Materials Chemistry and Physics 217 (2018) 90–97

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Materials Chemistry and Physics

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Improvement of physical and mechanical properties of geopolymer through T

addition of zircon
M.F. Zawraha,∗, Rabiee S. Faragb, M.H. Kohailb
a
National Research Centre, Ceramics Department, 12622-Dokki, Cairo, Egypt
b
Al Azhar University, Faculty of Science, Chemistry Department, Nasr City, Cairo, Egypt

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• Zircon up to 10 g/100 g metakaolin

improved microstructure and me-
chanical properties.
• No new phases were formed upon the
addition of zircon.
• Zircon didn't participate in geopoly-
merization reaction.
• Zircon entered between polysialate
networks and formed a rigid micro-
structure.
• Higher content of zircon (15 g/100 g
kaolin) lowered the compressive
strength.

A R T I C LE I N FO A B S T R A C T

Keywords: To improve physical and mechanical properties of geopolymer, an attempt to incorporate zircon-ZrSiO4 with
Geopolymer aluminum silicates in the matrix was addressed. Five geoploymer pastes containing different zircon contents
Zircon were prepared from Egyptian kaolin with alkali activators. XRF, XRD, FTIR and SEM attached with EDX unit
Metakaolin were used to investigate raw materials and prepared geopolymer. Bulk density and apparent porosity were tested
Compressive strength
according to Archimedes principle. Compressive strength of prepared geopolymer was also examined. XRD re-
X-ray
IR
sults indicated that no interconnected phases were formed between added zircon and starting aluminum silicates
or alkali activators. The presence of zircon up to 10 g/100 g metakaolin, led to improving the microstructure of
prepared geopolymer. Zircon entered between the polysialate networks and formed a rigid microstructure. This
consequently returned on compressive strength. The compressive strength was increased with increasing zircon
content up to 10 g per100 g metakaolin, and then decreased with higher zircon content. The maximum obtained
compressive strength value was 74 MPa for the sample that contains 10 g zircon. Addition of higher amount of
zircon (15 g/100 g metakaolin) hinders the progress of geopolymerization reaction to take place and conse-
quently decreases the compressive strength.

1. Introduction over the world [1]. Active minerals that contain mostly silica and
alumina in amorphous or semi crystalline forms could be used as a
Geopolymer technology has been developed and accelerated in a source for production of geopolymer after addition of alkali solutions.
short time and received great deal of interest by many researchers all Kaolin is the main mineral in the earth that can be used as precursor for

∗
Corresponding author.
E-mail address: mzawrah@hotmail.com (M.F. Zawrah).

https://doi.org/10.1016/j.matchemphys.2018.06.024
Received 21 April 2018; Received in revised form 5 June 2018; Accepted 10 June 2018
Available online 19 June 2018
0254-0584/ © 2018 Elsevier B.V. All rights reserved.
M.F. Zawrah et al.
geopolymer fabrication. Kaolin is converted into active metakaolin by
calcination at about 850 °C which leads to dehydroxylation and active
aluminosilicate formation according to the following equation:
Al2Si2O5(OH)4→Al2Si2O7 + 2H2O [2–5]. The reaction of alumino-si-
licate with alkali solutions involves dissolution, diffusion and poly-
condensation processes yielding geopolymer matrix (polysialate
forming species) with empirical formula: Mn{-(SiO2)z-AlO2}n, wH2O in
which M is an alkali atom, z is 1, 2 or 3 and n is the degree of poly-
merization or polycondensation [2,3,6,7]. The nature and amounts of
starting aluminum silicates and alkali solutions effect on the extent of
dissolution and consequently on the composition as well as properties
of the fabricated geopolymer.
Depending on their properties, the addition of new type of filler
materials could improve one or more properties of geopolymer through
chemical reaction or physical changes. The additives might be organic
or inorganic materials, solid or liquid, fine or coarse powders, micro or
nano particles in different shapes and so on. The additive selection
depends on the property wanted to be improved and the final appli-
cation [8–10]. Inorganic additives can homogenate with inorganic raw
materials better than organic additives and they may be favorable for
undergoing elevated temperatures [8,9]. Many inorganic materials such
as CaO, MgO, ZnO, silica fume, silicon carbide, nano clay, nano oxides
(TiO2, Al2O3 and SiO2) and nano carbon have been used for improving
the properties of geopolymer [11–18].
Zircon mineral (ZrSiO4) is occurring in a wide variety of sedimen-
tary, igneous, and metamorphic rocks and can be used in several ap-
plications such as geochemical investigations, gemstones, source of
zirconia, electronic applications, some ceramics and refractory mate-
rials and so on [19–22]. Zircon is tetragonal crystal, its chemical
structure is ZrSiO4 and it contains some trace elements include mainly
Hf then P, Y, U, Th, and lanthanides [23,24]. This mineral is stable up
to 1690 °C at ambient pressure and its dissociation temperature was
estimated to be above 1700 °C, consequently the thermal expansion of
zircon is quite low [23,25]. Due to its chemical stability and other fa-
vorable properties it has been used for improving the mechanical and
thermal properties of refractory materials [26].
The incorporation of insoluble silicates (zircon) in geopolymer is
still unknown. So, in this research, an attempt for improving the me-
chanical properties of geopolymer pasts is addressed by adding zircon
mineral (Zirconium silicate - ZrSiO4) as inorganic additive. Up to our
knowledge, there is no published research dealt with the addition of
zircon for improving the properties of geopolymer, but a few researches
have been conducted the effect of zirconia (ZrO2) addition on geopo-
lymer properties. In previous work, zirconia has been added to fly ash
based geopolymer and the results showed an improvement in me-
chanical properties without sharing of zirconia in the geopolymeriza-
tion reaction but an additional physicochemical and interfacial reaction
of zirconia within a 3D polysialate network could be happened. Only
3% of zirconia added to fly ash geopolymer could increase the com-
pressive strength by 30%. For understanding the chemical basis of in-
creasing the compressive strength, the author hypothesized that zir-
conia promotes 3D polysialate grid structure through formation of
insoluble sodium polysialate. This 3D polysialates reduce the move-
ment of sodium while maintaining structure stability and the charge
balance of the matrix [27].
In the present work, we focused on studying the effect of zircon
addition on the properties of metakaolin base geopolymer. Zircon is
considered as an economic source as compared with the expensive
zirconia.
2. Materials and experimental procedures
2.1. Raw materials
Egyptian kaolin was supplied from El-Nasr Mining Company,
Aswan, Egypt. The kaolin was crushed and sieved under 75 μm followed
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Materials Chemistry and Physics 217 (2018) 90–97
by calcination at 850 °C for 2 hs in electric furnace to convert it into
amorphous metakaolin to increase its activity toward geopolymeriza-
tion reaction. The final mean particle size (D50) of metakaolin was
26 μm. Pure zircon with mean particle size (D50) 1.92 μm was used. A
technical grade sodium silicate was purchased from Egyptian Saudi
Company for chemical industries, Badr city, Egypt. It composed of
31.04% SiO2, 15.96% Na2O, and 53% H2O. SiO2/Na2O weight ratio is
equal to 1.94 and its density is 1.51 g/cm3 at 25 °C. Analytical grade
sodium hydroxide pellets (NaOH) with purity 99% made in India was
used for preparing NaOH solution with concentration equals 8 mol/L.
8M NaOH and sodium silicate solutions were mixed together with
1:2 vol ratio, then kept for 48 h at room temperature to ensure good
activation of the alkaline solution toward reaction.
2.2. Procedure of preparing geopolymer samples
At the beginning, zircon was mixed with metakaolin by mechanical
mixer for 3 h unless ensuring of homogeneity. Then, the alkaline solu-
tion was added to the designed mixes and mixed by mechanical mixer
to complete homogeneity of the paste. The designed compositions are
illustrated in Table 1. The pastes were molded in acrylic mold as cubes
with volume 25x25 × 25 mm3. The pastes were poured as two layers
and each layer was vibrated well. The surface of cubes was covered by
polyethylene film to decrease the water loss by evaporation. The mold
was kept at 70 °C for 10 h then cured at room temperature for 28 days.
Finally, the cubes were dried at 105 °C for 24 h to stop geopolymer-
ization reaction and perform the tests without excess water.
2.3. Characterization of raw materials and prepared geopolymer pasts
Wavelength dispersive x-ray fluorescence (WDXRF) type Bruker S4
with an Rh source and tube of 2.2 kW power was used to quantitatively
analyze metakaolin and zircon raw materials. Phase identification of
raw materials and prepared geopolymers was investigated by XRD
technique. XRD diffractometer type Siemens appliance model D5000
with Ni filter, Cu Kα radiation at a scan speed of 0.5 min−1 was used.
The structural characteristic of raw materials and geopolymers was
examined by FT-IR spectra type JASCO FT/IR-6100. IR spectra were
recorded in the range 400–4000 cm−1 with a resolution of 4 cm−1 at
room temperature. Microstructure of raw materials and geopolymer
was investigated by scanning electron microscope model Quanta 250
FEG (Field Emission Gun) with accelerating voltage 30 kV, attached
with Energy Dispersive X-ray Analysis (EDAX) unit. Bulk density of
geopolymer aged for 28 days was determined by Archimedes methods,
while as compressive strength was measured by automatic hydraulic
testing machine type SHIMADZU with a maximum capacity of 1000 kN
by rate of 0.025 kN/mm2/s.
3. Results and discussion
3.1. Characteristics of raw materials
Quantitative chemical analyses of metakaolin, zircon and sodium
silicate are illustrated in Table 2. From the analyses, it is indicated that
the main constituents of metakaolin are alumina (39.45%), silica
Table 1
Mixing design of the geopolymer pastes.
Sample Metakaolin, g Zircon, g Alkaline solution, Si/Al Si/Na ZrO2, g
g
Zr0 100 0 42 2.80 9.32 0.00
Zr2 100 2 42 2.83 9.41 1.23
Zr5 100 5 42 2.87 9.56 3.06
Zr10 100 10 43 2.94 9.80 6.13
Zr15 100 15 43 3.01 10.04 9.19
M.F. Zawrah et al. Materials Chemistry and Physics 217 (2018) 90–97

