Applied Clay Science 138 (2017) 114–124

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Applied Clay Science

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

Research paper

Middle Eocene clay from Goset Abu Khashier: Geological assessment and
utilization with drinking water treatment sludge in brick manufacture
MA Tantawy a,⁎, Ramadan SA Mohamed b
a
Chemistry Department, Faculty of Science, Minia University, Egypt
b
Geology Department, Faculty of Science, Minia University, Egypt

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

Article history: This investigation aims to study the physico-ceramic properties of bricks that were made from the Goset Abu
Received 5 November 2016 Khashier clay (Qarara Formation, Middle Eocene deposits, El-Minia, Egypt) replaced with 15–60 wt% drinking
Received in revised form 30 December 2016 water treatment sludge (DWTS). The Qarara Formation deposits located in the east bank of the Nile River be-
Accepted 5 January 2017
tween Beni Suef and El-Minia Governorates, belong to the Middle Eocene deposits. The Qarara Formation de-
Available online 12 January 2017
posits in the Goset Abu Khashier area contain several million tons of clay deposits. The Qarara Formation is
Keywords:
composed of a grey to green shale (silty clay) grading upward to marl and limestone. The clay contains kaolinite
Clay (29 wt%), montmorillonite (20 wt%), albite (27 wt%) and quartz (23 wt%). The clay contains a high content of sil-
Qarara Formation deposits ica (49.41 wt%) and a low content of alumina (19.77 wt%) with considerable amounts of Fe2O3 (11.37 wt%) and
Drinking water treatment sludge fluxing oxides (3.7 wt%). Clay bricks containing 15–60 wt% DWTS were fired at a temperature of 700–1000 °C.
Bricks The ceramic properties of bricks were determined according to the ASTM specifications. The phase composition
Ceramic properties of bricks was determined by XRD, FTIR and SEM techniques. It was investigated that the incorporation of DWTS in
Microstructure the body of clay bricks moderates the ceramic properties of fired bricks to be in agreement with the limiting
values that were recommended for traditional bricks. XRD results illustrated that dehydration of kaolinite and
the formation of metakaolinite facilitates vitrification and contributes to brick densification. FTIR results showed
the formation of a wollastonite phase and indicated that increasing DWTS content facilitates the persistence of a
vitrified phase. SEM micrographs illustrated that the porosity and densification of brick matrix was affected by
the formation of amorphous vitreous phases and decreased with DWTS contents. It is recommended that the re-
placement of examined clay by 15–30 wt% of DWTS is considered as the appropriate percentage for building
bricks production and minimizes environmental impacts due to DWTS disposal into water bodies.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction of clay brick manufacture (Abdel Ghafour, 1995; Ramez and

Clay bricks are traditionally made by shaping, drying and firing mix-
ture of clay and sand to a temperature in the range of 900–1100 °C
(Jackson, 1984). The ceramic properties of clay bricks are primarily de-
termined by the mineralogical composition of raw clay and fired clay
bricks (Janos, 1971; Galal et al., 1985). Abbuoda (1991) and Kamel et
al. (1995) studied the Middle Eocene clay deposits, in east Beni Mazar
and in east Maghagha, El-Minia, Egypt. They recommended that these
clay deposits were suitable for the manufacturing of clay bricks
(Abbuoda, 1991; Kamel et al., 1995). The physico-ceramic properties
of the Qarara Formation clay deposits in El-Mohasham area, Middle Eo-
cene, Middle Egypt, El-Minia were investigated (Othman et al., 2003).
The results obtained indicated that the deposits consist of low grade
clay that can produce heavy bricks with relatively low mechanical prop-
erties. This limits the utilization of the Qarara Formation clay in the field
⁎ Corresponding author.
E-mail address: matantawy75@yahoo.com (M.A. Tantawy).
Ramchandran, 1993). Hence, much effort must be conducted to find
suitable additives that must be added to the Qarara Formation clay to
improve the mechanical properties of clay brick. After the innovation
of high performance concrete, traditional clay bricks no longer satisfy
the requirements of modern, sustainable building technology, because
of its heavy weight and limited thermal insulation properties (Bories
et al., 2014). Many additives have been added to clay to improve certain
properties of clay bricks (e.g. reducing brick weight and increasing its
thermal insulation ability). According to Chiang et al. (2009), the
amount of brick inner pores is a controlling factor. The nature and
amount of the additives have a direct impact on the physical properties
of the bricks. Lightweight bricks were usually manufactured by adding
combustibles as pore forming agents and agricultural wastes (e.g. corn
cob (Nkayem et al., 2016), seeds (Saiah et al., 2010), grass (Demir,
2008), olive mill solid residue (La Rubia-García et al., 2012), sunflower
seed shell (Banhidi and Gomze, 2008), rice husk (Chiang et al., 2009),
rice husk ash (Sutas et al., 2012) and rice peel (Banhidi and Gomze,
2008)) as well as industrial wastes (e.g. sawdust (Demir, 2008), bagasse

http://dx.doi.org/10.1016/j.clay.2017.01.005
0169-1317/© 2017 Elsevier B.V. All rights reserved.
 M.A. Tantawy, R.S.A. Mohamed / Applied Clay Science 138 (2017) 114–124
Goset Abu Khashier
Fig. 1. The geologic and location map of the studied area (modified after EGPC-Conoco, 1987).
(Eliche-Quesada et al., 2011), kraft pulp residues (Demir et al., 2005),
recycled paper processing residues (Sutcu and Akkurt, 2009), polysty-
rene (Veiseh and Yousefi, 2003) and sewage sludge (Weng et al.,
2003)). It is necessary to find a compromise between its thermal and
mechanical properties in order to produce a good quality lightweight
brick (Bories et al., 2014). DWTS is a waste of drinking water treatment
industry that uses alum coagulant in clarification of raw water
(Goosens, 1996). The amount of DWTS reaches about 5 wt% of the
total untreated water quantity (Vaebi and Batebi, 2001). DWTS com-
poses of inorganic substances (e.g. silica, aluminum and iron hydrox-
ides) and organic substances (Miroslav, 2008). The common practice
in handling with DWTS in developing countries is disposing it to the
nearest water stream. This practice has an adverse impact on the envi-
ronment due to rising the concentrations of aluminum and heavy
metals in raw water (Prakhar and Arup, 1998). The problem of DWTS
disposal can be resolved by reusing DWTS as an additive in brick making
(Elangoven and Subramanian, 2011; Hegazy et al., 2012; Anyakora,
2013). The aim of this work is to study the physico-ceramic properties
of bricks that were made from the Goset Abu Khashier clay, replaced
by 15–60 wt% of DWTS and fired at 700–1000 °C as well as the determi-
nation of crystalline phases composition of bricks by XRD, FTIR and SEM
techniques. Other works (Elangoven and Subramanian, 2011; Hegazy et
al., 2012 and Anyakora, 2013) measured only the ceramic properties of
115
fired bricks without analyzing fired bricks. In the present study the
DWTS addition will be raised to 60% and the ceramic properties of
fired bricks will be aided and explained by XRD, FTIR and SEM analyses
of fired bricks.
2. Location and geological setting
The outcrops of Middle Eocene deposits were exposed in the east
bank of the Nile River between Beni Suef and El-Minia Governorates.
This area displays a complex variation in lithology and hence has been
given formational names (e.g. Samalut, Maghagha, Qarara, and El-
Fashn Formations) (Bishay, 1966; El-Ayyat, 1998). The term “Qarara
Formation” was described as the succession that underlies the El-
Fashn Formation and overlies the Maghagha Formation at Gebel Qarara
that forms the Northern boundary of Maghagha district and extends to
Gebel Merier and Wadi Tarfa in the Eastern Desert (Bishay, 1966). Ac-
cording to a recent investigation, the Qarara Formation was described
as the succession that overlies the Samalut Formation and underlies
the building stone horizon (the Observatory Formation) (El-Ayyat,
1998). The Qarara Formation clay deposits, which cover more than
200 km2, are composed of grey to green shale at its base and grading up-
ward to marl and limestone at the top. Representative clay samples
were collected from the Qarara Formation shale deposits in Goset Abu
116 M.A. Tantawy, R.S.A. Mohamed / Applied Clay Science 138 (2017) 114–124

Fig. 2. The litho-stratigraphic sections of the Qarara Formation at Goset Abu Khashier.

Khashier area, Middle Egypt (Lat. 28° 28′ 48.6″ N, Long. 30° 57′ 20.7″ E) accessible are located about 60 km Northeast Minia town, Middle
as illustrated in the geologic and location map of Goset Abu Khashier Egypt. Goset Abu Khashier clay deposits extend roughly NW-SE as sep-
area (Fig. 1) (Egyptian General Petroleum Corporation, EGPC-Conoco arated hills and scarps covering about 1 × 1.6 km2 with an average
Coral, 1987). Goset Abu Khashier clay deposits which are easily thickness of 8–35 m containing several million tons of clay deposits

Fig. 3. (a) The panoramic view of subdivisions of the Qarara Formation sediments at Goset Abu Khashier, (b) The Qarara Formation lower unit at Goset Abu Khashier.
 M.A. Tantawy, R.S.A. Mohamed / Applied Clay Science 138 (2017) 114–124 117

700-1000 oC

573 oC

30 min 60 min 24 hr
Time

Fig. 6. The heating curve used in bricks firing.

veins and little plant remains and carbonaceous matter (Fig. 3b). This
shale is laminated and rippled, and blocky in weather surfaces
enveloped by a thin dark grey silcrete. The middle unit is represented
Fig. 4. Microscopic photo of the Qarara shale at Goset Abu Khashier.
by green glauconitic sand intercalated by green shale. The upper unit
composes of oyster nodular nummulitic limestone. The microscopic
photo of the Qarara shale at Goset Abu Khashier shows that the shale
(El-Ayyat, 1998). The Qarara Formation was subdivided into three infor-
matrix is composed of clay fraction ranges from 52.23 to 94.56 wt%
mal local units (from the base to top); homogeneous grey to green
and silt fraction (quartz and feldspars) from 5.45 to 15.14 wt%. The
shales, sandy marl and bedded to poorly cross bedded sandstones, inter-
calated with highly fossiliferous oyster limestone bands (Mansour et al.,
1983). The stratigraphic sections of the Qarara Formation at Goset Abu
Table 1
Khashier are represented by about 50 m in thickness of Middle Eocene Chemical composition of investigated clay and
(Lutetian) (Fig. 2). The Qarara Formation is composed of three units as DWTS.
illustrated in the panoramic view of subdivisions of the Qarara Forma-
Weight, wt%
tion sediments at Goset Abu Khashier (Fig. 3a). The lower unit composes Oxide
of green, yellowish-grey and dark grey shale (about 20 m) containing Clay DWTS

lenticular patches of reddish yellow clay rich in iron oxide, gypsum SiO2 49.41 59.70
Al2O3 19.77 10.52
CaO 0.61 6.01
Fe2O3 11.37 4.38
Clay and DWTS MgO
SO3
1.74
0.62
2.20
2.85
Na2O 0.48 1.53
K2O 0.87 1.16
Cl− 0.56 0.12
Drying LOI
Total
14.17
99.60
11.10
99.57

Grinding and sieving Q

(125 µm sieve)
Relative Intensity, %

Q
Blending and mixing
Clay
Al
Mt
Addition of 10% water Kao Q
Kao Q Mt
Kao Kao Kao Kao Q Q
Kao

Pressing (20 kg/cm2) Al

Q
DWTS Q
Q Q
Q
C Q

Drying in air for 24 hours and

at 105oC for 24 hours
0 10 20 30 40 50 60 70
Firing in muffle furnace at 2
700-1000 oC
Fig. 7. XRD pattern of clay and DWTS (Al albite, C calcite, Kao kaolinite, Mt.
Fig. 5. Clay brick preparation process. montmorillonite and Q quartz).
118 M.A. Tantawy, R.S.A. Mohamed / Applied Clay Science 138 (2017) 114–124

3. Materials and experimental techniques

Clay

Four clay samples were taken from the bottom to top of the Goset
Relative transmittance, %

Abu Khashier clay location. The collected samples were subjected to

Q
Q various analytical techniques for textural, petrographic, mineralogical
R
W and chemical analyses. One representative sample was prepared by
A
K DWTS K mixing equal proportions by weight of the collected clays. Wet DWTS
K K HQ
W
K was collected from drinking water treatment plant that uses alum coag-
ulant in water treatment process. DWTS was dried and milled in steel
G C S ball mill to fine powder. The clay brick preparation process was de-
scribed as follows (Fig. 5). Dried clay and DWTS with particle sizes
G less than 125 μm were blended to produce homogenous mixes contain-
G
S ing DWTS additions of 0, 15, 30, 45, and 60% (by weight) on a dry basis.
S These clay mixes were symbolized as C, A1, A2, A3 and A4 respectively.
Pressed samples were prepared by adding 10% water (by weight) to the
4000 3600 3200 2800 2400 2000 1600 1200 800 400 dry powder and uni-axially pressed at 20 kg/cm2 for 1 min using a man-
ual hydraulic press machine to form 23 mm diameter cylindrical test
Wavenumber, cm-1 specimens that were approximately 13 mm in height. Taking into con-
Fig. 8. FTIR spectra of clay and DWTS (Al albite, C calcite, H hematite, Kao kaolinite, Mt sideration that working on small cylindrical specimens should produce
montmorillonite, Q quartz, R carbonaceous matter, S silica and W water). bricks with lower compressive strength than that which would be ob-
tained if standard brick sizes (25 × 12 × 6.5 cm) were used due to size
silty quartz grains were sub-rounded to angular and concentrated into effect (Neville, 1989). The heating curve used in bricks firing is as fol-
discrete silty laminae while the reminders are abundant in a clay matrix lows (Fig. 6). The temperature was raised at a constant rate of 100 °C/
(Fig. 4). h in an electric furnace with a dwell at 573 °C for 30 min to overcome

Clay

266 864
69 493

1 DWTS
2

3
4

Fig. 9. TGA/DrTGA/DTA thermograms of clay and DWTS.

 M.A. Tantawy, R.S.A. Mohamed / Applied Clay Science 138 (2017) 114–124 119

C A1 A2 A3 A4 C A1 A2 A3 A4
15 8

Linear shrinkage, %
max. 15% max. 8%

Ignition loss, %
13 6

11 4
9 2
7 0
550 700 850 1000 1150 550 700 850 1000 1150
Firing temperature, °C Firing temperature, °C

Fig. 10. Ignition loss and linear shrinkage of bricks fired at 700–1000°C.

peaks, using X'Pert HighScore Plus software and JCPDS-ICDD data

C A1 A2 A3 A4
base. The standard deviation was ±5%. Fourier transform infrared anal-
ysis was performed using a spectrometer Perkin Elmer FTIR System
28
Spectrum X in the range 400–4000 cm−1. Scanning electron microscope
Water absorption, %

analysis was carried out using a Jeol-Dsm 5400 LG apparatus. Thermo-

24
20
max. 20%
16
12
550 700 850
Firing temperature, °C
Fig. 11. Water absorption of bricks fired at 700–1000°C.
the deleterious cracking which arises from α-β quartz inversion. The
soaking time after reaching the desired temperature (700, 850 and
1000 °C) was 1 h. Fired test specimens were left in the muffle to cool
down to room temperature, then removed from the muffle furnace,
and stored in a desiccator. For each mix composition, a set of four test
specimens were prepared and fired. Three specimens were used for de-
termination of the physico-ceramic properties and one specimen was
kept as a reference. The ceramic properties of the fired bricks in term
of linear shrinkage, ignition loss, bulk density, apparent porosity,
water absorption and compressive strength were determined according
to the ASTM specifications (Standard C210-95, 1995; Standard C373-88,
1988). X-ray fluorescence analysis was carried out using a Philips
PW1606 X-ray fluorescence spectrometer. X-ray diffraction analysis
was carried out using a Philips X-ray diffractometer PW 1370, Co. with
Ni filtered CuKα radiation (1.5406 Å). The semi-quantitative phase de-
termination was estimated by measuring the areas of representative
gravimetric analysis/differential thermal analysis (TGA/DrTGA/DTA)
were measured by Shimadzu corporation thermo analyzer with DTG-
60H detector with 10 °C/min heating rate from room temperature up
to 1000 °C, under air atmosphere at 40 ml/min flow rate, the hold
time at the appropriate temperature is zero.
4. Results and discussion
1000 1150
Clay is composed of high content of silica (49.41 wt%) and low con-
tent of alumina (19.77 wt%) in addition to considerable amounts of
Fe2O3 (11.37 wt%) and about 3.7 wt% of fluxing oxides (alkali and alka-
line earth oxides) (Table 1). Therefore, the investigated clay sample can
be considered as low-grade ferruginated clay. DWTS contains higher
SiO2 content (59.70 wt%), lower content of Al2O3 (10.52 wt%) and
Fe2O3 (4.38 wt%) as well as higher content of fluxing oxides
(10.9 wt%) and loss on ignition (LOI) (11.1 wt%) when compared with
clay. As the chemical composition of DWTS is similar to clay, its poten-
tial use as partial replacement of clay in clay brick manufacturing is pos-
sible. It can be predicted that DWTS (being has significant loss on
ignition) effectively can be used as pore forming agent in clay bricks.
The crystalline phases that were detected from the XRD pattern of
clay sample (Fig. 7) are kaolinite (29 wt%), montmorillonite (20 wt%),
albite (27 wt%) and quartz (23 wt%). The crystalline phases that were
detected in DWTS are quartz (50 wt%), albite (30 wt%) and calcite
(21 wt%). The main constituents that were detected from the FTIR spec-
tra of clay (Fig. 8) according to their characteristics absorption bands are
quartz (794, 694 and 470 cm− 1), albite (428 cm− 1), hematite
(535 cm−1), kaolinite (3697, 3622, 1034 and 915 cm−1) and montmo-
rillonite (3445 cm−1) (Ravisankar, 2009). The characteristic stretching
vibration band of (OH−) of (Al\\Al\\OH) and (Al\\Mg\\OH) groups

C A1 A2 A3 A4 C A1 A2 A3 A4

2.0 41
Apparent porosity, %
Bulk density, g/cm3

1.9 1.8 - 2.0 g/cm3

37
1.8
33
1.7
1.6 29
1.5 25
550 700 850 1000 1150 550 700 850 1000 1150
Firing temperature, °C Firing temperature, °C

Fig. 12. Bulk density and apparent porosity of bricks fired at 700–1000°C.
120 M.A. Tantawy, R.S.A. Mohamed / Applied Clay Science 138 (2017) 114–124

C A1 A2 A3 A4 mineral structure of montmorillonite and kaolinite. The endothermic-

exothermic ‘S’ shaped peak at 900–1000 °C is attributed to structural re-
600 organization and formation of the Al\\Si spinel phase due to incorpora-
Compressive strength,

500 tion of Si in the γ-Al2O3 (Basta et al., 1982). In case of DWTS, the first
weight loss (at 34–258 °C) is due to loss of moisture. The second weight
400
kg/cm2

loss (around 489 °C) is due to formation of boehmite (AlOOH) by the

300
200 min. 100 kg/cm2
100
0
550 700 850 1000
Firing temperature, °C
Fig. 13. Compressive strength of bricks fired at 700–1000°C.
of montmorillonite at 3624 cm−1 overlaps with the stretching vibration
band of inner (OH−) groups of kaolinite (Vaculikova and Plevova,
2005). Absorption bands at 3425 and 1630 cm− 1 are attributed to
stretching and bending vibrations of (OH−) groups of absorbed water
(Madejova and Komadel, 2001). Absorption band at 1384 cm−1 attrib-
uted to carbonaceous matter (Sankaran and Ramasamy, 2000). In case
of DWTS, the absorption bands of silica appear at 1105, 800 and
474 cm−1 which are attributed to asymmetric stretching vibration of
Si\\O\\Si, symmetric stretching vibration of Si\\O\\Si, and bending vi-
bration of O\\Si\\O respectively (Baltakys et al., 2007). The absorption
bands of gibbsite [Al(OH)3] at 530, 1628, and 3458 cm−1 are attributed
to the Al\\O stretching vibration, bending vibration of water molecules
chemically associated with Al(OH)3 as well as OH stretching of Al(OH)3
respectively (Parveen et al., 2013). The absorption band of carbonate
appears at 1442 cm−1 (Gadsden, 1975). The TGA/DrTGA/DTA thermo-
grams of clay and DWTS (Fig. 9) illustrates the thermal behavior of
clay. The endothermic peak existing at 69 °C is attributed to the loss of
adsorbed water that exists in the inter layer spaces of montmorillonite
structure. The weak endothermic peak at 266 °C is attributed to the de-
hydroxylation of iron hydroxides and/or gibbsite. The endothermic
peak existing at 493 °C is attributed to the dehydroxylation of the clay
dehydroxylation of Al(OH)3 (Violante and Huang, 1993). The third
weight loss (around 625 °C) is due to the formation of Al2O3 (Yusoff
and Muslimin, 2007). The fourth weight loss (around 938 °C) is due to
decomposition of carbonate (Platret and Deloye, 1994). Results of ther-
mal analysis are in agreement with that obtained by XRD and FTIR anal-
1150
yses. The ignition loss and linear shrinkage (Fig. 10) decrease with
DWTS content but increase with firing temperature. During firing, clay
particles fuse together leading to greater proximity and thus enhancing
linear shrinkage (Martínez et al., 2012). DWTS has lower ignition loss
compared to clay as reported in XRF results (Table 1). Therefore, as
the DWTS content increases the ignition loss decreases. The ignition
loss and linear shrinkage increase rapidly after 850 °C due to the decom-
position of clay minerals (Sabrah et al., 1982). Clay bricks without addi-
tion of DWTS show high ignition loss, which could induce densification
of the fired bricks that could affect compression properties and weaken
the structure of the fired bricks (Lin, 2006). