Gado 2020

materials
Article
Alkali Activation of Waste Clay Bricks: Influence of
The Silica Modulus, SiO2/Na2O, H2O/Na2O Molar
Ratio, and Liquid/Solid Ratio
R. A. Gado 1, *, Marek Hebda 2 , Michal Łach 2 and Janusz Mikuła 2
1 Department of Refractories, Ceramic and Building Materials, National Research Center (NRC), 12311 Dokki
Cairo, Egypt
2 Institute of Materials Engineering, Faculty of Materials Engineering and Physics, Cracow University of
Technology, 31-155 Kraków, Poland; [email protected] (M.H.); [email protected] (M.Ł.);
[email protected] (J.M.)
* Correspondence: [email protected]; Tel.: +20-102-042-2388; Fax: +20-233-370-931

Received: 18 November 2019; Accepted: 23 December 2019; Published: 14 January 2020
Abstract: This study was conducted to investigate the influence of various reaction conditions, namely
the silica modulus SiO2 /Na2 O, H2 O/Na2 O molar ratio, and liquid/solid ratio on the geopolymerization
reaction of the waste fired clay bricks (Grog). The starting raw material and the generated geopolymer
specimens produced by different geopolymerization reaction conditions have been characterized
using different techniques: X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR),
scanning electron microscope (SEM) and thermal analysis. Furthermore, physico–mechanical
characterization has been carried out through the determination of bulk density, porosity, water
absorption, and compressive strength for each sample at interval curing times of up to 28 days. The
results indicated that the geopolymerization system of the waste fired clay bricks is influenced by the
investigated reaction conditions at room temperature. The compressive strength of the geopolymer
sample produced at optimum conditions increased significantly by up to 37.5 MPa, in comparison
with 4.5 MPa for other conditions. Finally, an optimum recommendation and useful conclusions
concerning the recycling and utilization of this waste material through the geopolymerization process
are made for compatibility with construction applications.
Keywords: geopolymer; waste fired clay bricks (Grog); silica modulus (Ms); H2 O/Na2 O molar ratio;
liquid/solid ratio; geopolymerization rate
1. Introduction
Waste fired clay bricks (Grog) are classified as a waste material generated by the clay bricks
manufacture process and are accumulated in large amounts. Annual production of this industrial
by-product makes up approximately 5 wt.% of the total mass production of clay bricks. Hence, this
waste material causes many critical environmental problems due to its disposal over a large landfill
area as well as contamination of the surrounding region. In addition, Grog is classified chemically as
an alumina-silicate material that is related to its original formation as a result of the mixing process
of sand and raw clay (a mixture of different clay minerals) during the production of clay bricks in a
factory [1,2].
Geopolymer materials are considered to be a class of inorganic polymer materials consisting
mainly of an amorphous phase composed of a silicon or aluminum atom linked to four oxygen atoms
by covalent bonds [3]. A three-dimensional network microstructure product was generated upon
alkaline activation of an aluminosilicate source material at an ambient or higher temperature through
an alkaline activation reaction called geopolymerization. An alkaline media solution is most often
Materials 2020, 13, 383; doi:10.3390/ma13020383 www.mdpi.com/journal/materials

Materials 2020, 13, 383 2 of 26
used with a mixture of liquid sodium silicate (Na2 SiO3 ) and sodium hydroxide (NaOH) at different
molar ratios. Many previous studies [4–8] showed that a geopolymer matrix can be produced using
geopolymerization involving many different raw silico-aluminates and alumino-silicates materials,
as well as industrial by-product or waste materials essentially composed of alumina silicate source
materials. Generally, geopolymers are attractive materials for this process due to their superior
physico–mechanical properties and ability to achieve high durability, thermal stability, and acid
resistance in comparison with traditional and conventional cementitious based materials. Schmucker
and MacKenzie [9] showed that the composition of geopolymers is practically unchanged during firing
to a high temperature of 1200 ◦ C. Furthermore, due to a notably lower calcium content, a geopolymer
matrix is much more acid resistant than a cement-based binder material [10].
The basic geopolymerization process generally involves three reaction steps: the dissolution of the
starting alumina silicate material at high pH; dissolved species hydrolysis; and condensation between
tetrahedral (AlO4 ) and (SiO4 ) units of the gel phase, which is typically the “X-ray amorphous phase”.
Furthermore, alkali hydroxide is required for the dissolution step of alumino-silicates material while a
sodium silicate solution acts as a binder agent, alkali activator, and a dispersant or a plasticizer medium.
The properties of geopolymer products are significantly affected by the specific surface area and
chemical composition of the initial raw materials and the relative amount of alkali activator solution
used during the initial period of the geopolymerization process [11]. Moreover, the liquid-to-solid
(L/S) ratio and the ratio of Na2 SiO3 -to-NaOH have a significant effect on the compressive strength
of the final geopolymer product, as well as influencing the workability of the geopolymer paste or
slurry [12]. Meanwhile, some studies have been carried out to establish the effect of water content on
the geopolymerization reaction using different base materials. The water content has been reported
to play an active part in enhancing the dissolution process of Al-Si species, not by taking part in the
polymerization reaction but by being released during the polymerization reaction of the alkali-activated
product. The geopolymerization process rate is influenced by different reaction parameters such as
alkali concentration, water content, curing temperature, liquid/solid ratio, Si/Al ratio, pH, and the type
of activators used, which are also important factors in developing the physico–mechanical properties
of any geopolymer product. Furthermore, the compressive strength of any geopolymer matrix is a
common indicator of the success of any geopolymerization process [13].
Generally, fresh geopolymer paste prepared with a high liquid/solid ratio has a low viscosity
system, while geopolymer paste with a low liquid/solid ratio results in a high viscosity system and
consequently, also affects its workability [11]. Moreover, the variation in the liquid/solid ratio of any
geopolymer system will have a direct influence on the dissolution rate of the starting material, which
significantly accelerates or retards the formation of binder and the geopolymerization rate [14]. On the
other hand, different ratios of sodium silicate to sodium hydroxide mainly affect the pH conditions
of the prepared alkaline solution and thus could have some effects on the properties of the resulting
geopolymer product. In addition, it is well-known that variation of the silica modulus Ms = SiO2 /Na2 O
molar ratio significantly modifies the degree of polymerization of the dissolved species in a silicate
solution, which plays a significant part in determining the structure and properties of geopolymers [15].
Grog is an alumino-silicate by-product waste material, and its recycling has significant impacts on
the environmental and industrial sectors. In general, there is a variation in the chemical composition of
grog for each region based on the raw material mineralogy used, but the majority of the composition is
still an alumino-silicate by-product. Recycling this material for the production of geopolymer products is
worthy of environmental consideration [16]. In the previous study, Grog-based geopolymers have been
produced and synthesized with the different inclusion ratio of another industrial by-product known as
granulated blast-furnace slag, which is classified as a high alkali-activation material [2]. Therefore, the
aim of this study was to investigate the influence of key parameters on the geopolymerization reaction
of the Grog itself without the mixing or inclusion of other alkali-activation materials. In this analysis, the
parameters are the silica modulus SiO2 /Na2 O, H2 O/Na2 O molar ratio, and liquid/solid ratio. Moreover,
the chemical and microstructural properties of synthesized geopolymer specimens were investigated
Materials 2020, 13, 383 3 of 26
with respect to their physico–mechanical properties, phase composition, and microstructure. The
results obtained from this study will contribute to the development and improvement of optimum
geopolymerization condition parameters for this type of waste material. Moreover, the aim was to
provide a potential replacement of traditional cementitious binders by using an alternative binder
material based on a safe recycling process, which has practical implications and advantages in the
environmental sector.
2. Experimental and Methodology
2.1. Starting Materials

The starting material used for the geopolymer synthesis process was an industrial by-product which
is well known as Grog. The material was provided by an Egyptian clay bricks manufacture (Misr-Brick
Company, Helwan, Giza, Egypt). The Grog was ground in a ball mill (Fritsch planetary-Pulverisette
6, FRITSCH GmbH, Idar-Oberstein, Germany) for one hour to obtain a powder with small particle
sizes. X-ray fluorescence (XRF, Malvern Panalytical B.V., Almelo, Netherlands) was used to determine
the chemical oxide compositions of the starting material. In addition, the crystalline mineral phases
were identified by X-ray diffraction technique using a Panalytical X’pert Pro (Malvern Panalytical Ltd.,
Malvern, UK) diffractometer with a Ni filter, as well as Cu Kα radiation with a wavelength of 1.5406 Å,
at a scan speed of 0.5 min−1 , operated at 40 kV, 40 mA, and a 2 theta range of 4–70◦ . In addition, the
infrared spectrum (FTIR) was recorded in the wavelength range of 400–4000 cm−1 by using a JASCO
FT/IR-6100 (FRITSCH GmbH, Idar-Oberstein, Germany). The particle size distribution was determined
by the laser diffraction wet-dispersion method, in accordance with ISO 13320, using Fritsch Analysette
22 Micro-Tec plus (Fritsch GmbH, Idar-Oberstein, Germany). Blain surface area was measured by an
equipment supplied from ELE International (Leighton Buzzard, UK). Scanning electron microscopy
(SEM, JEOL-JSM-5510LV, JEOL Ltd., Tokyo, Japan) coupled with energy dispersive spectroscopy
(EDS) model IXRF 500 (NTC Tech Inc., Rancho Cordova, CA, USA), was used for investigation of the
morphology structure of the Grog. The investigated samples were coated with a thin gold layer using
sputter coater to make them conductive and ensure there was no arching or image instability during
the SEM observation process [17].
The dissolution rate of Si and Al from the starting aluminosilicate source material plays a crucial
role in geopolymerization reactions. Hence, the extent of dissolution rate of the source materials in
alkaline mediums at low solid/solution ratios can be used for prediction of their behavior at high
solid/solution ratios. Therefore, the reactivity of the starting material (Grog) for geopolymerization
was assessed by testing the dissolution extents of Si and Al species from the solid source materials
in sodium hydroxide, through inductively coupled plasma atomic emission spectroscopy (ICP-OES).
The leaching of the Grog was conducted by immersing 1.00 (±0.0001) g of the dry powder sample in
40 mL of 1 M NaOH solution in a glass beaker and magnetically stirring at room temperature. After
5 h of mechanical stirring, the solution was acidified, filtered, and diluted. Afterwards, ICP-OES was
employed to analyze the Al and Si concentrations in the filtrated solution [18]. Commercially available
sodium hydroxide (NaOH flakes, PCC Rokita, Brzeg Dolny, Poland), distilled water, and liquid sodium
silicate with a specific gravity of 1.46 g/cm3 at 20 ◦ C and an initial silica modulus ratio (Ms = SiO2 /Na2 O)
of 2.50 were used for the preparation of the different alkaline activator solutions and were allowed to
cool at room temperature (25 ± 2 ◦ C) for 24 h prior to the geopolymer preparation process.
2.2. Preparation of Alkaline Activator Solutions

Different alkaline activator solutions were prepared by mixing different proportions of sodium
hydroxide solution (NaOH, 10 M) and sodium silicate solution (Ms = 2.5). To investigate the effects of
the silica modulus molar ratio, the total silica modulus ratios of the prepared alkaline activator solutions
were 0.50, 0.75, 1.00, 1.25, 1.50, 2.00, and 2.50 with a fixed H2 O/Na2 O molar ratio [19]. Moreover, the
influence of different H2 O/Na2 O molar ratios on the geopolymerization reaction of the waste fired clay
Materials 2020, 13, 383 4 of 26
bricks was investigated with the optimum silica modulus molar ratio (Ms = SiO2 /Na2 O) obtained in
terms of the highest value of mechanical performance. The H2 O/Na2 O molar ratio ranged from 10–20,
and the proportion of solid powder to alkaline activator solution by mass was fixed at a liquid/solid
ratio of 0.35 to allow a full geopolymerization process to occur [12]. In addition, an investigation of
the influence of the liquid to solid ratio on the geopolymerization reaction of Grog at the optimum
silica modulus (Ms = SiO2 /Na2 O) and H2 O/Na2 O molar ratio was carried out. A total of sixteen
different geopolymer mixes were formulated in the current study. Moreover, the effects of a different
total silica modulus (Ms = SiO2 /Na2 O), H2 O/Na2 O molar, and liquid to solid ratio (L/S) on the Grog
geopolymerization reaction were monitored through determination of the setting time (initial and
final setting time) as well as the characterization of generated geopolymer specimens to establish a
recommendation for optimum geopolymerization reaction conditions.
2.3. Geopolymer Synthesis and Characterization Procedures

The synthesis of different geopolymer pastes was carried out using mixtures of starting source
material (Grog) and different alkaline activator solutions. Immediately after adding the alkaline
activator solution to the dry powder and mixing manually for about 5 min, the pastes were casted into
12.5 × 12.5 × 12.5 mm molds in two layers [20]. The molding process was followed by compacting
vibrating, using a vibration table for approximately 2 min, and subsequent wrapping in plastic film
sheets to avoid moisture evaporation at ambient temperature (25 ◦ C). The molds were opened after
24 h and the de-molded specimens were preserved at ambient temperature until we tested their
physico–mechanical properties at curing time intervals.
The method described by the American Society for Testing and Materials [21], based on Archimedes’
principle, was used to measure the bulk density and apparent porosity of the final geopolymer
specimens [22]. The water absorption of all geopolymer specimens was calculated based on the
percentage increase in the weight of the complete surface dry samples at a temperature of 80 ◦ C in the
oven for 24 h, as well as after the sample had been boiled for 2 h and submerged in water for 24 h [23].
Compressive strength tests were carried out using a MATEST (Model C-104 with Cyber-plus evolution
program, MATEST S.p.A., Arcore, Italy) universal crushing machine, with a 0.05 KN/s loading rate.
The average failure load per cross-sectional area (MPa) of the three geopolymer specimens were then
recorded for the compressive strength values [20]. After that, the fractions of the geopolymer specimens
were characterized by using various techniques: X-ray diffraction (XRD, Panalytical X’pert Pro, Malvern
Panalytical Ltd., Malvern, UK); Fourier transforms infrared spectroscopy (FTIR, JASCO FT/IR-6100,
FRITSCH GmbH, Idar-Oberstein, Germany); Scanning electron microscope (SEM, JEOL-JSM-5510LV,
JEOL Ltd., Tokyo, Japan); Thermal analysis involving thermogravimetry and differential scanning
calorimetry (TG & DSC, STA 409 CD (Netzsch) advance coupling techniques, NETZSCH-Gerätebau
GmbH, Selb, Germany) as well as dilatometry curve of the geopolymer specimen produced by the
optimum conditions. The calorimetric curves were recorded with a DSC using a closed alumina
crucible (85 µL, with a 50 µm hole in the lid), with about 150 mg of a sample under a dynamic air
atmosphere (80 mL/min). The temperature was in the range of 30–1000 ◦ C at a heating rate of 10 ◦ C/min.
An empty closed alumina crucible was used as a reference. The apparatus was calibrated in accordance
with the methodology presented in previous studies [24,25]. A dimensional change behavior test of
the optimum geopolymer specimen was performed in a horizontal NETZSCH 402 C dilatometer. The
process was carried out under the same conditions as the TG/DSC measurements. Moreover, the data
were analyzed using Proteus software (ver. 5.2.0) supplied by Netzsch.
2.4. Monitoring the Geopolymerization Rate

The alkali activator solution is known to play a major role in the kinetics of the geopolymerization
reaction [26]. The reaction rates of geopolymerization and hardening of synthesized geopolymer paste
with a different silica modulus ratio, H2 O/Na2 O molar ratio, and L/S ratio were monitored by the
direct determination of initial and final setting time using Vicat0 s apparatus according to the ASTM
Materials 2020, 13, 383 5 of 26
methods [27] but during the test, different alkaline activator solutions were used instead of water. The
initial and final setting times were estimated by measuring the penetration depth of the Vicat0 s needles
into geopolymer pastes.
3. Results and Discussions
3.1. Starting Material Characterization

The main oxides composition of the starting raw material (Grog) is given in Table 1. The waste
fired clay bricks composed mainly of aluminosilicate with some chemical oxides (Fe2 O3 , CaO, and
Na2 O). The measured specific gravity and Blaine surface area of the starting material were 2.38 g/cm3
and 7600 cm2 /g, respectively. Moreover, the particle size distribution is presented in Figure 1 and the
majority2019,
Materials of the
12, xparticle
FOR PEERsize distribution was recorded in the range of 0.5–10 µm.
REVIEW 6 of 27
Figure 1. The particle size distribution of the starting material (Grog).

Figure 1. The particle size distribution of the starting material (Grog).
Table 1. Chemical oxide composition of waste fired clay bricks (Grog), mass %.
Oxides SiO2 Al2 O3 Fe2 O3 CaO Na2 O K2 O TiO2 MnO MgO SO3 BaO P2 O5 Cl LOI a
Grog 50.16 15.95 15.09 4.39 2.43 1.48 2.10 0.16 2.13 2.78 0.06 0.24 0.46 2.15
a loss on ignition at 950 ◦ C.
The (XRD) pattern of the starting material, as shown in Figure 2, indicates that the major crystalline
phase present was a quartz phase (SiO2 ), which was mainly related to sand addition during the raw
meal preparation step for producing the clay brick units. In addition, the presence of some minor
peaks corresponding to some minor constituents such as albite (NaAlSi3 O8 ) and iron oxide in the form
of hematite and maghemite minerals was observed. However, iron-bearing materials such as iron-rich
geological material (40% Fe2 O3 ), fly ash (10% Fe2 O3 ), and ground granulated blast-furnace slag (0.5%
Fe2 O3 ) were used to produce geopolymers, as the presence of iron oxides might play important roles
in the microstructure and overall properties of the product, although substitutions of Al by Fe have not
yet been fully studied [28]. Otherwise, the XRD pattern does not show any crystalline phases related
Materials 2020, 13, 383 6 of 26
to the clay mineral structure, which completely transfers to an amorphous aluminosilicate structure
generated upon theFigure
firing1.step
The at
particle
aboutsize
900distribution
◦ C during of thebrick
clay starting material (Grog).
manufacturing [29].
Figure 2.
Figure XRD pattern
2. XRD pattern of
of the
the starting
starting material
material (Grog).
(Grog).
Figure 3 shows the FTIR spectra of the starting material. The main broad band centered at
Figure 3 shows the FTIR spectra−1of the starting material. The main broad band centered at a
a wavenumber of around ≈ 1100 cm and other bands located at 460 cm−1 were associated with
wavenumber of around ≈ 1100 cm−1 and other bands located at 460 cm−1 were associated with
asymmetric Si–O stretching in the tetrahedral structure [10]. Otherwise the bands at wavenumber
asymmetric −1Si–O stretching in the tetrahedral structure [10]. Otherwise the bands at wavenumber
450–750 cm−1 related to the vibration mode of Al–O–Si bonds of any aluminosilicate powder
450–750 cm related to the vibration mode of Al–O–Si bonds of any aluminosilicate powder material
material [30]. Moreover, other main broad bands at 3548 and 3455 cm−1 related to the adsorbed
hydroxyl group associated with the band at 1630 cm−1 indicate the presence of a water molecule due
to the humidity in the starting material. Furthermore, the presence of two minor bands approximately
at wavenumbers 2925 and 2856 cm−1 corresponded to the antisymmetric stretching vibration and
symmetric stretching vibration of the methylene group (CH2 ) arising from the presence of organic
impurities [2].
Figure 4. illustrates the microstructure morphology of Grog as well as their microanalysis (EDX).
SEM images show the irregularly and angularly shaped microstructure morphology with a flaky grains
appearance and an approximately 2.5 µm particle size distribution. In addition, the EDX shows the
presence of silicon (Si), aluminum (Al), oxygen (O), and iron (Fe) as the main constituents of starting
material with a minor presence of sodium (Na), calcium (Ca), and magnesium (Mg). The results
obtained from SEM observation are consistent with the oxides composition analysis (XRF) given in
Table 1 and the particle size distribution range, as shown in Figure 1.
On the other hand, the concentrations of alumina and silica in the form of Al3+ and Si4+ ions which
leached into the solution and were used to measure the reactivity of Grog for the geopolymerization
reaction were 30 and 82.60 mg/L, respectively. As expected, the concentration of Al3+ ions was much
lower than that of Si4+ ions. This phenomenon is mainly due to a lower alumina content in the Grog, at
approximately one-third of the silica content. Furthermore, the weight percentage of Si4+ ions leached
into solution was about 16.52% of the total silica content in the Grog. This was mainly due to the
considerable percentage of crystalline silica in the quartz phase, which reflects the total number of
Materials 2020, 13, 383 7 of 26
dissolved Si4+ ions after the geopolymerization reaction. In particular, the lower amorphous fraction
of silica ions relied upon the mix design of the clay bricks raw meal and the sand that was used as
a non-plastic filler in an additional step during the clay brick manufacturing process. In general,
the extent of dissolution of Al3+ and Si4+ from source materials at a lower concentration of alkaline
media at 1 M can be used to predict their behavior during a geopolymerization reaction in a high
concentration (2.5–12 M) of alkaline media. In this way, the extent to which the starting material
Materials 2019, 12, x FOR PEER REVIEW 7 of 27
is affected by the alkaline solution can be evaluated [18]. Therefore, the alkali concentration of the
geopolymer
[30]. Moreover, system
otherinmain
terms of the
broad silica
bands at modulus molar
3548 and 3455 cmratio = SiO
(Ms to
−1 related 2 /Na2 O), hydroxyl
the adsorbed H2 O/Na2 O, and
group
liquid/solid ratio are significant parameters in controlling the process of dissolution
associated with the band at 1630 cm indicate the presence of a water molecule due to the humidity
−1 of alumina and
silica from the starting material (Grog), the subsequent geopolymerization
in the starting material. Furthermore, the presence of two minor bands approximately at rate, and the mechanical
properties
wavenumbers of the2925
final and
hardened
2856 cmgeopolymer productto[31].
−1 corresponded the The results of the
antisymmetric reactivityvibration
stretching test indicated
and
that the dissolution of the starting material (Grog) is sufficient in high alkaline concentration
symmetric stretching vibration of the methylene group (CH2) arising from the presence of organic media
rather than in
impurities [2].low concentration media.
Figure 3. FTIR spectra of the starting material (Grog).

Figure 3. FTIR spectra of the starting material (Grog).
3.2. The Influence of Silica Modulus (Ms = SiO2 /Na2 O), H2 O/Na2 O Molar Ratio and L/S Ratio on
Geopolymerization Rate the microstructure morphology of Grog as well as their microanalysis (EDX).
Figure 4. illustrates
SEMThe images
initialshow the irregularly
and final and
setting times angularlygeopolymer
of prepared shaped microstructure morphology
paste specimens generatedwith a flaky
by different
grains appearance and an approximately 2.5 μm particle size distribution. In addition, the EDX
alkaline activator solutions with a variation in the silica modulus (Ms = SiO2 /Na2 O) molar ratio rangingshows
the presence
from 0.5–2.5 areofpresented
silicon (Si), aluminum
in Figure 5. As(Al), oxygen
can be (O),geopolymerization
seen, the and iron (Fe) as theratemain constituents
and setting of
times are
starting material with a minor presence of sodium (Na), calcium (Ca), and magnesium (Mg). The
strongly dependent on the silica modulus molar ratio. In general, the setting times of the geopolymer
results obtained from SEM observation are consistent with the oxides composition analysis (XRF)
pastes significantly decreased with an increase in the solution silica modulus molar ratio. The alkaline
given in Table 1 and the particle size distribution range, as shown in Figure 1.
activator solution with a silica modulus molar ratio of Ms = 0.5 had the highest setting time value of
around 400 min for the initial setting and about 600 min for the final setting time, which indicated
a lower rate for the geopolymerization process. In contrast, the alkaline activator solution with a
silica modulus molar ratio Ms = 2.5 had the smallest value of setting time at approximately 25 min
for initial setting and 75 min for final setting, which indicated a faster rate for the geopolymerization
process mainly due to the increases in free Si4+ ions in the geopolymer matrix. Furthermore, the
alkaline activator solution became viscous as a result of an increasing silica modulus molar ratio, which
was mainly related to increases in the content of sodium silicate in the alkaline activator. This effect
decreases the workability of the paste and reduces the setting time. On the other hand, the alkalinity of
Materials 2020, 13, 383 8 of 26
the alkaline activator solution increased as the silica modulus molar ratio decreased, which is mainly
caused by the presence of OH groups that play a key part in the dissolution of starting material and
improve the solubility of silica and alumina during the geopolymerization process [11].
(a)
(b)
Figure 4. Cont.
Materials 2020, 13, 383 9 of 26
(c)
(d)
Figure 4. SEM images of the starting material (Grog) at magnification (a) ×5000, (b) ×8500, (c) ×10,000,
and (d) its EDX analysis.
The setting times for geopolymer pastes prepared from different alkaline activator solutions with
a fixed silica modulus molar ratio, Ms = 1.25, that had the highest physico–mechanical properties and
a H2 O/Na2 O molar ratio ranging from 10–20 are shown in Figure 6. The setting time figure shows that
the initial and final setting times decreased significantly as the H2 O/Na2 O molar ratio increased from
10 to 20. The initial setting times of the prepared geopolymer specimens with different H2 O/Na2 O
molar ratios (10, 12.5, 15, 17.5, and 20) were 600, 440, 195, 125, and 50 min, respectively, and their final
2
Materials 2020, 13, 383 10 of 26
molar ratio, which was mainly related to increases in the content of sodium silicate in the alkaline
activator. This effect decreases the workability of the paste and reduces the setting time. On the other
setting times were 800, 630, 320, 245, and 115 min, respectively. Consequently, as the molar ratio of
hand, the alkalinity of the alkaline activator solution increased as the silica modulus molar ratio
H2 O/Na2 O decreased from 20 to 10, the viscosity of the alkaline solution increased, which led to a
decreased, which is mainly caused by the presence of OH groups that play a key part in the
decrease of the workability of the geopolymer paste and a decrease of the ion mobility in the matrix,
dissolution of starting material and improve the solubility of silica and alumina during the
which was mainly connected with the increase of the setting time [11].
geopolymerization process [11].
700
Intial setting time Final setting time
600
Fixed H2O/Na2O molar ratio and L/S ratio
500
Setting time, min
400
300
200
100
0
0.5 0.75 1 1.25 1.5 2 2.5
Silica
Materials 2019, 12, x FOR PEER REVIEW modulus (Ms= SiO2/Na2O, molar ratio) 10 of 27
Figure5.5.The
Figure Thegeopolymerization
geopolymerizationrate
rateinin
correlation with
correlation silica
with modulus
silica modulus = SiO
(Ms(Ms 2 /Na
= SiO 2 O,2O,
2/Na
molar ratio).
molar
ratio). 900
Intial setting time Final setting time
800 times for geopolymer pastes prepared from different alkaline activator solutions
The setting
FixedMs
with a fixed silica modulus molar ratio, Ms= SiOthat
= 1.25, 2/Nahad
2O, the
molar ratiophysico–mechanical
highest and L/S ratio properties
700
and a H2O/Na2O molar ratio ranging from 10–20 are shown in Figure 6. The setting time figure shows
Setting time, min
that the initial

600and final setting times decreased significantly as the H2O/Na2O molar ratio increased
from 10 to 20. The initial setting times of the prepared geopolymer specimens with different
500 ratios (10, 12.5, 15, 17.5, and 20) were 600, 440, 195, 125, and 50 min, respectively,
H2O/Na2O molar
and their final
400setting times were 800, 630, 320, 245, and 115 min, respectively. Consequently, as the
molar ratio of H2O/Na2O decreased from 20 to 10, the viscosity of the alkaline solution increased,
which led to300
a decrease of the workability of the geopolymer paste and a decrease of the ion mobility
in the matrix, which was mainly connected with the increase of the setting time [11].
200
100
0
10 12.5 15 17.5 20
H2O/Na2O molar ratio
Figure 6. The geopolymerization rate
Figure 6. rate in
in correlation
correlation with
with the
the H
H22O/Na22O molar ratio.
Figure
Figure 77 shows
shows the
the rate
rate of
of geopolymerization,
geopolymerization, in in terms
terms ofof the
the initial
initial and
and final
final setting
setting times,
times, of
of
geopolymer pastes made with different liquid/solid ratios using alkaline activator
geopolymer pastes made with different liquid/solid ratios using alkaline activator solutions with solutions witha
afixed
fixed silica
silica modulus
modulus molar
molar ratioratio
(Ms (Ms = and
= 1.25) 1.25)a and
fixedaHfixed
2O/Na H2O2 O/Na
molar 2 Oratio
molar ratio
(12.5) (12.5)
which which
provided
provided good physico–mechanical properties. As seen in Figure 7, the initial and
good physico–mechanical properties. As seen in Figure 7, the initial and final setting time increased final setting time
increased
remarkably as the liquid/solid ratio increased from 0.25 to 0.40 which indicates that the
geopolymerization
geopolymerization raterateisisalso
alsostrongly
strongly affected
affected byby
thethe liquid/solid
liquid/solid ratio.
ratio. This This
agrees agrees with work
with prior prior
work that shows
that shows thatthe
that as as liquid
the liquid to solid
to solid ratio
ratio increases,
increases, thethe settingtimes
setting timesofofgeopolymer
geopolymer pastepaste also
also
significantly
significantly increase
increase [32]. Increasing the
[32]. Increasing the liquid/solid
liquid/solid ratio
ratio of
of the
the geopolymer
geopolymer paste paste above
above 0.30
0.30 leads
leads
to a reduction of the alkali concentration of the geopolymeric system, which makes the paste more
fluid and negatively affects the rate of geopolymerization reaction, which in turn leads to an
increased setting time and reduced compressive strength for the final geopolymer product [33].
1200
fixed silica modulus molar ratio (Ms = 1.25) and a fixed H2O/Na2O molar ratio (12.5) which provided
good physico–mechanical properties. As seen in Figure 7, the initial and final setting time increased
geopolymerization rate is also strongly affected by the liquid/solid ratio. This agrees with prior work
Materials 2020, 13, 383
that shows that as the liquid to solid ratio increases, the setting times of geopolymer paste11also of 26
significantly increase [32]. Increasing the liquid/solid ratio of the geopolymer paste above 0.30 leads
to
to aa reduction
reduction of of the
the alkali
alkali concentration
concentration of
of the
the geopolymeric
geopolymeric system,
system, which
which makes
makes the
the paste
paste more
more
fluid and negatively affects the rate of geopolymerization reaction, which in turn leads
fluid and negatively affects the rate of geopolymerization reaction, which in turn leads to an increased to an
increased
setting timesetting time andcompressive
and reduced reduced compressive strength
strength for forgeopolymer
the final the final geopolymer product [33].
product [33].
1200
Initial setting time Final setting time
1000
Fixed Ms= SiO2/Na2O and H2O/Na2O molar ratio
Setting time, min
800
600
400
200
0
0.25 0.30 0.35 0.40
Liquid/solid ratio
Figure 7. The geopolymerization rate in correlation with the liquid/solid ratio.
Figure 7. The geopolymerization rate in correlation with the liquid/solid ratio.
3.3. The Influence of Silica Modulus (Ms = SiO2 /Na2 O), H2 O/Na2 O Molar Ratio and L/S Ratio on the
Physico–mechanical Properties of Geopolymers
The physical and mechanical properties of grog-based geopolymers generated from different
alkaline solution compositions, in term of various silica modulus (Ms = SiO2 /Na2 O) molar ratio ranging
from 0.50–2.5, at different interval curing times are presented in Figure 8. As the results indicate, the
bulk density of the geopolymer increased from 1.94 to 2.09 g/cm3 as the silica modulus molar ratio of
the used alkaline solution increased from 0.5 to 1.25–1.5 and the curing time increased to 28 days for all
synthesized geopolymer specimens. Consequently, as a result of the increasing bulk density of the
geopolymer, the apparent porosity decreased from 42.7% to 27–28%. Moreover, the water absorption of
the prepared geopolymer specimen decreased from 28.5% to 15% as the silica modulus of the alkaline
solution increased from 0.50 to 1.25–1.5, and the curing time decreased as well. Consequently, as the
physical properties of the geopolymer specimens were enhanced by increasing the silica modulus up
to 1.5 and the curing time up to 28 days, the compressive strength improved. Hence, the compressive
strength shows a corresponding increase up to a silica modulus of 1.25. After that, a reduction in
the compressive strength can be observed. Furthermore, the compressive strengths after 28 days
curing for specimens synthesized with alkaline activator solutions with a silica modulus of 1.25 and
1.5 were 28.5 and 25.8 MPa, respectively, and the strength of the geopolymer specimen made with a
0.5 silica modulus was much lower, at around 4.5 MPa. As seen in Figure 8, the physico–mechanical
properties of synthesized geopolymer matrixes improved with the increasing silica modulus ranging
from 0.75–1.5 and the optimum value at 1.25. It was previously reported that the increase of silica
modulus usually leads to an improvement in the geopolymerization reaction rate, but it can reduce the
geopolymerization rate at a high silicate concentration ratio of over 2.0. Subsequently, the results were
in good agreement and had consistency with the previous investigation [34].
Materials2019,
Materials 13,x383
2020,12, FOR PEER REVIEW 1212ofof2726
2.1 50
3 days 3 days
45
2.05 7 days 7 days
40
14 days 14 days
Apparent porosity, %
2 35
Bulk density, g/cm3
28 days 28 days
30
1.95 25
20
1.9
15
1.85 10
5
1.8 0
0.5 0.75 1 1.25 1.5 2 2.5 0.5 0.75 1 1.25 1.5 2 2.5
Ms = SiO2/Na2O, molar ratio Ms = SiO2/Na2O, molar ratio
(a) (b)
30 3 days 30 3 days
7 days 7 days
25 25
14 days 14 days
Compressive strength, MPa
20 28 days 28 days
20
Water absorption , %
15 15
10 10
5 5
0 0
0.5 0.75 1 1.25 1.5 2 2.5 0.5 0.75 1 1.25 1.5 2 2.5
Ms = SiO2/Na2O, molar ratio Ms = SiO2/Na2O, molar ratio
(c) (d)
Figure
Figure8.8. The
Thephysico–mechanical
physico–mechanicalproperties
properties((a)
((a)bulk
bulkdensity,
density,(b)
(b)apparent
apparentporosity,
porosity,(c)
(c)water
water
absorption
absorption and (d) compressive strength) of synthesized geopolymer specimens in correlationwith
and (d) compressive strength) of synthesized geopolymer specimens in correlation with
silica
silicamodulus
modulus(Ms(Ms==SiO
SiO 2 /Na
2/Na 2O,O,
2 the molar
the ratio.
molar ratio).
The physico–mechanical properties of waste fired clay bricks-based geopolymers made using
different alkaline solution compositions, in terms of various H2 O/Na2 O molar ratios of 10–20 and a
fixed silica modulus Ms = 1.25 at different interval curing times, are presented in Figure 9. There were
clear differences in the physico–mechanical properties, which shifted with an increasing H2 O/Na2 O
molar ratio of up to 20. From the presented data, the highest bulk density value was 2.12 g/cm3 ,
the lowest apparent porosity percentage was 27.8%, and the water absorption was 15.1% for the
geopolymer specimen synthesized using a 12.5 H2 O/Na2 O molar ratio and with 28 days of curing
time. Accordingly, the highest compressive strength 32 MPa was measured for the same specimen
after 28 days of curing time. It is also notable that the physico–mechanical properties were enhanced
in a range of H2 O/Na2 O molar ratio of 10–12.5. On the other hand, the high-water content at the molar
ratio H2 O/Na2 O of 20 resulted in the lowest compressive strength, at around 19 MPa.
Materials 2020, 13, 383 13 of 26
2.15 3 days 40 3 days