Table 2
Chemical composition of raw materials.
Oxides Content Wight (%)

Metakaolin Zircon Na2SiO3.nH2O

ZrO2 – 61.3 –
SiO2 55.71 33.82 31.04
Al2O3 39.45 0.89 –
TiO2 3.16 0.38 –
Fe2O3 0.65 0.18 –
MgO 0.01 0.05 –
CaO 0.35 0.2 –
Na2O 0.01 – 15.96
K2O 0.01 – –
P2O5 0.09 0.2 –
SO3 0.06 – –
H2O – – 53
HfO2 – 1.95 –
Y2O3 – 0.14 –
LOIa 0.17 0.84 –

Total 99.68 99.95 100 Fig. 2. FT-IR metakaolin and zircon.

a
LOI = loss on ignition at 1000 °C.

(55.71%) and titania (3.16%) with trace amounts of other oxides. On

the other hand, zircon is composed of zirconia (61.3%) and silica
(33.82%) with small amount of other oxides; whileas sodium silicate
contains 31.04% SiO2, 15.96% Na2O and 53% H2O. This means that the
molar ratio of SiO2/Al2O3 in metakaolin is 2.40 and the molar ratios of
SiO2/Na2O and H2O/Na2O in alkaline solutions are 1.33 and 12.26,
respectively. From these ratios, SiO2/Al2O3 and Na2O/Al2O3 ratios in
geopolymer pastes could be calculated (Table 1). For the paste con-
taining zero zircon, the molar ratios of SiO2/Al2O3 and Na2O/Al2O3 are
2.80 and 0.3 respectively; but for the pastes containing 2, 5, 10 and Fig. 3. SEM images of raw materials (a) metakaolin and (b) zircon.
15% zircon, the molar ratios of SiO2/Al2O3 are 2.83, 2.87, 2.94 and
3.01, respectively.
pattern. On the other hand, the pattern of zircon exhibits all main peaks
Fig. 1 shows XRD patterns of metakaolin and zircon raw materials.
of zircon phase at 2θ≈27°, 20°, 35.5°, 53.5° and 43.7° [19]. XRD pat-
The pattern of metakaolin exhibits a characteristic broad reflection
terns confirm the results of XRF analysis and reflect the quality of raw
hump between 2θ = 20°–30° which is assigned to amorphous phase
materials.
[28]. Also, characteristic peaks of quartz phase at 2θ = 26.7° and 21°
FTIR spectra of raw materials recorded between 400 and 4000 cm−1
are detected in the pattern of metakaolin. Furthermore, small peak at
are shown in Fig. 2. Three bands at wave number 850, 607 and
2θ = 12.3° which may refer to uncalcined kaolin, is appeared in the
430 cm−1 are appeared in IR spectrum of zircon. Bands at 850 and
607 cm−1 band are assigned to Si-O-Zr stretching mode and Zr-O bond,
respectively [29], while the band at 430 is assigned to Si-O bending
bond. The bands appeared in the metakaolin spectrum are 1065, 776,
630 and 434 cm−1. The broad band at 1065 cm−1 is assigned for
asymmetric stretching vibration of Si-O bond produced by disorder
induced by dehydroxylation process of kaolin and formation of amor-
phous structures. The small band at 776 cm−1 is ascribed to the vi-
bration of tetrahedral unit containing Al-O bond. The band at 434 is
attributed to bending of Si-O bond [30,31].
Fig. 3 depicts SEM images of metakaolin and zircon raw materials.
This microstructure is important as a reference to be comparable with
the microstructure of prepared geopolymers. The size of zircon particle
is about 1–3 μm and of metakaolin is in the range between15-150 μm.
This confirms the original particles size as supplied raw materials as
indicated in the experimental section. Metakaolin grains appear as
aggregate with defined edges while zircon grains as fine tapered grains
with sharp edges.

