zeolite X and zeolite NaeP1) in the
case of pastes and mortars of alkali-activated slag with metakaolin
exposed to 1 M NaOH. Zeolite NaeP1 also formed in pastes with fly
ash after the same exposure. Zeolite NaeP1 and hydroxysodalite
were observed in fly ash-based geopolymers, and after the expo-
sure to sulfate solutions, chabazite was also identified (Bakharev,
2005b). Zeolite NaeP1 and chabazite appeared in the fly ash-
based geopolymer activated with sodium silicate after its expo-
sure to 5% sulfuric acid solution (Bakharev, 2005c). The presence of
NaSO4, in turn, in an activating solution retarded the formation of
N-A-S-H gel in alkali-activated fly ash, but accelerated its trans-
formation into zeolites, such as Na-chabazite, zeolite NaeP1 and
hydroxysodalite (Criado et al., 2010).
The increasing content of lead immobilized in fly ash-based
geopolymers hampered the formation of hydroxysodalite (Lee
et al., 2016b). In fly ash-based geopolymers immobilizing arsenic
(1 wt%), the formation of hydroxysodalite and herschelite was not
disturbed (Fernandez Jiminez et al., 2004). The formation of zeolite
A was shown in water treatment residue-based geopolymers, and
NaeZn-exchanged zeolite A in the case of zinc immobilization in
geopolymeric matrix (Waijarean et al., 2017). Bell et al. (2008)
mixed metakaolin with cesium silicate solution and cured the
mixture at 50
C for 24 h. After heating the obtained geopolymer to
1100
C, the formation of pollucite was observed. Pollucite (CsAl-
Si2O6), a Cs-bearing zeolitic phase, has a significant industrial in-
terest as an encapsulant for radioactive 137Cs as well as a refractory
material, because of a high melting point and very low coefficient of
thermal expansion. A unit cell of pollucite is built of a network of 48
corner-shared SieO or AleO tetrahedra with 16 Csþ ions located in
cavities, 12-coordinated to oxygen. The cavities are formed since
the tetrahedra are linked to form 4-, 6-, and 8-membered rings. The
8-membered rings create elongated cages that permit large cations
(Csþ and Rbþ) to pass through 6-membered rings. It is assumed that
only minor atomic rearrangements in geopolymer structure are
required for its transformation into crystalline pollucite due to the
similarities in short and medium range order between these two
phases (Bell et al., 2008). Ofer-Rozovsky et al. (2016) activated
metakaolin with the solution of NaOH and CsOH at 40
C and
observed the formation of Cs analogue of a zeolite F (CsAlSiO4$H2O)
in the case of 50%-substitution of Na by Cs in an activation solution.
At lower Cs content (7%) also zeolite A and zeolite X were detected,
while at the lowest (1%) only zeolite A and zeolite X. Zeolite F (EDI
framework) has a relatively open structure. The EDI structure has
two sets of channels, which are comprised of bent 8-membered
rings. The minimal distance between oxygen atoms is large
enough for the inclusion of hydrated Cs or Na cations. Shiota et al.
(2017a) prepared geopolymers based on municipal solid waste
incineration (MSWI) fly ash and dehydrated pyrophyllite (a 2:1
layer aluminosilicate [Al2[Si4O10](OH)2] with repeating layers of an
[AlO6] sheet between two [SiO4] sheets). Faujasite and sodalite
 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
were found in this material also in the presence of radioactive ce-
sium (0.1% CsCl). At high CsCl addition (40%) sodalite and albite
formed, and in this case also pollucite crystallized. Faujasite and
sodalite (Na8Al6Si6O24Cl2) were also identified in the same MSWI
fly ash-dehydrated pyrophyllite system geopolymer aimed to
immobilize Pb (Shiota et al., 2017b).
2.3. Hydrothermal treatment of geopolymers
When geopolymerization is conducted at room temperature
and under atmospheric pressure, water/solid ratio is often insuffi-
cient for achieving the crystallization conditions, so geopolymers
are maintained in a metastable state. However, when a hydro-
thermal treatment (HT) is applied, the geopolymer transforms into
zeolite crystals more readily (Yan et al., 2012). This process pro-
motes the depolymerization of SieAl radical ions as well as en-
hances the formation of zeolite grains and supports the growth of
crystals in geopolymer matrix (Liu et al., 2016a). It is usually carried
out in a Teflon-lined hydrothermal reactor (autoclave). The syn-
thesis of geopolymer-supported zeolites follows a typical two-step
procedure: (1) synthesis of bulk geopolymers, and (2) nano-
structural conversion of the part of geopolymeric gel into zeolites
under hydrothermal conditions (Khalid et al., 2018). In a one-step
procedure, in turn, geopolymeric slurries are immediately put un-
der hydrothermal conditions for direct nucleation of some alumi-
nosilicate oligomers into zeolites, while the rest of oligomers
polymerize into amorphous geopolymeric gel. Then, some of the
geopolymeric gel may transform to zeolites at a later stage of hy-
drothermal treatment as well (Khalid et al., 2018). A schematic
diagram of these procedures is presented in Fig. 5. This section
summarizes different approaches made to obtain zeolitic phases
via hydrothermal treatment of geopolymers.
Qiu et al. (2014) synthesized fly ash-based geopolymers (curing
at 90
C for 24 h) and treated them hydrothermally (80e110
C for
6e48 h) in order to obtain blocks with zeolite NaeP1. Zeolite
formed regardless SiO2/Al2O3 ratio (1.0e2.2) of geopolymers, but
with the best crystallinity at 1.4. Zeolite NaeP1 was obtained even if
deionized water was used as a reaction solution during HT, but
NaOH solution (1.0, 2.0, 2.5 M) gave greater amounts of a zeolitic
phase. At the highest alkalinity of the solution (3.0, 4.0 M) also
hydroxysodalite was present in the samples. The optimal temper-
ature of hydrothermal treatment was 100
C, while time 24 h. Liu
et al. (2016a) obtained a faujasite block from a fly ash-based geo-
polymer as well. The geopolymeric slurry was molded and cured in
air for 12 h and in 80
C for another 12 h. The obtained samples
were hydrothermally treated (60e100
C, 1e24 h) with water or
NaOH solution. The optimal conditions were: 70
C, 24 h, 1 M NaOH
solution, which gave a compressive strength of 5 MPa. It was also
Fig. 5. Schematic diagram of geopolymer-zeolites composites preparation process via hydrothermal treatment.
567
shown that, in these conditions, the increasing SiO2/Al2O3 molar
ratio of geopolymer caused a gradual increase in the intensity of
diffraction peaks corresponding to faujasite. At 100
C it was
possible to obtain FAU-type as well as NaeP1 zeolite phases. Lee
et al. (2016a), in turn, investigated fly ash/blast furnace slag mes-
oporous geopolymer-zeolite materials. Geopolymeric pastes were
cured at 80
C for 24 h, and then hydrothermally treated at 90
C
also for 24 h. The presence of zeolite NaeP1 and hydroxysodalite
was observed in the samples with and without slag, while faujasite
and chabazite only in the sample without slag. The compressive
strength was substantially improved by the addition of slag (from
2 MPa for the sample without slag to 15 MPa for the sample with
40% of slag). Alkali-activated hydroceramics based on slag-
metakaolin-fly ash systems for waste immobilization were pre-
pared by Wang et al. (2016). The materials were prepared by acti-
vation of aluminosilicate precursors blends, precured at room
temperature and hydrothermally treated (150e210
C for 12e60 h).
Zeolite NaeP1 was a dominant phase in the samples treated below
180
C but analcime was also present. From 180 to 210
C the
diffraction peaks of analcime became stronger, while those of
zeolite NaeP1 weaker till to complete disappearance at 210
C. The
treatment time was also an important factor e the longer the time,
the greater the amount of analcime and smaller of zeolite NaeP1.
De Rossi et al. (2018) prepared geopolymers based on biomass fly
ash (75 wt%) and metakaolin (25 wt%) and cured them at RT for
24 h. Then, the samples were cured in hydrothermal conditions in
hermetic glass container for 3, 7 and 28 days at 60
C. Such a
treatment caused the formation of zeolite NaeP1 and faujasite
regardless the curing time, however, the higher time of the treat-
ment (28 days) enhanced their formation. Tang et al. (2016) syn-
thesized zeolite ZSM-20 in two-part procedure, i.e. the synthesis of
metakaolin-based geopolymer (Si/Al ¼ 2.0, activation with sodium
silicate solution with modulus of 1.1, H2O/Na2O molar ratio of 7.5,
curing at 40
C for 3 days), and its hydrothermal treatment (140
C,
10 h). ZSM-20 zeolite resembles faujasite in certain structural as-
pects, but it has a higher Si/Al ratio. The hexagonal ring remains
stable in low-alkalinity media, so the synthesis of ZSM-20 should
be conducted under appropriate conditions. Different conditions
allowed to obtain other zeolites such as analcime, faujasite, zeolite
NaeP1, and hydroxysodalite. Kolousek et al. (2007) applied hy-
drothermal conditions (100 or 140
C for 1e7 days) for metakaolin-
based geopolymers. Such treatment enhanced the reactivity of
quartz, and caused the formation of chabazite and phillipsite in
short-term period (1e4 days) or analcime and hydroxysodalite in
long-term period (7 days, 140
C). Geopolymers synthesized from
Al2O3eSiO2 powders fabricated via sol-gel method, which allowed
to obtain geopolymers with low Si/Al ratio and to overcome the
disadvantages related to the use of impure raw materials, were,
568 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579