7 days 35 7 days
2.1
14 days 30 14 days
28 days
Bulk density, g/cm3
2.05 25 28 days
20
2
15
1.95 10
5
1.9
0
10 12.5 15 17.5 20
10 12.5 15 17.5 20
H2O/Na2O, Molar ratio H2O/Na2O, Molar ratio
(a) (b)
25
3 days 35 3 days
7 days
20 30 7 days
14 days
Water absorption , %
14 days
25
15 28 days 28 days
20
10
15
5 10
5
0
0
10 12.5 15 17.5 20
10 12.5 15 17.5 20
H2O/Na2O, Molar ratio
H2O/Na2O, Molar ratio
(c) (d)
Figure 9.
Figure Thephysico–mechanical
9. The physico–mechanicalproperties
properties((a)
((a)bulk
bulkdensity,
density,(b)
(b)apparent
apparentporosity,
porosity, (c)
(c) water
water
absorptionand
absorption and(d)
(d)compressive
compressivestrength)
strength)of
ofsynthesized
synthesizedgeopolymer
geopolymerspecimens
specimensin
incorrelation
correlationwith
with
H O/Na
H2O/Na
2 2O,O, the molar ratio.
2 the molar ratio.
The physico–mechanical properties of waste fired clay bricks-based geopolymers produced using
The physico–mechanical properties of waste fired clay bricks-based geopolymers produced
different liquid/solid ratios ranging from 0.25–0.40, a 1.25 silica modulus, a 12.5 H2 O/Na2 O molar ratio,
using different liquid/solid ratios ranging from 0.25–0.40, a 1.25 silica modulus, a 12.5 H2O/Na2O
and different interval curing times are presented in Figure 10. It is well known that the liquid/solid ratio
molar ratio, and different interval curing times are presented in Figure 10. It is well known that the
of any binder material system is one of the most important factors, along with the curing conditions,
liquid/solid ratio of any binder material system is one of the most important factors, along with the
that significantly influences the physico–mechanical properties of the resulting hardened paste [11].
curing conditions, that significantly influences the physico–mechanical properties of the resulting
As the results
hardened pasteindicate,
[11]. As the
the physico–mechanical properties of the geopolymer
results indicate, the physico–mechanical properties specimens in terms
of the geopolymer
of the bulk density, apparent porosity, water absorption, and compressive
specimens in terms of the bulk density, apparent porosity, water absorption, and compressivestrength were enhanced
when thewere
strength liquid/solid
enhanced ratio
whenrange
the was 0.25–0.30.
liquid/solid As range
ratio expected,
was above the liquid/solid
0.25–0.30. As expected,ratio of 0.30,
above the
there was a reduction
liquid/solid in thethere
ratio of 0.30, physico–mechanical
was a reductionproperties of the geopolymer specimens.
in the physico–mechanical properties Usually,
of the
with an increase
geopolymer in the liquid/solid
specimens. Usually, with ratio,
an there is aninimprovement
increase in the
the liquid/solid workability
ratio, there is anofimprovement
a geopolymer
binder system’s paste, mortar, or concrete. However, it should be noted that in
in the workability of a geopolymer binder system’s paste, mortar, or concrete. However, it should the most cases, the
be
increase
noted thatininliquid/solid ratiothe
the most cases, consequently leads to anratio
increase in liquid/solid increase in the total
consequently porosity
leads of the system,
to an increase in the
Materials 2020, 13, 383 14 of 26
total porosity of the system, which reflects negatively on the compressive strength behavior of the
hardened paste. A significant difference can be observed between the highest 28 days cured
which reflects negatively on the compressive strength behavior of the hardened paste. A significant
compressive strength value recorded at around 37.5 MPa for the geopolymer specimen produced by
difference can be observed between the highest 28 days cured compressive strength value recorded at
a 0.25 liquid/solid ratio, and the lowest 28 days cured compressive strength value, recorded at around
around 37.5 MPa for the geopolymer specimen produced by a 0.25 liquid/solid ratio, and the lowest
25.5 for the geopolymer specimen made with a 0.40 liquid/solid ratio. When high liquid/solid ratios
28 days cured compressive strength value, recorded at around 25.5 for the geopolymer specimen made
in the 0.35–0.40 range were applied, there was an increase in the amount of fluid medium rather than
with a 0.40 liquid/solid ratio. When high liquid/solid ratios in the 0.35–0.40 range were applied, there
solid content in the paste, as a result of contact between the alkaline activator solution and the
was an increase in the amount of fluid medium rather than solid content in the paste, as a result of
reacting solid material, which was limited due to the large volume of fluid medium. Furthermore,
contact between the alkaline activator solution and the reacting solid material, which was limited
the dissolution of solid material was slow, and the geopolymerization rate was slow. This explains
due to the large volume of fluid medium. Furthermore, the dissolution of solid material was slow,
the low 28-days compressive strength of a geopolymer specimen with a liquid/solid ratio of 0.40. In
and the geopolymerization rate was slow. This explains the low 28-days compressive strength of a
contrast, when lower liquid/solid ratios in the 0.25–030 range were used, the solid material content
geopolymer specimen with a liquid/solid ratio of 0.40. In contrast, when lower liquid/solid ratios
increased in the geopolymer paste. The interaction between the alkaline activator solution and
in the 0.25–030 range were used, the solid material content increased in the geopolymer paste. The
reacting solid material led to an enhancement in the physico–mechanical properties of the
interaction between the alkaline activator solution and reacting solid material led to an enhancement
geopolymer specimens. Therefore, an optimal liquid/solid ratio in the 0.25–0.30 range exists for waste
in the physico–mechanical properties of the geopolymer specimens. Therefore, an optimal liquid/solid
fired clay bricks based geopolymers [11].
ratio in the 0.25–0.30 range exists for waste fired clay bricks based geopolymers [11].
2.12 3 days 40 3 days

2.1 7 days 35 7 days
14 days
2.08 30 14 days
Bulk density, g/cm3
28 days 25
2.06 28 days
20
2.04
15
2.02
10
2 5
1.98 0
0.25 0.30 0.35 0.40 0.25 0.30 0.35 0.40
Liquid/solid ratio Liquid/solid ratio
(a) (b)
25
3 days
40 3 days
20 7 days
35
Water absorption, %
14 days 7 days
15 30 14 days
28 days
25 28 days
10 20
15
5
10
0 5
0.25 0.3 0.35 0.40 0

Liquid/solid ratio 0.25 0.30 0.35 0.40
Liquid/solid ratio
(c) (d)
Figure
Figure10.
10.TheThephysico–mechanical
physico–mechanical properties
properties ((a) bulk
((a) density,
bulk density,(b)(b)apparent
apparentporosity,
porosity,(c)(c)water
water
absorption
absorptionandand(d)
(d)compressive
compressivestrength)
strength)ofofsynthesized
synthesizedgeopolymer
geopolymerspecimens
specimensinincorrelation
correlationwith
witha a
liquid/solid
liquid/solidratio.
ratio.
Materials 2020, 13, 383 15 of 26
3.4. FTIR of the Generated Geopolymers

Figure 11 presents the FTIR spectra of the generated grog based geopolymers made with various
alkaline solutions, in term of silica modulus (Ms = SiO2 /Na2 O) molar ratios, at a curing time of 28 days.
In the FTIR spectra of the geopolymer products, the band centered at about 460 cm−1 , corresponding to
Si–O bending. Other bands, attributed to the formation of the geopolymer structure are at about 3450
and 1635 cm−1 and are associated with the bending and stretching bands of H2 O molecules that have
been either surface absorbed in the geopolymer structure cavities or bonded physically to the silanol
surface groups (≡Si–OH . . . .H2 O and ≡ Al–OH . . . ..H2 O) [35,36]. Furthermore, weak adsorption
bands at 600 and 780 cm−1 are assigned to Si–O–Al bending, indicating the formation of the main
geopolymer network structure that was generated during the geopolymerization reaction of a silica
aluminate material in a highly alkaline solution. The main band centered at 1100 cm−1 in the grog
spectrum shifted to a lower frequency at ≈ 850 cm−1 and broadened to ≈ 1350 cm−1 , confirming the
formation of a new geopolymer product. Furthermore, the FTIR spectra of the prepared geopolymers
showed a distinct intense broad band at approximately 850 and 1350 cm−1 for all samples associated
with the asymmetric vibration of Si–O–T units of the silicate framework of the formed geopolymer
network. Moreover, this peak is often used to determine the degree of polymerization because it
is easier to interpret than the Si–O–Si bonding peak at 450 cm−1 [37]. Moreover, the observed shift
towards a higher wavenumber can be connected with the generation of more condensed Si–O–Si units
in the geopolymer network. Based on the data presented in the FTIR spectra, broadening in this band
increases as a result of increasing the silica modulus of the used alkaline solution and the broadest band
occurs in the geopolymer sample prepared with an alkaline solution with a 1.25 silica modulus molar
ratio [38]. The FTIR bands at approximately 1450 cm−1 assigned to the vibration mode of O–C–O bonds,
and two minor peaks at 2355 cm−1 assigned to the stretching vibration mode of C=O bonds are related
to the carbonate formation process due to the reaction of alkali metal hydroxide with atmospheric
CO2 to produce Na2 CO3 , which was observed in all spectra of the generated geopolymer samples [10].
On the other hand, the intensity of these carbonate bands was reduced as the silica modulus increased
and it disappeared at higher silica modulus values (Ms ≥ 1.5), indicating less carbonate formation in
the geopolymer matrix.
Figure 12 shows the FTIR spectra of the prepared grog based geopolymers using various alkaline
solutions, in terms of H2 O/Na2 O ratio molar ratios, at 28 days curing time. The broad band appearing
at 850–1350 cm−1 , attributed to the asymmetric stretching vibration of Si–O–Si, indicates the formation
of a geopolymer network structure, which decreases as the molar ratio of H2 O/Na2 O increases from
10 to 20. Moreover, the bending vibration of Si–O–Si was identified at 460 cm−1 and the peak at
approximately 650 cm−1 which corresponds to the Si–O–Al bending vibration, were also observed,
especially at a 12.5 H2 O/Na2 O molar ratio. The geopolymerization degree affected the stretching
vibration band of Si–O–Si and the wavenumbers of the absorption bands increased with the degree
of geopolymerization. Furthermore, the intensity of the stretching vibration of O–C–O detected at
1420 cm−1 remarkably increased as the molar ratio of H2 O/Na2 O increased from 10 to 20, which was
mainly related to an increase in the ion mobility of the geopolymer samples and positively reflected on
the rate of the carbonation process. In addition, the broad bands which appeared at 3450 cm−1 and
1650 cm−1 , mainly assigned to entrapped water molecules in the geopolymeric network, increased as
a result of increasing the amount of the water molecules in the geopolymerization reaction through
increasing the molar ratio of H2 O/Na2 O.
Materials 2020, 13, 383 16 of 26
Figure 11. FTIR spectra of synthesized geopolymer specimens in correlation with the silica modulus
Figure 11. FTIR spectra of synthesized geopolymer specimens in correlation with the silica modulus
(Ms = SiO2 /Na2 O, the molar ratio) of Ms0.5 , Ms0.75 , Ms1 , Ms1.25 , Ms1.5 , Ms2.0 and Ms2.5 , respectively.
(Ms = SiO2/Na2O, the molar ratio) of Ms0.5, Ms0.75, Ms1, Ms1.25, Ms1.5, Ms2.0 and Ms2.5, respectively.
Figure 12 shows the FTIR spectra of the prepared grog based geopolymers using various alkaline
solutions, in terms of H2O/Na2O ratio molar ratios, at 28 days curing time. The broad band appearing
at 850–1350 cm−1, attributed to the asymmetric stretching vibration of Si–O–Si, indicates the formation
of a geopolymer network structure, which decreases as the molar ratio of H 2O/Na2O increases from
10 to 20. Moreover, the bending vibration of Si–O–Si was identified at 460 cm−1 and the peak at
approximately 650 cm−1 which corresponds to the Si–O–Al bending vibration, were also observed,
especially at a 12.5 H2O/Na2O molar ratio. The geopolymerization degree affected the stretching
vibration band of Si–O–Si and the wavenumbers of the absorption bands increased with the degree
of geopolymerization. Furthermore, the intensity of the stretching vibration of O–C–O detected at
1420 cm−1 remarkably increased as the molar ratio of H2O/Na2O increased from 10 to 20, which was
mainly related to an increase in the ion mobility of the geopolymer samples and positively reflected
on the rate of the carbonation process. In addition, the broad bands which appeared at 3450 cm−1 and
1650 cm−1, mainly assigned to entrapped water molecules in the geopolymeric network, increased as
aMaterials
result of increasing
2020, 13, 383 the amount of the water molecules in the geopolymerization reaction through
17 of 26
increasing the molar ratio of H2O/Na2O.
Figure 12.
Figure FTIRspectra
12. FTIR spectraof of synthesized
synthesized geopolymer
geopolymer specimens
specimens in
in correlation
correlation with
with H
H22O/Na
O/Na22O,
O,the
the
molar ratio, of 10; 12.5; 15; 17.5 and 20, respectively.
molar ratio, of 10; 12.5; 15; 17.5 and 20, respectively.
3.5. XRD of the Synthesized Geopolymers
3.5. XRD of the Synthesized Geopolymers
Figure 13 shows the XRD diffractograms of different geopolymer specimens synthesized with
Figure 13 shows the XRD diffractograms of different geopolymer specimens synthesized with
various alkaline solutions in terms of various silica modulus (Ms = SiO2 /Na2 O) molar ratios, with
various alkaline solutions in terms of various silica modulus (Ms = SiO2/Na2O) molar ratios, with 28
28 days of curing time. The XRD pattern shows that the main crystalline phases detected in all
days of curing time. The XRD pattern shows that the main crystalline phases detected in all
geopolymers were quartz (SiO2 ) and albite (NaAlSi3 O8 ). The crystalline phase observed in the
geopolymers were quartz (SiO2) and albite (NaAlSi3O8). The crystalline phase observed in the XRD
XRD pattern of the geopolymer specimens mainly contributed to the partial dissolution of the total
pattern of the geopolymer specimens mainly contributed to the partial dissolution of the total SiO2
SiO2 content of the starting material (Grog) that accumulated from two different sources (clay and
content of the starting material (Grog) that accumulated from two different sources (clay and sand)
sand) through a raw meal mix preparation step in the clay brick manufacture process. Although
Materials 2020, 13, 383 18 of 26
the conventional geopolymer mainly consists of amorphous phases [30], some crystalline phases
might be identified in the XRD pattern of geopolymer generated from some starting materials such as
circulating fluidized bed combustion (CFBC) bottom ashes [39], and volcanic ash [40,41]. Otherwise,
the disappearance of crystalline iron oxide peaks upon alkaline activation of the starting material
was mainly related to the dissolution of iron oxide into ionic monomers or oligomers, which then
polymerized based on the pH [42]. Nevertheless, many recent studies had reported that iron-rich
materials such as fly ashes can be activated in alkaline media for engineering applications [43,44].
Furthermore, the XRD pattern also indicated that the intensity of crystalline phases corresponding
to quartz and albite in the geopolymer specimens decreased as the silica modulus of used alkaline
solution decreased, and the alkalinity of the solution increased as a result. Therefore, the relatively low
and mild alkalinity of the alkaline solution hardly dissolved the crystalline phases in the waste fired
clay bricks material. Moreover, the resultant interface structure between the produced geopolymer
aluminosilicate network gel and remaining unreacted crystalline particles in the geopolymer matrix
was expected to have a positive influence in the binding capacity of the matrix and have a significant
bearing on the overall physico–mechanical properties of the resulting geopolymer specimen [45,46].
On another hand, the XRD pattern represented in Figure 14 of the geopolymer samples prepared
using different H2 O/Na2 O molar ratios also shows the presence of some diffraction peaks attributed to
the crystalline phases that remained as unreacted residues from the starting material. As mentioned
before, the effect of the H2 O/Na2 O molar ratio on the geopolymer system can be attributed to the
mobility of the ions in the synthesized matrix, which can be significantly observed through the
physico–mechanical properties.
3.6. SEM of the Synthesized Geopolymers

Figure 15 shows the SEM micrographs of the geopolymer samples generated with various silica
modulus solutions (Ms = 0.5, 1.25 and 2.5) and cured for 28 days at ambient temperature (20–25 ◦ C). The
geopolymer sample prepared with Ms = 0.5 shows a microstructure quite similar to SEM of the starting
raw material, with a few characteristics of amorphous phase microstructure related to a geopolymer
matrix. Moreover, some unreacted grog particles are clearly visible in the SEM image, which illustrates
the insufficiency in the geopolymerization reaction at this level of the silica modulus molar ratio.
Furthermore, this geopolymer sample had the lowest recorded value of compressive strength (4.5 MPa)
after 28 days of curing and a showed much less compacted microstructure composed of a large number
of particles barely consolidated with each other, creating a very weak compacted microstructure [10].
On the other hand, the geopolymer sample generated using an alkaline solution with Ms = 1.25
showed an irregularly fibrous shaped structure which mainly corresponds to a geopolymer amorphous
network microstructure. It was formed during production of a geopolymer gel which filled and was
deposited in pore spaces between the particles to form a denser microstructure and improve the overall
physico–mechanical properties. Furthermore, the interaction between the produced geopolymer gel
and the unreacted residues from raw material had a significant influence on the microstructure and
on the overall development of compressive strength [15]. As a result, this geopolymer specimen
had the highest recorded value of compressive strength (28.5 MPa) after 28 days of curing time and
showed a highly compacted microstructure in comparison with the other geopolymer specimens. In
addition, SEM images show the presence of some rod shapes in the microstructure which related to
efflorescence formation due to the carbonation process of unreacted sodium oxide. This efflorescence
was also confirmed by FTIR spectrums. On the other hand, the SEM micrographs of geopolymer
specimen prepared using alkaline solution with Ms = 2.5 showed an irregular microstructure and
morphology, which confirms the presence of a significant amount of remaining unreacted raw material
particles as a result of the insufficient geopolymerization reaction. These microstructural differences
observed in SEM micrographs were significant enough to justify the difference in physico–mechanical
behavior of geopolymer specimens prepared using various silica modulus molar ratio alkaline solutions.
Figure 16 shows the SEM micrographs of the geopolymer samples prepared with Ms = 1.25, a 12.5
Materials 2020, 13, 383 19 of 26
H2 O/Na2 O molar ratio, and a 0.3 liquid/solid ratio as well as being cured for 28 days at an ambient
temperature (20–25 ◦ C). Based on the SEM observation of this geopolymer sample, a more amorphous
aluminosilicate gel phase with a smaller amount of unreacted particles could be observed, which
indicated a significantly higher geopolymeric microstructure. Moreover, the sample homogeneity and
a less porous microstructure were the predominant features of this SEM micrograph in comparison
with the geopolymer
Materials specimens
2019, 12, x FOR PEER REVIEWmanufactured under different conditions in this study. 19 of 27
Figure
Figure 13.13. X-ray
X-ray diffraction
diffraction pattern
pattern of geopolymers
of geopolymers prepared
prepared withwith different
different silicasilica modulus
modulus (Ms (Ms
= =
SiOSiO 2 /Na
2/Na 2 O, molar
2O, the the molar
ratio)ratio)
of Msof
0.5, Ms 0.75,, Ms
Ms0.5 Ms10.75
, Ms, Ms , Ms
1.25, 1Ms Ms,2.0Ms
1.5,1.25 and , Ms
1.5 Ms and Ms2.5 , respectively.
, respectively.
2.52.0
Materials
Materials2019,
2020,12,
13,x383
FOR PEER REVIEW 20
20of
of27
26
Figure 14. X-ray diffraction pattern of geopolymers prepared with different H2 O/Na2 O molar ratios of
Figure 14. X-ray diffraction pattern of geopolymers prepared with different H 2O/Na2O molar ratios
12.5 and 17.5, respectively.
of 12.5 and 17.5, respectively.
3.7. Thermal Analysis of the Geopolymer Synthesized at Optimum Condition
3.6. SEM of the Synthesized Geopolymers
The DSC, TG, and dilatometric curves of the optimum geopolymer specimen (SiO2 /Na2 O = 1.25,
Figure 15 shows the SEM micrographs of the geopolymer samples generated with various silica
H2 O/Na 2 O = 12.5, liquid/solid ratio = 0.30) are presented in Figure 17. DSC analysis of geopolymer
modulus solutions
behavior from room (Ms = 0.5, 1.25 and
temperature 2.5)◦and
to 300 cured for
C showed 28 days
a large at ambientpeak.
endothermic temperature (20–25 °C).
In this temperature
The geopolymer
range, on the TGsample
curve, anprepared
intensivewith Ms =loss
weight 0.5 was
shows a microstructure
recorded. quite
Additionally, thesimilar to SEMchanges
dimensional of the
starting
presented about 1% linear shrinkage. This observed effect is well known and is associated withtothe
raw material, with a few characteristics of amorphous phase microstructure related a
geopolymer matrix. Moreover,
removal of absorbed water and some
waterunreacted
containedgrog particles
within are clearly
the pore networkvisible in theMoreover,
[47–49]. SEM image, the
which illustrates the insufficiency in the geopolymerization reaction at this level
sample size expansion recorded on the dilatometric curve (Figure 17) in the temperature rangedof the silica modulus
from
molar
300 ◦ Cratio.
to 600Furthermore, this geopolymer
◦ C can be attributed sample hadprocess
to a dehydroxylation the lowest recorded
and the value α-β
polymorphic of compressive
transition of
strength (4.5 MPa) after 28 days of curing and a showed much
an unreacted quartz phase or glass transition in the geopolymer matrix [50]. less compacted microstructure
composed of a large number of particles barely consolidated with each other, creating a very weak
compacted microstructure [10]. On the other hand, the geopolymer sample generated using an
alkaline solution with Ms = 1.25 showed an irregularly fibrous shaped structure which mainly
corresponds to a geopolymer amorphous network microstructure. It was formed during production
of a geopolymer gel which filled and was deposited in pore spaces between the particles to form a
denser microstructure and improve the overall physico–mechanical properties. Furthermore, the
interaction between the produced geopolymer gel and the unreacted residues from raw material had
a significant influence on the microstructure and on the overall development of compressive strength
[15]. As a result, this geopolymer specimen had the highest recorded value of compressive strength
(28.5 MPa) after 28 days of curing time and showed a highly compacted microstructure in comparison
Materials 2020, 13, 383 21 of 26
Materials
Materials 2019,2019,
12, x 12,
FOR x FOR
PEERPEER REVIEW
REVIEW 22 of22
27 of 27
(a) (a)
Ms0.5Ms0.5
(b) (b)
Ms1.25
Ms1.25
(c) (c)
Ms2.5Ms2.5
Figure
Figure
Figure15. 15.
15.SEM
SEM SEM micrograph
micrograph
micrograph of geopolymers
ofofgeopolymers
geopolymers prepared
prepared
prepared withwith
with a different
aadifferent
different silicasilica
modulus Ms ==Ms
modulus SiO
SiO /Na22/Na
=22/Na
SiO OO 2O
molar
molar ratioratio
((a) ((a)
0.5, 0.5,
(b) (b)
1.25 1.25
and and
(c) (c)
2.5) 2.5)
at at different
different magnification.
magnification.
molar ratio ((a) 0.5, (b) 1.25 and (c) 2.5) at different magnification.
(a) (a) (b) (b)
Figure 16. Cont.

