Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

Recycling and utilization assessment of waste red

clay bricks (Grog) with granulated blast-furnace
slag for geopolymer production

M.F. Zawrah a , R.A. Gado a, , N. Feltin b , S. Ducourtieux b , L. Devoille b

a National Research Center, Ceramics Department, 12311 Dokki, Cairo, Egypt
b Laboratoire National de Mtrologie et dEssais (LNE), 78197 Trappes, France

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

Article history: In the present study, the alkali-activation process potential of the industrial by-product
Received 3 May 2016 called waste red clay bricks (Grog) as well as the effects of the addition of another industrial
Received in revised form 22 July 2016 by-product known as granulated blast-furnace slag (S) on the properties of the nal products
Accepted 1 August 2016 has been studied. Granulated blast-furnace slag has been employed as 20%, 40%, 60% and
Available online 6 August 2016 80% replacement of waste red clay bricks (Grog) in the production of geopolymers. At the
same time, the effects of curing time on the properties of geopolymers were investigated.
Keywords: The study proved a successful method for the feasibility of recycling and valorization process
Waste red clay bricks (Grog) of two industrial by-products and converts them into valuable geopolymer products. These
Granulated blast-furnace slag potential recycling processes can generate signicant benets for environmental sector and
Recycling and valorization many economic impacts to the construction materials sector by using it as alternative raw
Geopolymer material resources for the production of the geopolymer.
Construction materials 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Brick is one of the most common masonry units as a building mate-
rial due to its properties as construction material. Conventional bricks
are produced from raw materials mixture of clay, as a plastic material,
with the addition of sand, as non-plastic material, and burned in the
kiln at ring temperature ranging from 850 to 950 C. The worldwide
annual production of bricks is currently about 1391 billion units and
the demand for bricks are expected to be continuously rising as the
construction process increasing over the worldwide (Zhang, 2013).
Waste red clay bricks (Grog) is a solid waste material produced dur-
ing the manufacturing process of clay bricks. These crushed portions of
grog are not of commercial use and considered as a solid waste material
which caused many serious environmental problems. In Egypt, a huge
amount of clay bricks is produced every year and used in construction
activities. The amount of waste red clay bricks (Grog) generated by the
Egyptian clay bricks industry sector is about 37% by weight of total
production, suggesting that millions of tons of such waste materials
are generated and disposed in huge landlls in Egyptian brick factories
each year (Farag et al., 2011). Recycling and valorization process of a
lot of industrial by-product and waste materials have become a prob-
lem urgently facing our future for environmental protection trends. In
the light of environmental standards aiming at limiting the use of the
dump, the creation of new techniques for recycling as well as wastes
valorization process capable also of exploiting the industrial wastes
into new valuable products acquires an increasing importance for the
industrial and environmental sectors (Abdul Kadir and Mohajerani,
2011).
Many attempts have been made to incorporate waste red clay
bricks (Grog) into the production process of different building mate-
rials. Recycling process for such industrial wastes by including them
into many building materials is considered as a practical solution for
many pollution problems. The utilization of these wastes will lead to
reducing many environmental problems due to their disposal. How-
ever, the waste materials can only be recycled if the properties and the
environmental behavior of the newly formed products comply with the
specic requirements and interrogated with the relevant environmen-
tal standards (Abdul Kadir and Mohajerani, 2011).
Ground granulated blast-furnace slag (S or slag), is a waste material
generated from the iron blast furnace and subsequently quenched, and

Corresponding author at: Ceramics and Building Materials Department, National Research Center, Egypt.
E-mail addresses: redagado@gmail.com, redagado@hotmail.com (R.A. Gado).
http://dx.doi.org/10.1016/j.psep.2016.08.001
0957-5820/ 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
238 Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251

its composition is essentially that of an overcharge balanced calcium

Table 1 Chemical composition of starting materials,
alumino-silicate framework. Sometimes added to geopolymer systems,
wt.%.
it is well known to increase compressive strength and enhance strength
development at ambient temperatures (Davidovits and Sawyer, 1985). Oxides Content (wt.%)
The use and assessment of many materials contain aluminosili- Waste red clay Ground granulated
cate mineral such as metakaolin, ground granulated blast-furnace slag bricks (G) blast-furnace slag (S)
and types of y ash as potential raw materials for the production of
geopolymer have been extensively investigated and reported (Pacheco- SiO2 50.16 26.15
Torgal et al., 2008; Bernal et al., 2012; Puertas and Fernndez-Jimnez, Al2 O3 15.95 7.43
2003; Lampris et al., 2009) and there is increasing interest in investi- Fe2 O3 15.09 1.31
gating the suitability of using other materials. Geopolymer technology CaO 4.39 44.38
Na2 O 2.43 0.75
is considered to be a relatively new technique, suitable for waste dis-
K2 O 1.48 0.53
posal process and for the full stabilization of substances that would
TiO2 2.10 0.98
otherwise cause much more environmental pollution. It is noted that
MnO 0.16 5.25
researchers have been studied many different industrial by-product
MgO 2.13 5.52
wastes containing silica and alumina, such as red mud (Hajjaji et al.,
SO3 2.78 2.90
2013), rice husk ash (He et al., 2013), coal ashes (Papa et al., 2014), glass
BaO 0.06 4.72
residue waste (Kourti et al., 2010), blast furnace slag (Hu et al., 2008), P2 O5 0.24 0.03
and y ash and blast furnace slag (Nath and Kumar, 2013), construc- Cl 0.46 0.00
tion and demolition wastes (Komnitsas et al., 2015) and ceramic waste LOIa 2.10 0.00
materials (Reig et al., 2013a,b). The results indicate that many of these
industrial by-product wastes are promising materials for the synthesis a
LOI, loss on ignition at 950 C.
of geopolymers.
Reig et al. (2013a,b) aimed to optimize the alkali-activation process
of waste red clay bricks by investigating the effects of different param-
eters on the mechanical strength and microstructure of produced this study will enrich the studies of geopolymer chemistry proper-
geopolymers. Puertas et al. (2006) investigated the alkali-activation pro- ties and provide a promising alternative way to reutilize industrially
cess of ceramic waste materials by using sodium hydroxide and sodium by-products waste economically and environmentally.
silicate solution. Although the achieved compressive strengths were
ranging between 7 and 13 MPa, it was concluded that further investiga-
2. Experimental procedure
tions were required to understand the inuence of different parameters
of the alkali-activation process on the nal properties of the binders
formed. 2.1. Materials and methods
Geopolymerization is a technology that relies on the chemical reac-
tion of amorphous silica and alumina rich solid materials with a The waste red clay bricks (G) used in this study were derived
high alkaline solution at ambient or slightly elevated temperatures to from Misr-Brick Company located in Helwan province, Egypt.
develop a new form of inorganic polymer or geopolymer which con- Water cooled granulated blast-furnace slag was sourced from
sidered as amorphous to a semi-crystalline aluminosilicate material. iron and steel factory located in Helwan province, Egypt. Fig. 1
Geopolymer is a three-dimensional silicon aluminate structure consist-
shows some photos for the starting materials which caused
ing of linked SiO4 and AlO4 tetrahedra by sharing all the oxygen atoms
huge environmentally problems in their factories and area sur-
(Davidovits, 1988, 1991, 1994; Duxson et al., 2007; Majidi, 2009; Shi et al.,
rounded. Due to the large volume of wastes and the limitation
2006; Dimas et al., 2009; He et al., 2012). Due to the sound properties
as well as signicant environmental benets of geopolymer products,
of available landll space, the disposal and utilization process
geopolymer technology has been drawing great interest (Andini et al., of such wastes is an important issue.
2008; Chindaprasirt et al., 2009; Somna et al., 2011). Geopolymer not The starting materials were prepared by crushing and pul-
only provides performance comparable to ordinary Portland cement in verization process in a ball mill for 30 min and for particle
many applications but has additional advantages, including abundant size screening, measured on a Mastersizer 2000 laser ana-
of raw material resources, a rapid hardening, high mechanical strength, lyzer (Malvern, UK). Fig. 2 shows the particle size distribution
excellent durability due to chemical attack resistance, contaminants of starting materials, the average particle size (d50 ) of milled
immobilization and signicantly reduction in energy consumed and waste red clay bricks (G) and granulated blast-furnace slag
greenhouse gas emissions. These characteristics and advantages have
(S) powders are 1100 and 2300 nm, respectively. The specic
made geopolymer of great research interest as a new ideal material
gravity of waste red clay bricks and granulated blast-furnace
for sustainable development (Zhang, 2013). Komnitsas and Zaharaki
slag were 0.6695 and 2.67 respectively. The specic surface
(2007) studied, geopolymers can generally deliver a great reduction in
CO2 emission and require less energy compared with ordinary Port- area of starting raw materials measured by BET technique
land cement products. Thus, geopolymers can be regarded as a green using (Micromeritics, ASAP2020), were 5.19 and 1.75 m2 /g with
concrete (Sumajouw et al., 2007). average particles size based on BET calculation 1155.90 and
The present work is aimed at assessment and utilization of some 3386.06 nm respectively, as shown in Fig. 3. The main oxide
industrial by-product wastes as source based material for geopolymer compositions of starting raw materials chemically analyzed by
production that could be used for construction or restoration purposes. XRF technique were reported in Table 1. The mineral compo-
In this study, waste red clay bricks (Grog) was creatively introduced sition phases of starting raw materials were identied by XRD
to recycling and valorization process and we discuss its suitability
technique using (Panalytical Xpert pro) diffractometer with Ni
for geopolymerization synthesis process in associated with a different
lter, Cu K radiation at a scan speed of 0.5 min1 . FTIR spectra
percentage of ground granulated blast-furnace slag (S). The starting
of starting raw materials were acquired using a JASCO FT/IR-
materials of industrially by-products waste involved in this study
were characterized by different techniques. Moreover, the geopoly-
6100. The IR spectra were recorded between 400 and 4000 cm1
mer products were characterized to determine the physico-mechanical with a resolution of 4 cm1 at room temperature.
properties; X-ray diffraction analysis (XRD); Fourier transform infrared For preparing geopolymer formulations, appropriate
spectroscopy (FTIR) analyses and scanning electron microscopy (SEM) amounts of starting raw materials in predetermined
with energy-dispersive X-ray spectroscopy (EDX). Results obtained in proportions, as shown in Table 2, were taken and ball
 Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251 239

Fig. 1 Photos of waste red clay bricks (G) and granulated blast-furnace slag (S).

30 (A) 30 (B)
Waste fired clay bricks (G) Ground granulated blast-furnace slag (S)
d50 = 2300 nm
d50= 1100 nm
25 25

20 20
Percent, %
Percent, %

15 15

10 10

5 5

0 0
400 800 1200 1600 2000 1000 1500 2000 2500 3000
Size, nm Size, nm

Fig. 2 The particle size distribution of (A) waste red clay bricks (G) and (B) ground granulated blast-furnace slag (S).

milled for 15 min using a top planetary ball mill (Fritsch
planetary mono mill pulverisette 6) for homogenization
process.
A technical grade of sodium silicate (Na2 SiO3 , water-
glass) solution was supplied by Egyptian-Saudi Company for
chemicals industries (ESACI), Egypt, with the chemical compo-
sition of 30.5% SiO2 , 9.5% Na2 O, and 60% H2 O with the modulus
SiO2 /Na2 O of 3.2, density at 20 C of 1.4 g/cm3 , and viscos-
ity at 20 C of 0.4 Pa s. The sodium hydroxide (NaOH) pellet
was extra pure, purity 99%, and was made in India. Distilled
240 Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251

A
16
AdsorptionB
14 DesorptionD

Quantity Absorbed (cm /g , STP)

12

Waste fired clay bricks (G)

3
10
2
BET surface area = 5,19 m /g
8
Average particle size = 1155.90 nm

0
0,0 0,2 0,4 0,6 0,8 1,0

Relative pressure P/P0

B
3,5
AdsorptionB
3,0 DesorptionD
Quantity Absorbed (cm /g , STP)

2,5
Ground granulated blast-furnace slag (S)
3

2,0 2
BET surface area = 1,75 m /g

Average particle size = 3386.06 nm

1,5

1,0

0,5

0,0
0,0 0,2 0,4 0,6 0,8 1,0

Relative pressure P/P0

Fig. 3 The specic surface area (BET) of (A) waste red clay bricks (G) and (B) ground granulated blast-furnace slag (S).

The ratio of Na2 SiO3 to NaOH used was 2.5 by volume

Table 2 The proportions of the formulation mixtures,
wt.%. (Nazari et al., 2011). The alkaline solution was prepared 24 h
prior to sample preparation to ensure good activation of the
Formulations Content (wt.%)
source material in the alkaline solution. The weight ratio of
Waste red clay Ground granulated alkaline liquid to powder mix used was xed at 0.30 for all the
bricks (G) blast-furnace slag (S) formulations (Hardjito et al., 2009).
GS0 100 0
The geopolymer paste was prepared by mixing the source
GS20 80 20 formulation material and the alkaline liquid in the appro-
GS40 60 40 priate proportions by hand in porcelain dish for a period of
GS60 40 60 approximately 5 min. The paste was then poured into PVC
GS80 20 80 mold 25 mm in width and 25 mm in height. The paste was
poured in two layers and each layer was vibrated on a vibrat-
water was used throughout all experiment. NaOH solutions ing table for a period of 1 min. The top surface of the samples
of desired concentrations of 8 mol/L was prepared and cooled was covered with polythene sheet to prevent excessive mois-
down to room temperature then employed in this investiga- ture loss. Finally after 24 h, the prepared cubes were demolded
tion to prepare activating alkaline solutions. for up to 90 days at ambient temperature for curing purpose.
 Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251 241

M: Melilite E: Merwinite hand, the X-ray diffraction pattern of ground granulated

M Ground granulated blast- blast-furnace slag (S) shows a halo hump ranging between
E furnace slag (S)
[(2) = 2040] indicated the amorphous nature of the material
E
with some crystalline phases. Crystalline components such
M M
E as merwinite 2CaOAl2 O3 SiO2 and melilite which consider a
M
solid solution series between gehlenite (2CaOAl2 O3 SiO2 ) and
akermanite (2CaOMgO3 SiO2 ) are present in ground granu-
lated blast furnace slag (S) mainly due to improper quenching
Quartz : Q Albite : A Hematite : H
or cooling stage in the production process (Allahverdi et al.,
Intensity

Q 2011).
A
Q A
AH
5 10 15 20 25 30
2-Theta-scale
Fig. 4 X-ray diffraction (XRD) pattern of starting materials.
3. Results and discussion
3.1. Starting raw materials characterization
Results from X-ray diffraction (XRD) analysis of supplied start-
ing materials, are shown in Fig. 4. The XRD data indicates that
quartz mineral (SiO2 ) is the major crystalline phase present
in waste red clay bricks (G) sample that is mainly due to
the nature of clay and the addition process of sand during
manufacture process of clay bricks. In addition to, amorphous
aluminosilicate materials formed upon the decomposition
and destroy of clay minerals during the ring in the kiln; the
not well crystallized aluminosilicate material is difcult to
observe by XRD technique due to amorphous nature as well as
the presence of albite (NaAlSi3 O8 ) and hematite (Fe2 O3 ) min-
erals as minor constituents (Heikal et al., 2013). On another
The X-ray diffraction analysis of ground granulated blast-
furnace slag (S) sample shows a complex structure with many
overlapping peaks reecting the crystalline phases present in
steel slag. These crystalline phases appear to be mainly due
to the chemical composition of steel slag and the slow cool-
Waste fired clay bricks (G)
ing rate applied during manufacture processing (Yildirim and
Prezzi, 2011).
H
Q Infrared spectra of the starting raw materials are shown in
Q H H
A Fig. 5; FTIR spectrum of waste red clay bricks (G) as received
state shows the presence of characteristic adsorbed hydroxyl
35 40 45 50 55 60 bands at 3548 and 3455 cm1 . The absorption bands observed
at 3455 cm1 and 1630 cm1 could be assigned to the hydroxyl
molecule in water due to the humidity which absorbed dur-
ing storage process at factory landll space. It can also be
noticed that the presence of two minor peaks around 2925
and 2856 cm1 , which are attributed to the antisymmetric
stretching vibration and symmetric stretching vibration of the
methylene group (CH2 ) in the organic impurities possibly
founded in the sample (Zawrah et al., 2014). In addition to, the
presence of some carbonate impurities observes in the spec-
trum at 2362 cm1 . Furthermore, FT-IR spectrum shows main
broadband at wavenumber in the region of 1110 cm1 as well
as other bands located at 460 cm1 which are both expresses
the vibration of SiOAl group of the aluminosilicate materi-
als (Allahverdi and Kani, 2009). In the 1110 cm1 and 1052 cm1
region, main functional groups were assigned to SiO in disor-
der tetrahedral sheet which can be seen from the broadening
of SiO stretching band in this region and this mainly due
to dehydroxylation process during the ring process of brick
manufacture (Nirmala and Viruthagiri, 2014). The doublet at
779710 cm1 as well as the peaks at around 673 cm1 and

Ground granulate blas t-furnace slag (S)

1639

710
1418

760
3422
Transmittance, %

940

513

Waste fired clay bricks (G)

2362, 2323
2925, 2856

1630
3548-3455

779-710
1110- 1052

673
578
460

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber, cm

Fig. 5 FTIR of starting materials.

242 Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251
Fig. 6 SEM micrographs of waste red clay bricks sample (G) with EDX microanalysis.
578 cm1 are attributed to SiOSi inter tetrahedral bridging
bonds in SiO2 which indicates the presence of quartz min-
eral (El-Al and Gado, 2016). On another hand, the spectrum
of the ground granulated blast-furnace slag (S) represents a
broadband at 940 cm1 which mainly characteristic for the
vibration bond of SiOT (where T is Si or Al) bonds of tetrahe-
dral silicates materials with the bands at 760 cm1 , 710 cm1
and 513 cm1 which attributed to the bending vibration mode
of the AlOSi bonds. A band at 1418 cm1 associated with the
asymmetric vibration mode of the OCO bonds in carbonates
was also observed. This is coherent with the partial carbon-
ation identied in this raw material (Bernal et al., 2011a,b)
as a consequence of weathering during storage. Further-
more bands at about 3422 cm1 and 1639 cm1 corresponding
to adsorbed atmospheric water (Torres, 2005; Bernal et al.,
2011a,b). The result illustrated in infrared spectra of the start-
ing raw materials was in agreement with data obtained from
X-ray diffraction analysis (Fig. 4).
Figs. 6 and 7 show the SEM micrographs and EDX micro-
analysis for the starting raw materials. It can be observed
from SEM images of waste red clay bricks waste (G) that
all the particles have nonhomogeneous and angular-shaped
structure morphology as well as a aky appearance with the
presence of brous morphology detrital grains with parti-
cle size distribution ranging from 700 to 1220 nm, as shown
in Fig. 6. Moreover, the SEM micrographs illustrate the wide
range of particle size distribution observed in the sample.
In addition, the line spectrum of the sample, determined by
using EDX unit, indicated the presence of oxygen (O), sili-
con (Si) and aluminum (Al) as a main element in the sample
with a trace of sodium (Na), calcium (Ca), magnesium (Mg)
and iron (Fe) as impurities element. Moreover, SEM micro-
graphs of the ground granulated blast-furnace slag (S) sample
shows a massive stone-shaped morphology as well as angu-
lar irregular particle texture with particle size ranging from
1230 to 2390 nm, as shown in Fig. 7. Furthermore, the line
spectrum of the sample determined by using EDX unit indi-
cated the presence of oxygen (O), silicon (Si) and calcium (Ca)
which appeared with a strong peak at 3.69 keV as a main
element in the sample with a small amount of magnesium
(Mg) and aluminum (Al). These results are consistent with
the chemical composition analysis (XRF) of starting materials
reported in Table 1 and the particle size distribution, as shown
in Fig. 2.
3.2. Characterization of prepared geopolymer
specimens
Cured geopolymer specimens at room temperature were
investigated by different techniques. These included: deter-
mination of physico-mechanical properties (ASTM C20) at
interval cured ages of 3, 7, 28 and 90 days. After the density
determination, the cube specimens were tested to determine
the compressive strength (ASTM: C109/C109M). The compres-
sive strength was measured using automatic hydraulic testing
machine of type SHIMADZU of maximum capacity 1000 kN
by rate of 0.025 kN/mm2 /S. Three specimens for each series
were crushed on a digital compression testing machine and
the average value was reported. After the mechanical test-
ing, parts of fractured specimen were chosen, crushed by hand
with a metallic mortar and pestle. The ground powders were
characterized by X-ray diffraction; Fourier transform infrared
 Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251 243

Fig. 7 SEM micrographs of ground granulated blast-furnace slag sample (S) with EDX microanalysis.