3.2. Characteristics of prepared geopolymers

3.2.1. Bulk density and apparent porosity

Fig. 4 shows bulk density and apparent porosity of prepared geo-
Fig. 1. XRD patterns of metakaolin and zircon. polymers aged for 28 days at room temperature. It appears that the

92
M.F. Zawrah et al.
Fig. 4. Bulk density and apparent porosity of the prepared geopolymers.
density increases with increasing the amount of added zircon. The ob-
tained density values are ranged between 1.72 and 1.81 g/cm3. The
density of geopolymer is an important factor which is considered as the
reflection of geopolymer composition, polymerization process and
porosity. Zircon has higher density (4.65 g/cm3) than metakaolin
(2.62 g/cm3) and geopolymer itself, so its addition leads to increasing
the bulk density [32]. Also, as indicated from SEM images of meta-
kaolin and zircon (Fig. 3), zircon has particle size about 1–3 μm which
is lower than that of metakaolin (15–150 μm). These fine particles of
zircon lead to increasing the packing of formed geopolymer and con-
sequently increase the density and decrease porosity. The obtained
trend of porosity is opposite to that of density. The obtained porosity
range is 27.83–26.58%. Moreover, zircon might have an effective role
in packing of polysialate structure produced from polymerization of
metakaolin with alkali solution and forming a rigid network which
tends to increase the density and lower the porosity.
3.2.2. Phase composition of geopolymer
The amorphous state of aluminum silicates makes the geopoly-
merization proceeds faster [33]. After polymerization, the amorphous
or crystalline phases of metakaolin raw material might be the same or
change their peak intensities in XRD patterns due to the formation of
Fig. 5. XRD patterns of the prepared geopolymers as compared with that of raw
materials.
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Materials Chemistry and Physics 217 (2018) 90–97
Fig. 6. FT-IR spectra of Zr0 and Zr10 geopolymers.
amorphous aluminosilicate gel, semi-crystalline geopolymer and un-
reacted crystalline phases. Fig. 5 shows XRD patterns of prepared
geopolymers cured for 28 days at room temperature. It appears that the
quartz phase is detected in all geopolymer specimens (2θ ≈ 26.7° and
21°) [28]. Its amount decreases in the specimens Zr0, Zr2 and Zr5; then
relatively increases in the specimens Zr10 and Zr15. The decreasing of
quartz in geopolymer having low zircon content is attributed to its
consuming in the geopolymerization reaction; but its higher amount in
Zr15 might due to the possibility of hindering the polymerization re-
action after addition of higher zircon content. On the other hand, the
peaks of zircon phase are detected only in Zr5, Zr10 and Zr15 speci-
mens (2θ≈27° then 20°, 36° and 53°). Its amount increases with the
quantity of added zircon mineral.
3.2.3. FTIR analysis of geopolymer
FTIR spectra of prepared Zr0 and Zr10 geopolymers aged for 28
days at room temperature are shown in Fig. 6. The broad band at about
3455 cm−1 is attributed to the stretching vibration of O-H bond while
that at 1630 cm−1 is assigned to bending vibration of O-H which might
be produced from alkali [5]. Due to the reaction between alumino-si-
licates and alkaline solutions, the spectra exhibit fingerprint band of
geopolymer matrix at about 990 cm−1 [31,34], i.e. the formation of
broad asymmetric T-O-Si (T = Al or Si) band for three-dimensional
geopolymer network of sodium aluminium silicate hydrate gel (N-A-S-H
gel). In both samples, the small band at 880 cm−1 is probable due to the
symmetric stretching vibration of CO2 produced from atmospheric CO2
reacted with alkalis. Also, the bands at about 684–688 cm−1 are due to
symmetric stretching vibration of Si-O-Si. There is a small band ap-
peared at 609 cm−1 in the sample Zr10 which assigns to the vibration of
Zr-O unit as appeared in the zircon spectrum [29]. No peaks assignment
is detected for Al-O-Zr or Si-O-Zr stretching modes.
3.2.4. Microstructure of prepared geopolymers
Figs. 7–9 show SEM images and EDX analyses of prepared Zr0, Zr2,
Zr5 and Zr10 geopolymers. Generally, all images of geopolymers ex-
hibit amorphous geopolymer gel in the presence of a few unreacted
metakaolin particles with some hollow spheres which produced from
the evaporation of water during curing process (aging time). These
spheres are partially disbanded and form pores in the matrix. Also,
these spheres can bring some unreacted grains in their hollow cavities.
The geopolymerization is usually started from the surfaces of particles.
Faster polymerization process might cause covering of unreacted grains
by formed geopolymer gel and consequently might prevent complete
geopolymerization for some of starting particles. Also, less reactivity of
starting materials (not amorphous) or lower amount of alkali activator
increases the amount of unreacted grains and lower the geopolymer-
ization. Slight amount of unreacted grains is detected in the micro-
structure. The amorphous fraction of starting materials determines the
quantity of dissolved SiO2 and Al2O3 and consequently the amount of
M.F. Zawrah et al. Materials Chemistry and Physics 217 (2018) 90–97

Fig. 7. SEM images and EDAX analysis of Zr0 geopolymer.

Fig. 8. SEM images (different magnifications) and EDAX analysis of Zr10

geoploymer.

94
M.F. Zawrah et al.
Fig. 9. SEM images Zr2 (a, b and c) and Zr5 (d, e and f) geopolymers.
formed geopolymer gel. The added zircon appears as white fine grains
embedded in the matrix or contacted with other grains. Its amount
increases as we going from Zr0 to Zr10. So, denser microstructure is
obtained for the sample containing higher amount of zircon (Zr10-
Fig. 8). The suitable particle size of starting materials is also an im-
portant factor for geopolymer formation and dense microstructure ob-
taining. Its EDAX analysis indicates the presence of zirconium in ad-
dition to silica and alumina as compared with that of Zr0 which exhibits
only silica and alumina (Fig. 8c). It is worth to mention that the amount
of needed activated liquid (water containing alkali activator) to get
suitable workability was higher for the samples containing zircon
(Table 1). As a consequence, the formed geopolymer has relatively
higher shrinkage with consequent reduced interface adhesion between
initial raw grains. This leads to increasing the possibility of geopoly-
merization and the compactness of microstructure. The microstructures
of the specimens Zr2 and Zr5 (are relatively similar and exhibit lower
compact microstructure with relatively higher porosity. Some cracks
are appeared in Zr5, it is expected that this is due the breaking of cube
95
Materials Chemistry and Physics 217 (2018) 90–97
sample during the test of compressive strength. The obtained micro-
structure is reflected on the mechanical properties of the prepared
geopolymer.
3.2.5. Compressive strength of geopolymer
As a concept, geopolymer is 3D network of polysialate species
produced through the reaction of aluminum silicates with alkali solu-
tions. For ensuring complete geopolymerization, the compressive
strength test was performed after 28 days curing age at room tem-
perature. Generally, in composite materials, the reinforcement phase is
responsible for improving the mechanical properties of composites
[35–47]. Similar concept could arise in geopolymer incorporated by
filler materials beside the possibility of physicochemical interaction of
filler with the formed geopolymer. Fig. 10 shows compressive strength
of prepared geopolymer as a function of added zircon percent. The
compressive strength increases with increasing zircon content up to
10 g/100 g metakaolin then decreases with 15 g/100 g metakaolin. The
geopolymer specimen without zircon exhibits 60MPa compressive
M.F. Zawrah et al.
Fig. 10. Compressive strength of the prepared geopolymers.
strength while the specimens containing 10 and 15 g zircon exhibit 74
and 61MPa, respectively. As indicated by XRD results, no new phases
are formed due to the chemical interaction between the added zircon
and geopolymer species. This means that the zircon is interacted only
physically with matrix of geopolymer. It acts as filler which can pre-
cipitate and enter between the formed 3D network polysialate struc-
tures leading to increasing the compaction of microstructure and rigid
the product. Also, this might higher the binding of geopolymer gel with
other solid phases in the matrix. Moreover, the adsorption of sodium
silicate on the surface of zircon is possible that can help in improving
the mechanical properties [48]. Addition of higher amount of zircon
(15 g/100 g metakaolin) hinders the progress of geopolymerization re-
action to take place as indicated for the specimen (Zr15) that contains
15 g zircon which exhibit 61MPa compressive strength. This means that
the limit amount of zircon to give high strength is 10 g/100 g meta-
kaolin after which the added zircon retards the reaction between alu-
minum silicate and alkali activator to form geopolymer.
4. Conclusion
It is concluded that the addition of zircon (ZrSiO4), as insoluble
silicate, improved the mechanical properties of metakaolin-based geo-
polymer. No new phases were formed upon the addition of zircon. This
means that the zircon didn't participate in the geopolymerization re-
action but it acted as filler that entered between the polysialate net-
works and formed a rigid microstructure which consequently increase
the compressive strength. The compressive strength increased with in-
creasing zircon content up to 10 g per 100 g metakaolin, and then de-
creased with higher zircon content (15 g per100 g metakaolin). The
maximum obtained value was 74 MPa. The higher content of zircon
hindered the geopolymerization process and lowered the compressive
strength.
Acknowledgement
The authors are appreciating the support and fund of academy of
scientific research and technology for the student M.Hasan Kohail
under scientists for next generation program.
References
[1] V.P. Anirudhan, A. Unnithan, Review on Development of Geopolymer Composites
from Aluminosilicate Materials vol. 4, (2016), pp. 2014–2017 no. 3.
[2] J. Davidovits, Geopolymers - inorganic polymeric new materials, J. Therm. Anal. 37
96
Materials Chemistry and Physics 217 (2018) 90–97
(8) (1991) 1633–1656.
[3] H. Xu, J.S.J. Van Deventer, The geopolymerisation of alumino-silicate minerals, Int.
J. Miner. Process. 59 (3) (Jun. 2000) 247–266.
[4] C.Y. Heah, K. Hazlinda, Potential application of kaolin without calcine as greener
concrete: a review, Aust. J. Basic Appl. Sci 5 (7) (2011) 1026–1035.
[5] A. Palomo, M.T. Blanco-Varela, M.L. Granizo, F. Puertas, T. Vazquez,
M.W. Grutzeck, Chemical stability of cementitious materials based on metakaolin,
Cement Concr. Res. 29 (7) (1999) 997–1004.
[6] C. Li, H. Sun, L. Li, A review: the comparison between alkali-activated slag (Si +
Ca) and metakaolin (Si + Al) cements, Cement Concr. Res. 40 (9) (2010)
1341–1349.
[7] J.L. Provis, J.S.J. van Deventer, Geopolymers, Woodhead Publishing Limited, 2009.
[8] S.J. Herbert, N. Sakthieswaran, B.G. Shiny, Review on geopolymer concerte with
different additives, Int. J. Eng. Res. 1 (2) (2015) 21–31.
[9] F.U.A. Shaikh, Review of mechanical properties of short fibre reinforced geopo-
lymer composites, Construct. Build. Mater. 43 (2013) 37–49.
[10] O. Mikhailova, P. Rovnaník, Effect of polymer admixtures on metakaolin-based
geopolymer, Mater. Sci. Forum 865 (2016) 67–71.
[11] H.M. Khater, Effect of calcium on geopolymerization of aluminosilicate wastes, J.
Mater. Civ. Eng. 24 (1) (2012) 92–101.
[12] F.P. Du, S.S. Xie, F. Zhang, C.Y. Tang, L. Chen, W.C. Law, C.P. Tsui, Microstructure
and compressive properties of silicon carbide reinforced geopolymer, Compos. B
Eng. 105 (2016) 93–100.
[13] M.M. Hassaan, H.M. Khater, M.S. El-Mahllawy, A.M. El Nagar, Production of geo-
polymer composites enhanced by nano-kaolin material, J. Adv. Ceram 4 (4) (2015)
245–252.
[14] P. Duan, C. Yan, W. Luo, W. Zhou, Effects of adding nano-TiO2 on compressive
strength, drying shrinkage, carbonation and microstructure of fluidized bed fly ash
based geopolymer paste, Construct. Build. Mater. 106 (2016) 115–125.
[15] T. Phoo-ngernkham, P. Chindaprasirt, V. Sata, S. Hanjitsuwan, S. Hatanaka, The
effect of adding nano-SiO2 and nano-Al2O3 on properties of high calcium fly ash
geopolymer cured at ambient temperature, Mater. Des. 55 (2014) 58–65.
[16] M. Saafi, L. Tang, J. Fung, M. Rahman, F. Sillars, J. Liggat, X. Zhou, Graphene/fly
ash geopolymeric composites as self-sensing structural materials, Smart Mater.
Struct. 23 (6) (2014) 65006.
[17] S. Yan, P. He, D. Jia, Z. Yang, X. Duan, S. Wang, Y. Zhou, Effect of reduced graphene
oxide content on the microstructure and mechanical properties of graphene-geo-
polymer nanocomposites, Ceram. Int. 42 (1) (2016) 752–758.
[18] H.A. Abdel-Gawwad, Effect of reactive magnesium oxide on properties of alkali-
activated slag-cement pastes, J. Mater. Civ. Eng. (2014) 37–47.
[19] R.M. Khattab, S.B. Hanna, M.F. Zawrah, L.G. Girgis, Alumina-zircon refractory
materials for lining of the basin of glass furnaces: effect of processing technique and
TiO2 addition, Ceram. Int. 41 (1) (January 2015) 1623–1629 Part B.
[20] M.F. Zawrah, Effect of zircon additions on low- and ultra-low cement alumina and
bauxite castables, Ceram. Int. 33 (2007) 751–759.
[21] M.F. Zawrah, L.G. Girges, R.M. Kattab, Development of magnesia-zircon-alumina
refractory compositions, Interceram 56 (6) (2007).
[22] M.F. Zawrah, L.G. Girges, R.M. Khattab, Refractory compositions based on mag-
nesia-zircon system, The Refractories Engineer (2005) 14–19 September issue.
[23] R.J. Finch, Structure and chemistry of zircon and zircon-group minerals, Rev.
Mineral. Geochem. 53 (1) (2003) 1–25.
[24] R.W. Hinton, B.G.J. Upton, The chemistry of zircon: variations within and between
large crystals from syenite and alkali basalt xenoliths, Geochem. Cosmochim. Acta
55 (11) (1991) 3287–3302.
[25] Y. Kanno, Thermodynamic and crystallographic discussion of the formation and
dissociation of zircon, J. Mater. Sci. 24 (7) (1989) 2415–2420.
[26] M.F. Zawrah, Effect of zircon additions on low and ultra-low cement alumina and
bauxite castables, Ceram. Int. 33 (5) (2007) 751–759.
[27] J.W. Phair, J.S.J. Van Deventer, J.D. Smith, Mechanism of polysialation in the in-
corporation of zirconia into fly ash-based geopolymers, Society 39 (8) (2000)
2925–2934.
[28] Z. Yunsheng, S. Wei, C. Qianli, C. Lin, Synthesis and heavy metal immobilization
behaviors of slag based geopolymer, J. Hazard Mater. 143 (1–2) (2007) 206–213.
[29] D.M. Pickup, G. Mountjoy, G.W. Wallidge, R.J. Newport, M.E. Smith, Structure of
(ZrO2)x(SiO2)1-x xerogels (x=0.1, 0.2, 0.3 and 0.4) from FTIR, 29Si and 17O MAS
NMR and EXAFS, Phys. Chem. Chem. Phys. 1 (10) (1999) 2527–2533.
[30] P. Rovnaník, Effect of curing temperature on the development of hard structure of
metakaolin-based geopolymer, Construct. Build. Mater. 24 (7) (2010) 1176–1183.
[31] W.K. Part, M. Ramli, C.B. Cheah, An overview on the influence of various factors on
the properties of geopolymer concrete derived from industrial byproducts, Handb.
Low Carbon Concr. 77 (2016) 263–334.
[32] R.J. Finch, J.M. Hanchar, P.W.O. Hoskin, P. Burns, Rare-earth elements in sinthetic
zircon: Part 2. A single crystal X-ray study of xenotime substitution, Am. Mineral.
86 (2001) 681–689.
[33] H. Xu, J.S.J. Van Deventer, Geopolymerisation of multiple minerals, Miner. Eng. 15
(12) (2002) 1131–1139.
[34] H. Wang, H. Li, F. Yan, Synthesis and mechanical properties of metakaolinite-based
geopolymer, Colloid. Surface A Physicochem. Eng. Aspect. 268 (1–3) (2005) 1–6.
[35] Mohammed A. Taha, Amira H. Nassar, M.F. Zawrah, Effect of milling parameters on
sinterability, mechanical and electrical properties of Cu-4 wt.% ZrO2 nanocompo-
site, Mater. Chem. Phys., Volume 181, 15 September 2016, Pages 26–32.
[36] M.F. Zawrah, H. Ahmed, N.E. El-Baly, Fabrication of Al2O3-20 Vol.% Al nano-
composite powder using high energy milling, Mater. Res. Bull. 47 (2012) 655–661.
[37] Mohammed A. Taha, Amira H. Nassar, Mahmoud F. Zawrah, Improvement of
wetability, sinterability, mechanical and electrical properties of Al2O3-Ni nano-
composites prepared by mechanical alloying, Ceram. Int. 43 (2017) 3576–3582.
M.F. Zawrah et al.
[38] M.F. Zawrah, Raghieba A. Essaway, Hamdia A. Zayed, Amira H. Abdel Fattah,
Mahmed A. Taha, Mechanical alloying, sintering and characterization of Al2O3-
20wt.-%Cu nanocomposites, Ceram. Int. 40 (2014) 31–38.
[39] M.F. Zawrah, Hamdia A. Zayed, Raghieba A. Essaway, Amira H. Abdel Fattah,
Mahmed A. Taha, Preparation by mechanical alloying, characterization and sin-
tering of Cu–20 wt.-% Al2O3 nanocomposites, Mater. Des. 46 (2013) 485–490.
[40] M.M.S. Wahsh, R.M. Khattab, M.F. Zawrah, Sintering and technological properties
of alumina/zirconia/nano TiO2 ceramic composites, Mater. Res. Bull. 48 (4) (April
2013) 1411–1414.
[41] R.M. Khattab, A. El-Rafei, M.F. Zawrah, In-situ formation of sintered cordierite-
mullite nano-micro composites by utilizing of waste silica fume, Mater. Res. Bull. 47
(9) (2012) 2662–2667.
[42] M.F. Zawrah, A.A. Elkheshen, Densification, phase composition and properties of
borosilicate glass composites containing nano-alumina and titania, J. Mater. Sci.
97
Materials Chemistry and Physics 217 (2018) 90–97
Mater. Electron. 20 (2009) 637–643.
[43] M. Awaad, M.F. Zawrah, N.M. Khalil, In situ formation of zirconia-spinel-mullite
ceramic composites, Ceram. Int. 34 (2008) 429–434.
[44] M.F. Zawrah, Synthesis and characterization of WC-Co nanocomposites by novel
chemical method, Ceram. Int. 33 (2007) 155–161.
[45] M.F. Zawrah, El Maghraby, Utilization of rice straw ash in production of advanced
porous ceramics composites, Interceram 56 (4) (2007) 250–255.
[46] M.F. Zawrah, M.H. Aly, In-situ formation of Al2O3- SiC-mullite from Al-Matrix
composites, Ceram. Int. 32 (1) (2006) 21–28.
[47] M.F. Zawrah, Khalil, Processing, sintering and properties of CaZrO3/MgO and ZrO2/
MgO composites, Interceram 55 (4) (2006) 254–257.
[48] J.W. Phair, J.S.J. Van Deventer, J.D. Smith, Interaction of sodium silicate with
zirconia and its consequences for polysialation, Colloid. Surface A Physicochem.
Eng. Aspect. 182 (1–3) (2001) 143–159.