after curing at 60
C for 24 h, treated hydrothermally in Teflon
bottles with water at 90
C for 6 h, which caused the formation of
faujasite (at SiO2/Al2O3 ratio of 3) and zeolite A (at SiO2/Al2O3 ratio
of 2) (Yan et al., 2012; Xuemin et al., 2011). Ge et al. (2014) applied
the geopolymer-gels-conversion method to obtain large-sized
analcime. The chemosynthetic geopolymers were prepared as
described above, cured at 70
C for 72 h, and hydrothermally
treated at 240
C for 6 h. It was shown that the grain size of anal-
cime can exceed 1 mm when the time of hydrothermal treatment
exceeded 48 h at 240
C.
Zhang et al. (2014) prepared a self-supporting zeolite X mem-
brane in a form of a thick film (10 mm thickness). The geopolymer
slurry was cured at 60
C for 24 h, then solidified geopolymers were
treated hydrothermally at 90
C for 9e15 h. It was shown that by
extending the hydrothermal treatment time, the relative crystal-
linity and surface density of the membrane can be enhanced. Blast
furnace slag was used by Azarshab et al. (2016) as a precursor
material for geopolymer-zeolite membrane synthesis. The pre-
pared geopolymeric paste (slag activated with NaOH solution) was
formed into discs (diameter of 25 mm, thickness of 3 mm), kept at
ambient temperature for 24 h, and then hydrothermally treated at
90
C for another 24 h. Hydrothermal treatment resulted in the
transformation of geopolymer, which was mainly amorphous with
a small amount of metaheulandite zeolite (CaAl2Si7O18$3.5H2O,
HEU framework), into a geopolymeric membrane coated with
yagawaralite zeolite (CaAl2Si6O16$4H2O, UYG framework) layers of
5 mm thickness on both sides. It was stated that metaheulandite
zeolite in hardened geopolymer gel acted as initial seeds for the
formation and growth of yugawaralite zeolite in the membrane.
Self-supported ECR-1 zeolite membrane was obtained via hydro-
thermal treatment of geopolymers based on silica fume and met-
akaolin (Zhang et al., 2019). ECR-1 zeolite is a synthetic zeolite
consisting of alternating mazzite and mordenite layers with Si/Al
molar ratio of 3.5e4.5.
It is also possible to obtain a foamed geopolymer-zeolite blocks
and spheres. The first ones were obtained via hydrothermal treat-
ment of geopolymer foams based on fly ash and fly ash with 20 wt%
substitution of granulated blast furnace slag (Zhang et al., 2016).
Zeolite NaeP1 was detected in the autoclaved samples. It was
observed that the addition of slag reduced the amount of zeolite
phase, but increased compressive strength to 20 MPa (in compar-
ison to 12 MPa for the sample without slag). Zeolite NaeP1 spheres
were prepared via hydrothermal treatment of metakaolin-based
geopolymer spheres (Tang et al., 2015). Activator (sodium silicate)
was added to metakaolin together with sodium dodecyl sulfate
(K12) in order to obtain foamed slurry, which was dosed in droplets
to polyethylene glycol (PEG-600) in water bath (70
C). The droplets
were suspended and retained a spherical shape due to the fact that
the densities of the droplets and PEG-600 were approximately
equivalent. The separation of the spheres from the PEG-600 me-
dium was facilitated by their rapid solidification. The spheres were
then cured at 60
C for 3 days. The final step was hydrothermal
treatment at 140
C for 10 h.
Khalid et al. (2018) applied hydrothermal treatment (100 and
125
C for 24 and 48 h) for the preparation of fly ash/slag
geopolymer-supported zeolites using one-step method (without
pre-curing). The major formed crystalline phase was zeolite NaeP1,
while Na-chabazite, analcime and hydroxysodalite were present as
minor phases in the samples containing 80 wt% of FA and 20 wt% of
BFS. The increase in the content of slag (to 60 wt%) caused a sig-
nificant decrease in the intensity of zeolite NaeP1 peaks, and
hydroxysodalite became a major phase. This was related to the
presence of Ca in slag, which has a tendency to hamper the for-
mation of zeolites. Ca also contributes to the creation of C-A-S-H
gel, which is why this sample achieved the highest compressive
strength (ca. 25 MPa). The specimens with 20 wt% of BFS had a
slightly lower strength, i.e. between 15 and 20 MPa. Wang et al.
(2018) presented one-step geopolymer-gels-conversion of pre-
shaped (by curing in oven for 30 min) metakaolin-based geo-
polymer gel in hydrothermal conditions. This allowed to obtain
zeolite X monoliths with relatively high compressive strength. The
authors studied the synthesis parameters such as Na2O/SiO2 molar
ratio, H2O/Na2O molar ratio, hydrothermal treatment duration and
temperature, and the optimal conditions were 1.0, 70, 18 h and
90
C, respectively, giving the compressive strength of 38.5 MPa.
Some examples of zeolites obtained via hydrothermal treatment
with the properties of geopolymer-zeolite composites are sum-
marized in Table 3.

Table 3
The properties of geopolymer-zeolite composites obtained in hydrothermal conditions.

Obtained zeolites Starting Curing conditions Compressive strength BET surface area (m2/ Porosity (cm3/ Ref.
material (MPa) g) g)

NaeP1 FA (1) 60
C, 24 h 23.21 50.46 0.092 Qiu et al. (2014)

(2) HT 100
C, 24 h, 2 M
NaOH
Faujasite FA (1) RT, 12 h 5.14 174.35 0.14 (Liu et al., 2016a,
(2) 80
C, 12 h 2016b)
(3) HT 70
C, 24 h, 1 M NaOH
NaeP1 FA, BFS (1) 80
C, 24 h 16.57 114.16 0.27 Lee et al. (2016a)
(2) HT 90
C, 24 h
Faujasite, NaeP1 Biomass FA, MK (1) RT, 24 h 9.78 56.35 e De Rossi et al. (2018)
(2) HT 60
C, 28 d
ZSM-20 MK (1) 40
C, 3 d e 78.52 0.23 Tang et al. (2016)
(2) HT 140
C, 10 h, water
Zeolite X MK (1) 60
C, 24 h 19.6 63.31 0.229 Zhang et al. (2014)
(2) HT 90
C, 15 h, water
ECR-1 MK, FS (1) 50
C, 24 h e 84.26 0.019 Zhang et al. (2019)
(2) HT 180
C, 24 h, water
NaeP1 MK (1) 60
C, 3 d e 42.08 e Tang et al. (2015)
(2) HT 140
C, 10 h
NaeP1, chabazite and FA, BFS (1) HT 100
C, 48 h 15.3 76.6 0.24 Khalid et al. (2018)
analcime
Zeolite X MK (1) oven, 30 min 38.46 482 0.25 Wang et al. (2018)
(2) HT 90
C, 18 h
 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
2.4. Mechanism of zeolites formation in geopolymers
Geopolymers structure is very similar to zeolite ones and thus
both materials are formed in a similar manner (Kro l et al., 2018; van
Jaarsveld et al., 1997). Most authors agree that it involves a three
step model of dissolution, orientation and hardening (Provis et al.,
2005; van Jaarsveld et al., 1997). Some authors claim (Pacheco-
Torgal et al., 2008) that the exact reaction mechanism of alkali-
activated binders is not yet quite understood, although it depends
on both the type of starting materials and alkaline activator.
Generally, it can be stated that CeSeH phase is the main reaction
product in the CaOeSiO2 system, while zeolite like polymers are
formed in the Al2O3eSiO2 system. Although the mechanism of
zeolite formation in geopolymers is not yet fully understood, some
models have been presented so far.
Crucial aspect in the crystallization of zeolites is water excess.
Brough et al. (1994) detected high amounts of tobermorite,
hydroxysodalite and zeolite NaeP1 in the Na2OeAl2O3eSiO2eH2O
and Na2OeCaOeAl2O3eSiO2eH2O systems characterized by high
water/binder ratio. Rodríguez et al. (2013b) stated that the trans-
formation of amorphous aluminosilicate gel into zeolites is also
determined by the dissolution rate of a raw material. This is
controlled by at least two processes: (1) the breakage of surface
bonds breakage due to the solvent action, and the formation of
soluble species that leave the surface of the dissolving solid and (2)
the reaction of the species on/with the surface of the dissolving
solid (Rodríguez et al., 2013b). The occurrence of solid phase
transformation mechanism presumes the development of a poly-
merized hydrogel between the silicate and aluminate phases
following the crystallization condition, including the rearrange-
ment of the aluminosilicate skeleton into a crystalline framework of
zeolites (Yan et al., 2012). Provis and van Deventer (Provis and van
Deventer, 2007a; Provis and van Deventer, 2007b) confirmed that
the initial geopolymer gel is transformed over time into a more
ordered phase.
As mentioned, the geopolymerization-crystallization mechanism
of zeolite formation involves three steps (Duan et al., 2015; van
Jaarsveld et al., 1997; Xu and Van Deventer, 2003):
1. The dissolution-hydrolysis: the release of silicate and aluminate
monomers under an alkaline attack, the hydrolysis firstly occurs
on shells of solid particles. This is essential for the solid particles
conversion into a geopolymeric gel.
2. The hydrolysis-polycondensation: Then dissolved species cross-
link to form oligomers, which then form N-A-S-H gel. This stage
includes gel generation, and simultaneous setting and hard-
ening due to polycondensation and the formation of the 3D
aluminosilicate network. The resulting geopolymer gel has a
zeolite-like structure.
3. The polymerization-crystallization: with the polymerization
progress, the three dimensional aluminosilicate networks keep
short-range ordering. During the geopolymerization water acts
as a reagent and also as a reaction byproduct e the dissolution of
substrates uses water, but the polymerization releases water (Xu
and Van Deventer, 2003).
Fernandez-Jime
nez et al. (2005) confirmed that under the in-
fluence of the alkaline solution on the fly ash as raw material, a
dissolution process occurs. Then, the molecules condense into a
geopolymer gel. The alkaline attack opens the fly ash spheres,
exposing small spheres inside them, which will be also dissolved.
With the formation of reaction products inside and outside the
sphere the amorphous phase is completely dissolved. The same
research team stated (Palomo et al., 2008) that the geo-
polymerization process may be considered as a zeolitization with
569
Fig. 6. Model of zeolite A formation mechanism from geopolymer spheres. Repro-
duced with permission from Ref. (Liu et al., 2017b). Copyright 2017 John Wiley and
Sons.
the last stage missed due to slow dissolution and condensation
reactions when the hardening take place.
Other mechanism of zeolite formation in geopolymeric spheres
has been developed as well (Liu et al., 2017b; Pacheco-Torgal et al.,
2008). During the formation of zeolites, at first a stable ordered
nanocrystal nucleus is formed in the geopolymer gel. This geo-
polymer is composed of N-A-S-H gel, dissolved aluminosilicate
particulates, free sodium ions, voids, and water. In high alkalinity
regions e where free sodium ions fill in the voids in significant
amounts e the aluminosilicate gel particles dissolve and generate
[SiO4] and [AlO4] tetrahedra. They induce polymerization and
rearrange on the surface of the particles when these two types of
tetrahedra are sufficiently concentrated close to the theoretical
composition of a zeolite forming the ordered nanocrystalline core.
With an increase in SieO and AleO polymers, the nanocrystals
gradually grow into zeolites. This depends mainly on the transport
of water molecules. They tend to diffuse to the surface of geo-
polymer spheres. The formation of a nanocrystalline core occurs
more likely in the surface of the spheres followed by gradual inside
growth. Fig. 6 shows the model of zeolite A formation mechanism
from geopolymer spheres.
3. Resistance of zeolites in the geopolymeric matrices
Geopolymers exhibit good thermal and fire resistance up to
1300
C (Provis and Van Deventer, 2009), sulfate resistance
(Bakharev, 2005b; Fernandez-Jimenez et al., 2007; Grutzeck et al.,
2002) and acid resistance (Roy, 1999). For comparison conventional
concrete shows some disadvantages such as low chemical resis-
tance to acids and salts, low thermal and fire resistance, especially
at temperatures over 500
C. These unique properties of geo-
polymers owe to structural similarity to zeolites. In addition, the
presence of zeolite phases in the geopolymeric matrix gives this
type of composites catalytic, sorption or molecular sieve properties.
Therefore, the stability of zeolite phases is important from the point
of view of the potential use of such materials in catalysis or envi-
ronmental protection.
Zeolite phases have limited resistance to acids. Bakharev
(2005c) observed the complete disappearance of zeolitic phases
(zeolite NaeP1, hydroxysodalite) in fly ash-based geopolymers
exposed to 5% acetic acid solution. The similar situation was
observed in the case of exposure to 5% sulfuric acid solution, but
570 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579

only for the geopolymer activated with NaOH. When sodium hy-
droxide was used together with potassium hydroxide as an acti-
vator, zeolite NaeP1 did not disappeared. Sturm et al. (2018)
observed the disappearance of zeolite A after the exposure of
microsilica-based geopolymer to sulfuric acid. Dissolution of sili-
cates in general includes: (1) leaching of non-framework cations,
i.e. the substitution of Naþ by H3Oþ in the case of zeolite A,
hydroxysodalite and geopolymeric gel; (2) removal of Al from the
framework by hydrolysis of SieOeAl bonds; (3) hydrolysis of
SieOeSi bonds, if such bonds are present in the structure. For
zeolite A, step (2) causes the complete destruction of the frame-
work, since each Si is bonded to four Al via SieOeAl bonds (only
Q4(4Al) silicate species occur in its structure). Gordon et al. (2014)
investigated the resistance of geopolymers exposed to carbon
capture solvents (monoethanolamine and potassium carbonate). In
the case of geopolymers based on metakaolin and granulated blast
furnace slag faujasite was detected in all the samples changing in
SiO2/Al2O3 ratio (3.0, 3.3 and 3.6), while Na-chabazite only in the
sample with the highest ratio. It was stated that the coexistence of
these zeolitic phases is possible due to the high Si/Al ratio, presence
of alkali-rich pore solution, and reduced extent of geo-
polymerization. Zeolites were not detected in samples exposed to
solvents, possibly due to the dilution (removal) of the alkaline pore
solution, which stopped zeolite growth reaction. The inhibition of
zeolite crystallization was also observed at the lowest Na2O content
(limited precursor dissolution) as well as reduced water content Fig. 7. The percentage of zeolite V (:) and faujasite (C) in NaK-geopolymer ther-
mally treated up to 1000
C. reproduced with permission from Ref. (Duxson et al.,
(steric restrictions). Brylewska et al. (2018) detected zeolite A and
2007). Copyright 2007 Elsevier.
hydroxysodalite in metakaolin-based geopolymers. The geo-
polymer sample was subjected to desilication (removal of Si from
the network with the use of NaOH) and dealumination (removal of spectra of geopolymers with and without zeolite A in the matrix are
Al with EDTA solution). The dealumination caused the destruction shown in Fig. 8b. To the vibrations of D6R rings in the framework of
of zeolite A, while hydroxysodalite remained unchanged, which zeolite X also bands at 880 and 750 cm1 were assigned (Kro l et al.,
suggests its higher stability. 2017a). The presence of hydroxysodalite is indicated by the pres-
Another factor affecting the durability of zeolites in the geo- ence of bands at 670 and 610 cme1 (Panagiotopoulou et al., 2015),
polymer matrices is temperature. The disappearance of hydrox- 725, 702, 663 cme1 (Kro l et al., 2017b), 739, 695, 661 cm1 (Rozek
_
ysodalite and zeolite NaeP1 was after the exposure of fly ash-based et al., 2018), and 753, 695, 667 cme1 (Fern andez-Jimenez et al.,
geopolymers to 800 and 1000
C (Bakharev, 2006). Faujasite and 2008), so between approximately 750 and 610 cme1. The forma-
zeolite V in NaK-geopolymer based on metakaolin were observed to tion of cancrinite can be related to the band at approx. 873 cme1,
disappear after heating to 200
C as shown in Fig. 7 (Duxson et al., which corresponds to stretching vibrations of OeCeO (Ye et al.,
2007). A significant structure transformation in geopolymers based 2014), and bands between 630 and 620 cme1 and at 515 cme1
on residue from the chlorosilane production was observed after were associated with vibrations of D6R structures in chabazite
heat treatment (Sturm et al., 2016). At 650
C all the peak intensities (Fernandez-Jime nez and Palomo, 2005).
of zeolite A decreased significantly, while the FWHM (full width at MAS NMR. The structure of zeolite A is formed by linking sodalite
half maximum) of the peaks increased, which can be attributed to cages through double four-membered rings, which present a signal
the structural breakdown. At 750
C a further phase transition was at around 89 ppm in 29Si NMR spectrum, which is associated with
observed. The presence of a new main phase, nepheline, was clearly the presence of Q4(4Al) units (each silicon tetrahedron is sur-
noticed, hydroxysodalite remained in the system, but no zeolite A. rounded by four aluminum tetrahedra), hence Si/Al ratio is equal to
1 (Fern andez-Jimenez et al., 2008). To hydroxysodalite, signals
4. Methods used to detect zeolites at 84 (Ferna ndez-Jimenez et al., 2008), 85 (Buchwald et al.,
2011; Garcia-Lodeiro et al., 2016) and 89 ppm (Granizo et al.,
XRD. The characteristic geopolymer “amorphous hump” (at 2014) were assigned. The FAU structure is formed by linking so-
approximately 28
2q) can be, at least in part, assigned to zeolite dalite cages through double six-membered rings. Faujasite can
nanocrystals less than 10 nm in size, which coexist with an amor- display up to five peaks, at 84, 88, 93, 98, and 103 ± 1 ppm,
phous gel phase (Provis et al., 2005). This crystallinity is below the which can be assigned to Si atoms surrounded by 4, 3, 2, 1, and
detection limit of XRD. When the conditions are favorable nano- 0 atoms of Al, respectively (Ferna ndez-Jime nez et al., 2008). In
crystals may transform into zeolites. The examples of diffraction other studies, to FAU structure peaks at 89 ppm (Zibouche et al.,
pattern corresponding to zeolite A is presented in Fig. 8a. 2009) and 84 (Buchwald et al., 2011) were assigned as well
FT-IR. The vibrations in the range 800e500 cm1 are believed to as 85, 89, 94, 99, and 103 ppm (Takeda et al., 2013). The
give structural information about the secondary building units peaks observed at the chemical shifts 87, 92, 97, 102,
(SBU) in zeolites (Buchwald et al., 2011). A band at around 560- and 107 ppm were attributed to zeolite NaeP1 (Takeda et al.,
550 cme1 is often assigned to zeolite A (Buchwald et al., 2011; 2013). The chlorosilane residue-based geopolymer-zeolite com-
Fernandez-Jime nez et al., 2008; Sturm et al., 2016; Zhang et al., posites were investigated by 1H, 23Na and 29Si MAS NMR to
2012; Ozer and Soyer-Uzun, 2015) since it corresponds to the vi- distinguish gel, zeolite phases and water species (Greiser et al.,
brations of double rings (D6R and D4R), also in faujasite (Buchwald 2017). The largest fraction of pore water was revealed in the a-
ndez-Jime
et al., 2011; Ferna nez et al., 2008; Liu et al., 2016a). The
 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
Fig. 8. Geopolymers with and without zeolite A formed: a) XRD patterns (A e zeolite A, S e hydroxysodalite, Q e quartz, C e calcite); b) FT-IR spectra (arrow e band corresponding
to vibrations in zeolite A).
Fig. 9. 29Si MAS NMR spectra of geopolymers (84 ppm assigned to faujasite and 85
to hydroxysodalite; B5 spectrum typical for amorphous gel). Reproduced with
permission from Ref. (Buchwald et al., 2011). Copyright 2011 Elsevier.
cages of the zeolite A and in the geopolymeric gel. Moreover, water
exists in the b-cages of the zeolites and is adsorbed at sodium ions.
Fig. 9 shows 29Si MAS NMR spectra of geopolymers.
SEM. Zeolitic phases are often not detected by SEM due to their

occurrence in form of small crystals (Alvarez-Ayuso et al., 2008) or
they present far from the perfect shape of pure zeolite (Zhang et al.,
2012). However, as can be seen in Fig. 10, when the conditions of
growth are favorable, zeolites can be observed clearly. Faujasite
exhibits octahedral crystal morphology (Fig. 10a), zeolite A forms as
cubic crystals (Fig. 10b), hydroxysodalite as lamellar wool ball-like
particles (Fig. 10c), crystals of zeolite NaeP1 has diamond-like
morphology, and analcime has icositetrahedral crystals.
5. Applications of geopolymer-zeolite composites
Geopolymer-zeolite hybrid materials are used as sorbents, both
in gaseous and aqueous systems. Zeolites are efficient adsorbents
due to their high surface area and cation exchange capacity (CEC).
They are usually synthesized under hydrothermal conditions by
alkali-activation of silica and alumina source materials. However,
571
zeolites in a form of granules or powders require porous supports
for their industrial application (Khalid et al., 2018) or they should be
transformed into specific macroshapes by pressurization, sintering,
or spray coating, which increases the complexity and cost of
manufacturing. The so-shaped materials can easily expand and
break in the acid and alkaline systems (e.g. in ventilation filtration
processes) and the generated residue can block the channels,
causing the decrease in the adsorption properties (Wang et al.,
2018). Moreover, powder adsorbents cannot be easily recovered
after use, thus a solid bulk-type adsorbents, such as geopolymer-
zeolite composites, can be a better alternative.
For instance, geopolymer-zeolite composites were utilized in
the promising low temperature capture of CO2 (Minelli et al., 2018).
Although the selectivity and capacity properties were not beyond
the state of the art for the capture of CO2 by monolithic adsorbents,
the combination of Na13X zeolite filler with a geopolymer matrix
can enhance the properties of both phases. The self-supporting
porous adsorbent monoliths with sufficient strength (3 MPa) can
overcome the drawbacks of conventional granules or packed beds
sorption systems. The geopolymer-supported zeolite X has been
also proposed as a desiccant for desiccant wheel in air conditioning
applications (Wang et al., 2018). Geopolymer with the addition of
5 A zeolite, in turn, exhibited good formaldehyde-purifying prop-
erty (Huang et al., 2012).
A proposed application of the geopolymer-zeolite composites is
a large-scale wastewater treatment. Bulk-type adsorbents can be a
substitute for traditional zeolite powder, which allows to avoid
secondary powder pollution (Liu et al., 2016a). The geopolymer-
faujasite monolith was proposed for the purification of water and
as zeolite sieves for the adsorption of heavy metals (Lee et al.,
2016a). The geopolymer-supported zeolites were applied as sor-
bents with high Pb2þ adsorption capacity (37.9 mg/g), higher than
that of other bulk-type adsorbents. It should be noted that the
microstructure of a sample (pore size and volume, surface area)
affects the adsorption capacity e heavy metal cations have to
diffuse through the geopolymeric matrix. Adsorption is not realized
only by zeolites (ion-exchange or selective sieving), but also N-A-S-
H gel contributes in adsorption, although with lower capacity
(Khalid et al., 2018).
Liu et al. (2016b) prepared faujasite blocks via hydrothermal
treatment of fly ash-based geopolymer. Geopolymer-zeolite block
had a higher Pb2þ removal efficiency than geopolymer without
zeolite, i.e. 143.3 and 118.6 mg/g, respectively (Fig. 11). Zhang et al.
572 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
Fig. 10. SEM images of zeolites formed in geopolymer matrices: a) faujasite (repro-
duced with permission from Ref. (Liu et al., 2016b). Copyright 2016 Elsevier); b) zeolite
A; c) hydroxysodalite.
Fig. 11. Pb2þ adsorption performance of fly ash (FA), fly ash-based geopolymer (GEO)
and geopolymer-supported faujasite (FAU). Reproduced with permission from Ref. (Liu
et al., 2016b). Copyright 2016 Elsevier.
(2016) treated hydrothermally geopolymer foams based on fly ash
or fly ash with blast furnace slag (20 wt% substitution). Zeolite
NaeP1 was identified in the autoclaved samples. Cation exchange
capacity (CEC) values of geopolymer-zeolite foams were measured.
CEC was substantially higher for the sample based on fly ash only
(54 vs 24 meq/100 g for the sample with slag), and was acceptable
for industrial wastewater treatment. Tang et al. (2015), in turn, used
hydrothermal treatment to obtain zeolite NaeP1 spheres from
metakaolin-based geopolymer spheres, prepared via suspension-
solidification method. Such geopolymer-zeolite spheres may be
utilized in softening water. The porous geopolymer-zeolite A
spheres were obtained in non-hydrothermal synthesis (Liu et al.,
2017b). They can be packed in column bed for continuous pro-
cesses and easily regenerated after using in the fields of adsorption
or catalysis. The utilization of geopolymer-zeolite composites in
catalysis was also suggested in the study (Brylewska et al., 2018).
Lee et al. (2017) prepared geopolymers based on fly ash and
blast furnace slag (weight ratio of 4:1). After curing at 80
C for 24 h,
they were hydrothermally treated at 90
C for 24 h. Peaks corre-
sponding to zeolite NaeP1, faujasite, chabazite and hydroxysodalite
were observed at the diffraction pattern of the final product. The
obtained mesoporous geopolymer-zeolite composite was used as
Csþ adsorbent. In the optimal conditions (a solution pH of 4, a
contact time of 24 h) the removal of Csþ was more than 90%
(adsorption capacity 15.24 mg/g). Haddad et al. (2017) applied
long-term curing of geopolymers at low temperature (40
C for 1
week, 1 month and 3 months). Moreover, solutions of CsOH in
different proportions with NaOH were used as activators in order to
assess the geopolymer ability of cesium immobilization. The ob-
tained geopolymers with 50 and 7% Cs replacement were
composed of an amorphous phase as well as Cs-bearing zeolite
being an analogue of zeolite F (framework type EDI). Zeolite A and
zeolite X were present in 7%-sample as well and were the only
zeolitic phases in the samples with 1% and 0% Cs replacement.
Leaching experiments showed that Cs is efficiently bound by zeolite
F and geopolymers can be utilized as waste forms for 137Cs. Geo-
polymers with Cs-bearing zeolites have been also described in the
studies (Bell et al., 2008; Ofer-Rozovsky et al., 2016; Shiota et al.,
2017a).
An important and promising field of geopolymer-zeolite com-
posites is their utilization as self-supporting membranes. Nowadays,
 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
membrane separation processes have found wide applications in
various fields. This separation is induced by the differences in
chemical and physical properties of the membrane and the perme-
able component. The permeation driving force can be concentration,
pressure, temperature or electrical potential gradient (Azarshab
et al., 2016). Zeolite membranes, which have been intensively
studied in recent decades, exhibit good separation properties in gas
permeation, dehydration and pervaporation processes (Xu et al.,
2017) and several advantages: (1) they do not swell like polymeric
membranes; (2) in strong alkaline or acidic systems they are more
chemically stable than polymeric membranes; (3) zeolites are more
stable at relatively high temperatures (Yan et al., 2012). The main
disadvantage of zeolite membranes is a costly and non-reproducible
synthesis process (Azarshab et al., 2016) and they are generally more
brittle than polymers (Yan et al., 2012).
Pervaporation, one of the membrane processes, is an energy-
efficient and effective technique, introduced by Kobber in 1917.
The mechanism of separation in a pervaporation process is
solution-diffusion. It is a method for conducting separations of
mixtures of liquids by partial evaporation through a membrane
(feed side). Usually, a carrier gas is used or a vacuum is created to
reduce a partial pressure in permeate side. This process has gained
increasing interest for several industrial applications and is used for
the removal of water from organics (dehydration of hydrocarbons).
As a result a high purity product can be obtained, e.g. ethanol,
isopropyl alcohol and ethylene glycol (Azarshab et al., 2016). Since
zeolites contain uniform, molecular-sized pores, zeolite mem-
branes are suitable for pervaporation (Yan et al., 2012). Zeolite
membranes can be formed as zeolite layers on microporous inor-
ganic supports (e.g. silica, alumina or stainless steel) (He et al.,
2013). These layers can be obtained by means of methods like
sol-gel, microwave and hydrothermal synthesis, which induce the
growth of zeolite crystals. In the hydrothermal method supports
seeded with zeolite precursor are kept in an autoclave at specified
temperatures (Azarshab et al., 2016). It is a highly efficient method
but defect-free membranes are hard to be obtained (Azarshab et al.,
2016; Xu et al., 2017). Because zeolite A membranes are highly
hydrophilic and selective, with pore size of 0.4 nm, they are suitable
for the removal of water from organic solutions by pervaporation
(Yan et al., 2012; Xu et al., 2017). Such membranes must have suf-
ficient mechanical strength without macroscopic defects, so self-
supported membranes in the form of geopolymer-zeolite com-
posites are promising for this application, and can be considered as
a substitute for self-supported zeolite membranes that are highly
fragile and lack strength. Self-supporting membranes are
composed of many zeolite layers (L1, L2 … …Ln in the vertical di-
rection, R1, R2 … ….Rn in the horizontal direction), including non-
zeolitic pores (He et al., 2013), as shown in Fig. 12. The number of
non-zeolitic pores is limited, and the distribution of these pores is
random, so the effect of non-zeolitic pore defects in the
geopolymer-supporting zeolite membrane could be eliminated
when the thickness of the zeolite membrane is of a certain size.
Xu et al. (2017) prepared zeolite A membrane by geopolymer-
gel-thermal-conversion (GGTC) without the need of hydrothermal
treatment. The geopolymeric gel was obtained by the alkali-
activation of chemosynthesized Al2O3eSiO2 powders and it was
coated on stainless steel supports in the process of dip-coating and
then cured at 60
C for 6 h. The geopolymer-supported zeolite A
membrane had a pervaporation effect on the desalination of NaCl
solution if it has a suitable thickness (9.4 mm with ion rejection of
99.5%) and high compressive strength (57 MPa). It can be therefore
used as a separation membrane for seawater desalination (water
flux of 3.86 kg me2$he1 at 90
C) (He et al., 2013). Yan et al. (2012)
compared the geopolymer membrane and the geopolymer-
supported zeolite A membrane. It was shown that the water flux
573
Fig. 12. Schematic of the self-supporting zeolite membrane with non-zeolitic pores.
Reproduced with permission from Ref. (He et al., 2013). Copyright 2013 Elsevier.
of the geopolymer membrane was nearly zero, while in the case of
the geopolymer-zeolite membrane the water flux was over
2 kg me2$he1 (20
C). Most of the geopolymer gel converted into
the zeolite phase after the hydrothermal process, while the rest of
the gel continued to provide strength for the membrane. The pre-
liminary separation results showed that ethanol solutions can be
significantly dehydrated by pervaporation. Also, the faujasite
membrane was found to effectively separate alcohol from water. A
self-supporting faujasite membrane was obtained via in situ hy-
drothermal treatment of a geopolymer and exhibited high strength,
good stability and efficient separation capability (water flux of
3.16 kg me2$he1 at 80
C) (Zhang et al., 2014). Yugawaralite zeolite
membrane was successfully used in the pervaporation separation
of ethanol/water mixture as well due to its low SiO2/Al2O3 ratio that
makes it hydrophilic (Azarshab et al., 2016). Also, ECR-1 zeolite
membrane was successfully used for seawater desalination (Zhang
et al., 2019). The porous geopolymer-zeolite composites based on
metakaolin and biomass fly ash were proposed not only for
membranes, but also for the adsorption of volatile organic com-
pounds and toxic metal compounds as well as CO2 capture (De
Rossi et al., 2018).
The application of geopolymer-zeolite composites as construc-
tion and building materials is not very popular, mostly due to un-
favorable mechanical properties of such materials. They may be,
however, used for heat insulating coatings, which is related to the
release of zeolitic water during heating. As such, zeolite-
geopolymer hybrid materials can be also used as building mate-
rials with the property of humidity control (Takeda et al., 2013).
Such materials can be also used as precursors for nepheline-type
ceramics manufacturing (Sturm et al., 2016). The alkali-activated
hydroceramics based on slag-metakaolin-fly ash systems were
used for waste immobilization as well and had a satisfying aqueous
stability and a low leachability (Wang et al., 2016).
6. Influence of zeolites on the properties of geopolymer-
zeolite composites
Table 4 presents the comparison of properties between geo-
polymers without zeolites and geopolymer-zeolite hybrid mate-
rials. As can be seen the presence of zeolites in some cases enhances
the compressive strength, but in some cases decreases it. The
transformation of amorphous gel into zeolites causes the reorga-
nization of local structure affecting the mechanical properties. It
574 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579

Table 4
Geopolymer without zeolites vs. geopolymer-zeolite composites e exemplary properties.

Geopolymer without zeolites Geopolymer-zeolite composite Zeolite Ref.

Compressive strength (MPa)

18.70 5.14 faujasite Liu et al. (2016a)
7.5 3.0 zeolite X, zeolite A Papa et al. (2018)
10.05 9.78 faujasite, NaeP1 De Rossi et al. (2018)
21.50 23.21 NaeP1 Qiu et al. (2014)
16.3 19.6 zeolite X Zhang et al. (2014)
21.66 32.46 zeolite X Wang et al. (2018)
49.1 57.6 zeolite A He et al. (2013)
BET surface area (m2/g)
1.07 174.35 faujasite Liu et al. (2016a)
13 211 zeolite X, zeolite A Papa et al. (2018)
40.69 56.35 faujasite, NaeP1 De Rossi et al. (2018)
0.26 50.46 NaeP1 Qiu et al. (2014)
4.18 78.52 ZSM-20 Tang et al. (2016)
0.43 63.31 zeolite X Zhang et al. (2014)
1.84 84.26 ECR-1 Zhang et al. (2019)
4.21 42.08 NaeP1 Tang et al. (2015)
0.4 482 zeolite X Wang et al. (2018)
20.48 174.35 faujasite Liu et al. (2016b)
6.57 97.81 zeolite A He et al. (2013)
Bulk density (g/cm3)
1.15 0.99 zeolite X, zeolite A Papa et al. (2018)
1.09 1.16 faujasite, NaeP1 De Rossi et al. (2018)
Apparent porosity (%)
38 47 zeolite X, zeolite A Papa et al. (2018)
44.36 50.38 faujasite, NaeP1 De Rossi et al. (2018)
Pore volume (cm3/g)
0.0024 0.14 faujasite Liu et al. (2016a)
0.302 0.470 zeolite X, zeolite A Papa et al. (2018)
0.0006 0.092 NaeP1 Qiu et al. (2014)
0.012 0.23 ZSM-20 Tang et al. (2016)
0.000386 0.229 zeolite X Zhang et al. (2014)
0.0011 0.019 ECR-1 Zhang et al. (2019)
0.001 0.25 zeolite X Wang et al. (2018)
0.070 0.14 faujasite Liu et al. (2016b)
Water absorption (%)
42.20 43.53 faujasite, NaeP1 De Rossi et al. (2018)

can be assumed that there is a certain limit of zeolite content that
can be bear by a geopolymeric matrix, after which it causes its

weakening (Alvarez-Ayuso et al., 2008). This weakening may be the
result of bonding strength. Moreover, zeolite crystalline phases may
act as a defect within the geopolymer matrix (Bortnovsky et al.,
2008). The compressive strength of geopolymers decreased also
with increasing zeolite crystallite size (Fig. 13), suggesting that
micromorphological features are also an important factor (Takeda
et al., 2013).
To some point, the presence of zeolites in the obtained materials
enhanced the compressive strength. However, a higher content of
zeolites, for instance in samples treated hydrothermally for 7 days,
decreased the compressive strength (Kolousek et al., 2007). Intense
zeolite formation reduces compressive strength due to their
microporous-crystalline structure based on 3D-cage system when
compared to the amorphous structure of geopolymer based on 3D-
network of silicate and aluminate tetrahedra (Istuque et al., 2016).
The relationship between amorphous product content and
compressive strength is presented in Fig. 14. However, in the study

Fig. 14. Comparison of amorphous reaction product content with compressive

Fig. 13. Relationship between the compressive strength and the crystallite size of strength. Reproduced with permission from Ref. (Bhagath Singh and Subramaniam,
zeolite in final materials (Takeda et al., 2013). 2016). Copyright 2016 Elsevier.
 P. Roz_ ek et al. / Journal of Cleaner Production 230 (2019) 557e579
Fig. 15. Relationship between zeolite NaeP1 content in geopolymers and BET surface
area of composites. Reproduced with permission from Ref. (Lee et al., 2016a). Copyright
2016 Elsevier.
(Takeda et al., 2013) the effect of zeolites content on the
compressive strength of a composite was not very clear. The
compressive strength of geopolymer can be increased because of
the increased crystallization contacts between zeolite and amor-

phous phase (Alvarez-Ayuso et al., 2008).
The formation of zeolites contributed to a significant increase in
BET surface area of geopolymer-zeolite composites compared to
geopolymer without zeolites in every case presented in Table 4. A
particular example of the effect zeolite NaeP1 content on BET
surface area is shown in Fig. 15. Zeolitic crystals accumulate to form
a large number of micro-pores and meso-pores, causing an increase
in BET surface area (Tang et al., 2016). For comparison BET surface
area of commercial zeolite Na-13X is 791 m2/g (Papa et al., 2018;
Minelli et al., 2018), and of commercial 13X molecular sieve
spheres is 545 m2/g with pore volume of 0.26 cm3/g (Wang et al.,
2018). The presence of zeolites in a geopolymeric matrix affects
bulk density and apparent porosity as well. Generally, the values of
porosity (%) and pore volume (cm3/g) increases in such composites
when compared to geopolymers without zeolites.
The weak adhesion of the geopolymeric coatings to the metal
substrates was related to the formation of zeolite A in metakaolin-
based geopolymer (Si/Al ratio of 1) (Temuujin et al., 2009) and
chabazite in fly ash-based geopolymer (Si/Al ratio of 1, too)
(Temuujin et al., 2010). The formation of zeolite (faujasite) was also
found to be responsible for the increase in shrinkage values of
geopolymers (Khater and Abd El Gawaad, 2016). This effect was
significantly lowered by the addition of carbon nanotubes. Zeolites
were also partly responsible for the degradation of metakaolin-
based geopolymeric foams because they are metastable compo-
nents (Delair et al., 2012).
The properties of geopolymer-zeolite composites depend on the
quantities of zeolites that formed in a matrix. These can vary
significantly and are determined by the reaction parameters. For
example fly ash/slag-based geopolymer treated hydrothermally
contained of 11.6% zeolite NaeP1 and 7.1% sodalite (Lee et al.,
2016a) or 13% zeolite NaeP1, 1% chabazite and 1% analcime
(Khalid et al., 2018), metakaolin-based geopolymers 80.6% zeolite
NaeP or 35.3% zeolite X (Takeda et al., 2013), and fly ash-based
geopolymer 30% Na-chabazite, 1.2% cancrinite and 1.8% hydrox-
ysodalite (Criado et al., 2007) (by weight).
7. Summary
The potential of geopolymer conversion to zeolite can be
exploited for the synthesis of geopolymer-zeolite composites. Such
575
hybrid bulk materials take advantage of both constituents: high
surface area, pore volume and adsorption capacity from zeolites,
and strength and support from geopolymer matrix. They can be
therefore used as bulk-type adsorbents, both in gaseous and
aqueous systems, and self-supporting membranes. There is a wide
range of research methods to study both the structure and prop-
erties of such materials. Since industrial by-products (ash, slag) can
be used for their synthesis, geopolymer-zeolite hybrid materials
exhibit some production and sustainability benefits: low cost and
efficient waste management.
This article reviews research papers published until the end of
2018. It presents an overview of the geopolymer-zeolite composites
synthesis approaches. They can be obtained in three ways: (1)
utilization of zeolites as raw materials for geopolymer synthesis;
(2) direct formation of zeolites parallel to geopolymerization; (3)
hydrothermal treatment of geopolymers. The main factors affecting
zeolite formation in geopolymeric matrix are: Si/Al ratio, the type
and content of an activator, curing conditions, the presence of ad-
ditives. Since all these issues have been discussed in this review, it
can be considered as a practical guide to geopolymer-zeolite
composites manufacturing. Some issues, however, need further
research. The application of these hybrid materials in the field of
catalysis and gas separation is very promising, but still barely
investigated.
Declarations of interest
None.
Acknowledgement
The authors acknowledges financial support from the National
Science Centre in Poland, Grant No. 2015/17/B/ST8/01200.
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