2.25 2.24 14.00

2.22
2.20
12.00
Bulk density, gm/cm+3

2.15 2.14
10.00
A. Porosity, %

2.10 2.09 3 days

3 days 7.88
8.00 7 days
2.05 2.04 7 days
6.77
28 days
28 days 6.00
2.00 5.42
90 days
90 days
1.95 4.00 3.66
3.19

1.90 2.00

1.85
0.00
GSo GS20 GS40 GS60 GS80
GSo GS20 GS40 GS60 GS80
Geopolymer specimens
Geopolymer specimens
Fig. 8 The bulk density of prepared geopolymer at
Fig. 9 The apparent porosity of prepared geopolymer at
different interval curing time.
different interval curing time.

and scanning electron microscopy (SEM, Zeiss-Ultra Plus) with

EDX analysis unit.
3.2.1. Physico-mechanical properties
The physico-mechanical properties of prepared geopolymer
samples at different interval curing time and the trends of the
results are shown in Figs. 811, respectively. From the results
of specimen observations, it is evident that the bulk density
conspicuously increasing as the percent of ground granulated
blast-furnace slag (S) increased in the matrix, as shown in
Fig. 8. As a result of increasing the curing time, the bulk density
of specimens increased also which indicate the densication
enhancement of specimens by curing time as well as the addi-
tion of ground granulated blast furnace slag (S), compared with
those conventional waste red clay bricks (GS0 ) specimen at
the early curing time. On the contrary, the porosity and water
absorption of prepared samples were decreased as a result of
244 Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251

9.00 increasing the bulk density, as illustrated in Figs. 9 and 10. As

8.00
expected, by using ground granulated blast-furnace slag (S) in
geopolymer system leads to a reduction in porosity as well as
7.00
water absorption for geopolymer specimens due to the forma-
5.95 tion of new phases with geopolymer network. Furthermore,
6.00
W. Absorpon , %

3 days
the amount of calcium oxide (CaO) content in the ground
5.00 7 days
granulated blast-furnace slag (S) precursor was found to have
3.90 28 days
4.00 the signicant impact on the resulting hardened geopoly-
90 days
3.00
mer (Nath and Sarker, 2014). The additional of calcium oxide
2.66
sourced from ground granulated blast-furnace slag (S) forms
2.00 1.75
1.42
hydrated products such as calcium silicate hydrates (CSH),
1.00 along with the aluminosilicate network formed in geopolymer
matrix (Yip et al., 2008; Granizo et al., 2002). The geopolymer
0.00
specimen (GS80 ) shows a little increasing in porosity value
GSo GS20 GS40 GS60 GS80
which reects on the value of water absorption by increasing,
Geopolymer specimens
this is mainly due to some crack appeared on the sample (GS80 )
Fig. 10 The water absorption of prepared geopolymer at at curing age 28 days, as shown in Fig. 12. This is not believed
different interval curing time. to be caused mainly due to the sample preparation process,
but rather due to the sample volume changes that could occur
when semi-crystalline phase mainly a type of calcium silicate
hydrates gel forming with a partially hardened amorphous
90.00 phase mainly geopolymer network (Yip et al., 2008).
83.00
80.00
The addition of granulated blast-furnace slag (S) to waste
red clay bricks (G)-based geopolymer system generally leads
70.00
to, an increase in bulk density, a decrease in the porosity
C. Strength, MPa

60.00 58.00 3 days

and water absorption of specimens which positively reect on
7 days the compressive strength, as shown in Fig. 11. Enhancement
50.00
45.00 28 days in compressive strength and decrease in total setting time
40.00 90 days was reported with the increase of calcium oxide content in
33.00
30.00
geopolymer matrix composition (Diaz et al., 2010). Hence, the
compressive strength shows a corresponding increase com-
20.00
15.00 pared with reference samples produced using waste red clay
10.00 bricks (G) as the sole precursor except GS80 specimens which
show deterioration in compressive strength due to the appear-
0.00
ance of some cracks in the sample.
GS0 GS20 GS40 GS60 GS80
As expected, the prolonged curing time improves the
Geopolymer specimens
formation of geopolymer in hard structure specimens. The
Fig. 11 The compressive strength of prepared geopolymer enhancement in compressive strength with curing time
at different interval curing time. occurs mainly because the later stages of geopolymerization
process involving gelation and transformation continue after

Fig. 12 Photographs of GS0 - and G/S2080 -based geopolymer specimens (25 mm 25 mm 25 mm) at 28 days curing time.
 Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251 245

the geopolymer sets (Kourti et al., 2010; Van Deventer et al.,
2007). The 90 days compressive strength values of geopolymer
specimen (GS0 ) gave a lower compressive strength (15 MPa)
than those activated with the inclusion of ground granu-
Quartz : Q (pdf : 87-2096)
Calcium silicate hydrate : CSH (pdf : 03-0594)
Sodium calcium aluminosilicate hydrate : NCASH (pdf : 78-0296)

NCASH
NCASH
lated blast-furnace slag (S). After specimens curing time for

NCASH
CSH
Q

CSH

CSH
CSH
CSH
Q GS
90 days, the highest compressive strength value was recorded Q 80

(83 MPa) for geopolymer specimen (GS60 ), the compressive

strength was duplicated by about six times than conven- Q

tional waste red clay bricks (GS0 ) specimen. The compressive

NCASH
NCASH

NCASH
CSH

NCASH
strength enhancement mainly due to the inclusion of ground

CSH
CSH

CSH

CSH
Q

CSH
Q GS
granulated blast furnace slag into the matrix which leads 60

to reinforcement of the geopolymer gel formed by the addi-

Q
tional calcium silicate hydrates (CSH) phase types added
with geopolymer network upon alkali activation process and

Intensity

NCASH

NCASH
consequently positively reect on the physico-mechanical

CSH

CSH
CSH
Q
Q Q
GS 40
properties of specimens. Generally, there was an enhance-
ment of physico-mechanical properties of specimens as the
Q
amounts of ground granulated blast-furnace slag (S) increases
in specimen up to 60% after that, the specimen shows dete-

NCASH
NCASH
rioration. These results indicate that a moderate addition up

CSH

CSH

CSH
Q GS
Q Q 20
to 60% of ground granulates blast furnace slag (S) in the waste
red clay bricks (G)-based geopolymer will improve the overall
Q
physical properties as well as the mechanical strength.

3.2.2. X-ray diffraction analysis Q GS 0

Q Q
The mineralogical composition of prepared geopolymer spec-
imens after curing time for 28 days at room temperature was 5 10 15 20 25 30 35 40 45 50 55 60

determined by X-ray diffraction analysis technique. Although 2Theta-scale

conventional geopolymers formed after the alkali-activation
processes were mainly amorphous to semi-crystalline, but
some very weak minor crystalline phases that could not be
clearly identied by JCPDS could still be observed (Yip et al.,
2005; Sun et al., 2013). The presence of semi-crystalline phases
due to the formation of new phases upon alkali-activation pro-
cess or as unreacted remain crystalline phases from starting
materials in geopolymer specimens has been detected and
illustrated in Fig. 13.
The XRD data in Fig. 13 shows that quartz mineral (SiO2 )
is the major crystalline mineral phase, and remained as unre-
acted phases in all of the samples after the alkali-activation
process in prepared geopolymer specimens. There is no new
crystalline phase formed as a product of the alkali-activation
process of waste red clay bricks (GS0 ) only in the absence
of ground granulated blast-furnace slag (S). The main peak
of quartz mineral phase in present work is distinguishable,
which mainly would be caused by unreactive of quartz mineral
(SiO2 ) to alkali-activation during geopolymerization process
(Reig et al., 2013a,b; Yao et al., 2009; Bell et al., 2008). XRD
pattern of geopolymer binders (GS20 GS80 ) which composed
of various amounts of starting materials are shown to have
the same XRD pattern features as those pattern generated
by alkali-activation of waste red clay bricks (GS0 ) only but
with the presence of some new semi-crystalline phases on
the geopolymer binder products. It can be observed that, as
the partial replacement of waste red clay bricks (G) and
the employed of ground granulated blast-furnace slag (S)
into the geopolymer matrix system, a new hydration prod-
uct formed in specimens (GS20 GS80 ) mainly composed of
coexisting alkali three-dimensional amorphous aluminosil-
icate nets, so-called geopolymer gel and types of calcium
silicate hydrate phases (CSH) gel which have intense peaks
centered around (2) = 29.2 . Other peaks indicating that cal-
cium silicate hydrate phase (CSH) is present are at (2) = 32.0 ,
42.7 , 49.8 and 55.3 associated with the formation of sodium
Fig. 13 XRD pattern of prepared geopolymer samples
cured for 28 days.
calcium aluminosilicate hydrate phase (NCASH). It is com-
monly acknowledged, that the semi-crystalline phases of
calcium silicate hydrate (CSH) are the major binding product
phase for alkali-activated of ground granulate blast-furnace
slag (S) with low calcium/silicon ratio (Kourti et al., 2011). In
sample (GS60 ), XRD indicates that the inclusion of 60% ground
granulated blast furnace slag (S) with 40% waste red clay
bricks (G) leads to the formation of a new semi-crystalline
phases of calcium silicate hydrate (CSH) and sodium cal-
cium aluminosilicate hydrate phase (NCASH) in parallel with
an amorphous product of geopolymer. This semi-crystalline
phase has a positive effect on the geopolymerization process
by acting as nucleation sites for the formation and accumu-
lation of the amorphous geopolymer products which nally
leads to reinforcing the specimen as well as enhance the
compressive strength. Yip et al. (2008) suggested that in the
presence of calcium oxide, calcium silicate hydrate (CSH) pre-
cipitates and acts as nucleation sites and this promotes the
rapid formation of geopolymer gel.
3.2.3. Fourier transform infrared spectroscopy (FTIR)
analysis
The FTIR spectrum of the selected geopolymer samples (GS0
and GS60 ) cured for 28 days are presented in Fig. 14. Signif-
icant broad bands of OH stretching and OH bending were
observed in the range of 3450 and 1630 cm1 corresponding
to water molecules associated with the reaction products in
all FTIR spectra of selected geopolymer samples. These bands
indicate the presence of water molecules which are surface
absorbed or entrapped in the large cavities of the polymeric
framework of geopolymer product (Fernandez-Jimenez and
Palomo, 2005; Swanepoel and Strydom, 2002). Consequently,
246 Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251
GS 60
3469-3417
Transmittance, %
GS
0
3548-3409
4000 3500
Fig. 14 FTIR spectrum of the selected geopolymer samples GS0 and GS60 cured for 28 days.
increasing this bands intensity in specimen GS60 , indication
for more hydrated calcium silicate products formed such as
calcium silicate hydrate (CSH); sodium calcium aluminosili-
cate hydrate phase (NCASH).
The observed bands at 1423 and 1489 are due to the stretch-
ing vibration of OCO bond in carbonate mineral which is
suggested to have occurred due to atmospheric carbonation
(Fernandez-Jimenez and Palomo, 2005). Moreover, increas-
ing contents of ground granulate blast-furnace slag (S) in
specimen also lead to the growth of the carbonate band at
1423 cm1 which is mainly due to the high percent of cal-
cium oxides in slag. The main band centered at 995 cm1 in
sample GS60 and at 1035 cm1 in sample GS0 are assigned to
the asymmetric stretching vibration of SiOT bands, where
T is tetrahedral silicon or aluminum. These peaks consider
as ngerprints of the geopolymeric network matrix and are
attributed to SiO stretching vibrations of SiO4 and TOSi
asymmetric stretching vibrations during geopolymerization
process which indicate the formation of an amorphous alu-
minosilicate phase. These shifting in FTIR bands were due
to the rise in the tetrahedrally positioned Al atom present
in the geopolymer system (Part et al., 2015). In addition, the
bands located at 777, 667, 600 and 460 cm1 in sample G0
which mainly due to bending vibration of SiOSi and OSiO
as well as the vibration of SiOAl group (Komnitsas et al.,
2015; Fernandez-Jimenez and Palomo, 2005; Van Jaarsveld
et al., 1999). Otherwise, the peak shifts in the FTIR of selected
geopolymer in comparison with spectra of starting materials
explains the changes in the structural nature of the matrix
after alkali-activation process. The main band for binder gel
formed in the specimen (GS60 ) was detected at about 995 cm1
which mainly related to asymmetric stretching mode of the
hydrated calcium silicate (CSH) structure while the geopoly-
mer gels formed in specimen GS0 appeared at 1035 cm1 (Van
Jaarsveld et al., 1999). The presence of unreacted quartz (SiO2 )
in both specimens was conrmed by FTIR by a series of bands
located at 1135, 790, 697 and 522 cm1 . This result correlates
well with the result of X-ray diffraction analysis.
1639,1619
2356, 2321
1423
790
600
995
522
1637,1619
1489, 1423
2362, 2323
2925, 2856
777
667
1135
600
460
1035
3000 2500 2000 1500 1000 500
Wavenumber, cm -1
3.2.4. Scanning electron microscope (SEM)
The morphological and microstructural features of selected
geopolymer samples (GS0 and GS60 ) cured for 28 days were
characterized by scanning electron microscope (SEM) with
energy-dispersive X-ray spectroscopy unit (EDX), which was
used to identify the reaction products, the relative images are
shown in Figs. 15 and 16. SEM investigations can help us to
get a better understanding of the morphologies of the formed
geopolymer composites.
Fig. 15 shows the SEM micrographs and EDX microanaly-
sis for the specimen (GS0 ). The SEM images clearly indicate
the formation of the new phase of geopolymer which totally
different in morphology than the starting material. The alka-
line activation process of the waste red clay bricks (G) lead to
the dissolution process for the aluminosilicate materials pro-
ducing a tetrahedral polymer that is linked together forming
three-dimensional chains spread over the surface of the spec-
imen as seen in the SEM images (Khater et al., 2016). The new
geopolymer phase occurs mainly in the sample as rosettes
of spherulitic aggregates lling the pore spaces of specimens
and binding in a network with the other particles. It is evident
from all SEM images that, the geopolymer gels are identied
in the entire sample, of which the microstructure is contin-
uous and homogenous with some crystals embedded in the
gel matrix. On the other hand, SEM micrograph shows some
large particles embedded in the matrix with partial reaction
during the alkaline activation process which indicates that
the particle size distribution has a main role in completing
the geopolymerization process. It seems that smaller particles
were reacted and dissolved completely during geopolymer-
ization process while the large particles are partially reacted
(Reig et al., 2013a,b). Zhang et al. (2016) reported that the
particle sizes, as well as the specic surface area of starting
raw materials, have the main inuence on its reactivity and
the properties of deriving geopolymer as they determine the
geopolymerization reaction rate and extent. The presence of
unreacted raw materials indicates that the geopolymerization
reaction in specimen GS0 was not complete, these results are
 Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251 247

Fig. 15 SEM micrographs of geopolymer sample (GS0 ) cured for 28 days with EDX microanalysis.

Fig. 16 SEM micrographs of geopolymer sample (GS60 ) cured for 28 days with EDX microanalysis.
248 Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251

Fig. 17 Elemental mapping of the waste red clay bricks sample (G), geopolymer specimens (GS0 ) and (GS60 ).
 Process Safety and Environmental Protection 1 0 3 ( 2 0 1 6 ) 237251
conrming by XRD results (Hajjaji et al., 2013; Slaty et al., 2013).
EDX microanalysis (arrow in Fig. 15) of a new phase formed
upon geopolymerization reaction indicates that the newly
formed geopolymer material is mainly composed of silicon
(Si), oxygen (O), aluminum (Al) and sodium (Na) with pres-
ence of potassium (K) and iron (Fe) which mainly originating
from unreacted raw material residual in specimen. Addition-
ally, the element mapping illustrated in Fig. 17 conrms and
support this result.
Fig. 16 shows the SEM micrographs and EDX microanalysis
for the specimen (GS60 ). SEM micrographs indicating that the
sample (GS60 ) containing 60% ground granulated blast furnace
slag (S) is more compact and massive as well as less porous
than the sample (GS0 ). Moreover, the SEM micrograph depicts
the presence of hydrated calcium silicate (CSH) with the shape
of brous structure morphology. The formation of additional
hydrated calcium silicate (CSH) with the geopolymer gel net-
work leads to enhancement the dense microstructure of the
specimen (GS60 ). This result corroborates and consistent with
that one of the compressive strength. The presence of cal-
cium associated with geopolymer gel network is conrmed
as shown in the EDX microanalysis. The intensity of cal-
cium line counts relative to silicon peak intensity, for instance
increased more than the specimen (GS0 ) which is mainly due
to the inclusion of ground granulated blast furnace slag (S)
in the specimen (GS60 ) and formed a gel more likely as cal-
cium silicate hydrate (CSH). Hence, it is clear that inclusion of
ground granulated blast furnace slag (S) into the sample leads
to the development of different products morphologies and
contributed to the additional binding product which reects
on the microstructure of the sample providing more mas-
sive structure (Nath and Sarker, 2014; Yang et al., 2009). In
other words, the percent of ground granulated blast furnace
slag (S) inclusion into the geopolymer matrix promote the
reaction of the geopolymer system to the formation of other
calcium rich semi-crystalline components which could be the
reasons for enhancement of matrix microstructure as well as
higher mechanical strength (Zhang et al., 2014). Elemental dis-
tribution maps as illustrated in Fig. 17 shows a high-density
calcium-rich layer in comparison with the specimen (GS0 ).
This evidence is more pronounced when the SEM, EDX and
element map image of the specimen (GS0 ) and the specimen
(GS60 ) are compared.
4. Conclusion
This study focuses on the potential of utilizing waste and by-
products from current industrial activities for the production
of geopolymer products. The article has presented the results
of an experimental study that was undertaken to investigate
the assessment of recycling and utilization of waste red clay
bricks (Grog) to produced geopolymer matrix. The geopoly-
merization process for the waste red clay bricks (G) with
alkali aqueous solution of NaOH/Na2 SiO3 was successfully
carried out leading to the production of geopolymer matrix.
The study also discusses its suitability for geopolymerization
synthesis process in associated with a different percentage
of another industrial by-product, ground granulated blast-
furnace slag (S).
This paper presents also an experimental study that aimed
to convert two industrial by-products caused many environ-
mental problems to a potentially useful construction material
through geopolymerization process, resulting in a new type
249
of geopolymer composites. The mineralogy composition and
microstructure morphology of the prepared geopolymer prod-
ucts were also characterized. Based on the experimental
results and observations obtained, the following conclusions
can be drawn:
1. The geopolymerization process of waste disposal material,
waste red clay bricks (Grog), was successfully carried out
leading to the production of geopolymer matrix but with
low compressive strength value within the range of 15 MPa
after curing time 90 days at ambient condition.
2. The characterization of prepared geopolymer matrix
indicates that the alkali-activation process in ambient tem-
perature was incomplete. Hence, further studies on the
chemistry and the condition of alkali-activation process for
waste red clay bricks (Grog) will be required to reach a high
degree of geopolymerization.
3. The inclusion of ground granulated blast-furnace slag (S)
into the waste re clay bricks (G) based geopolymer system
leads to improvement in the physico-mechanical proper-
ties of the geopolymer composite formed.
4. The highest compressive strength value was recorded
83 MPa for geopolymer specimen (GS60 ), which composed
mainly from 40% waste red clay bricks (Grog) and 60%
ground granulated blast-furnace slag (S), the compres-
sive strength was duplicated by about six times more
than conventional waste red clay bricks-based geopoly-
mer specimen (GS0 ).
5. The increasing in inclusion percent of ground granulated
blast-furnace slag (S) up to 80% leads to deterioration in
the specimens by appearing some cracks.
Acknowledgments
The authors wish to gratefully acknowledge the help and sup-
port of the Laboratoire national de mtrologie et dessais (LNE),
France regarding to the facility of characterization section by
using the scientic equipment at Carmen platform. The help
of the laboratory staff of LNE is gratefully acknowledged. The
authors also acknowledge to National Research Center (NRC)
and Institut Francais dEgypte (IFE) for their nancial support
during this study.
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