Materials 2020, 13, 383 22 of 26
(c) (d)
Figure 16. SEM images of geopolymers prepared with silica modules Ms = 1.25, a H2O/Na2O molar
ratio = 12.5, and an L/S ratio = 0.30. ((a) × 2000, (b) × 5000, (c) × 5000 and (d) × 10,000)
3.7. Thermal Analysis of the Geopolymer Synthesized at Optimum Condition

The DSC, TG, and dilatometric curves of the optimum geopolymer specimen (SiO2/Na2O = 1.25,
H2O/Na2O = 12.5, liquid/solid ratio = 0.30) are presented in Figure 17. DSC analysis of geopolymer
behavior from room temperature to 300 °C showed a large endothermic peak. In this temperature
range, on the TG curve, an intensive weight loss was recorded. Additionally, the dimensional changes
presented about 1% linear shrinkage. This observed effect is well known and is associated with the
removal of absorbed water and water contained within the pore network [47–49]. Moreover, the
sample size expansion recorded(c) on the dilatometric curve (Figure (d)17) in the temperature ranged from
300 °C to 600 °C can be attributed to a dehydroxylation process and the polymorphic α-β transition
Figure 16.
Figure SEM images
16. SEM images ofof geopolymers prepared with silica modules Ms =
geopolymers prepared 1.25, a H2O/Na
= 1.25, O/Na22O
O molar
molar
of an unreacted quartz phase or glass transition in the geopolymer matrix [50]. 2
ratio==12.5,
ratio 12.5,and
andananL/S ratio==0.30.
L/Sratio ((a)× ×2000,
0.30.((a) (b)× ×
2000,(b) 5000,
5000, (c)(c) × 5000
× 5000 andand
(d)(d) × 10,000).
× 10,000)
Furthermore, this effect is associated with a low mass decrease and a second endothermic
reaction. There was
Furthermore, this also aisrapid shrinkage
with abetween mass700 and 870
and°C, whichendothermic
was characteristic
reaction.of
3.7. Thermal Analysis of effect associated
the Geopolymer Synthesized low
at Optimum decrease
Condition a second
structural
There reorganization.
was also a rapid shrinkageThis result
between and700theand lack
870of◦ C,
changes in the
which was TG curve confirm
characteristic these
of structural
The DSC,
phenomena. TG, and dilatometric curves of the optimum geopolymer
reorganization. This result and the lack of changes in the TG curve confirm these phenomena. specimen (SiO 2/Na2O = 1.25,
H2O/Na2O = 12.5, liquid/solid ratio = 0.30) are presented in Figure 17. DSC analysis of geopolymer
behavior from room temperature to 300 °C showed a large endothermic peak. In this temperature
range, on the TG curve, an intensive weight loss was recorded. Additionally, the dimensional changes
presented about 1% linear shrinkage. This observed effect is well known and is associated with the
removal of absorbed water and water contained within the pore network [47–49]. Moreover, the
sample size expansion recorded on the dilatometric curve (Figure 17) in the temperature ranged from
300 °C to 600 °C can be attributed to a dehydroxylation process and the polymorphic α-β transition
of an unreacted quartz phase or glass transition in the geopolymer matrix [50].
Furthermore, this effect is associated with a low mass decrease and a second endothermic
reaction. There was also a rapid shrinkage between 700 and 870 °C, which was characteristic of
structural reorganization. This result and the lack of changes in the TG curve confirm these
phenomena.
(a)
Figure 17. Cont.
(a)
Materials 2020, 13, 383 23 of 26
(b)
(c)
Figure 17.
Figure 17. (a) DSC, (b) TG, and (c) Dilatometric curves of the optimum
optimum geopolymer
geopolymer specimen.
specimen.
4.
4. Conclusions
Conclusions
The
The current
current study
study investigates
investigates the
the optimum
optimum geopolymerization
geopolymerization reaction
reaction conditions
conditions for
for aa safe
safe
recycling
recycling process of the starting raw material (Grog). At this point, several geopolymerization factors
process of the starting raw material (Grog). At this point, several geopolymerization factors
affecting
affectingthe thefinal properties
final of geopolymer
properties specimens
of geopolymer were investigated
specimens and examined.
were investigated The properties
and examined. The
of the synthesized Grog-based geopolymers were mainly influenced by the silica
properties of the synthesized Grog-based geopolymers were mainly influenced by the silica modulusmodulus (Ms),
H 2 O/Na
(Ms), O molar
H22O/Na ratio of the alkaline solution, and the liquid /solid ratio. The recommended optimum
2O molar ratio of the alkaline solution, and the liquid /solid ratio. The recommended
geopolymer conditionsconditions
optimum geopolymer were selected
were based on the
selected achieved
based on theoverall properties
achieved overallofproperties
the synthesized
of the
geopolymer specimens. As the results indicate, the following conclusions were reached:
synthesized geopolymer specimens. As the results indicate, the following conclusions were reached:
• The optimum
The optimum silica
silica modulus
modulusand
andHH2O/Na
2
O/Na2O
O molar ratio of the alkaline solution were Ms = 1.25
2 molar ratio of the alkaline solution were Ms = 1.25
and 12.5,
and 12.5, respectively.
respectively.
 The optimum liquid/solid ratio was in the range 0.25–0.30.
• The optimum liquid/solid ratio was in the range 0.25–0.30.
 The 28 days compressive strength of the Grog-based geopolymer sample generated under
• The 28 days compressive strength of the Grog-based geopolymer sample generated under optimum
optimum conditions was 37.5 MPa in comparison with 5 MPa, which generated under random
conditions was 37.5 MPa in comparison with 5 MPa, which generated under random conditions.
conditions.
This study proposes a safe recycling process for waste material (Grog), which otherwise causes
a lot of environmental problems, through an optimum condition geopolymerization process.
Materials 2020, 13, 383 24 of 26
This study proposes a safe recycling process for waste material (Grog), which otherwise causes a lot
of environmental problems, through an optimum condition geopolymerization process. Consequently,
the generated binder material provides an alternative binder material that can be used in many
applications in the construction sector.
Author Contributions: This study was designed, directed, supervised and coordinated by R.A.G. and J.M.,
provided conceptualization and technical guidance for all aspects of the study. R.A.G., M.H., and M.Ł. planned
and performed the experimental and methodology parts. The experimental results and data were analyzed and
discussed by R.A.G., M.H., and J.M. The original draft manuscript was written by R.A.G. and reviewed & edited
by M.H., M.Ł. and J.M. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: The authors are grateful to the National Centre for Research and Development, Poland for
support from the project “Development of 3D printing technology for construction and facade prefabricated
elements made of concrete composites and geopolymers” no. POIR.04.01.04-00-0096/18. The help of the laboratory
staff and R. Bogucki is gratefully acknowledged. The authors also acknowledge the National Research Center
(NRC) and Academy of Scientific Research and Technology (ASRT) in Egypt for their support.
Conflicts of Interest: The authors declare no conflict of interest.
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Materials 2020, 13, 383; doi:10.3390/ma13020383 www.mdpi.com/journal/materials

2. Experimental and Methodology

2.1. Starting Materials

2.2. Preparation of Alkaline Activator Solutions

2.3. Geopolymer Synthesis and Characterization Procedures

2.4. Monitoring the Geopolymerization Rate

3. Results and Discussions

3.1. Starting Material Characterization

Figure 1. The particle size distribution of the starting material (Grog).

Figure 3. FTIR spectra of the starting material (Grog).

that the initial

2.15 3 days 40 3 days

2.12 3 days 40 3 days

0.25 0.3 0.35 0.40 0

3.4. FTIR of the Generated Geopolymers

3.6. SEM of the Synthesized Geopolymers

(a) (a) (b) (b)

Figure 16. Cont.

3.7. Thermal Analysis of the Geopolymer Synthesized at Optimum Condition

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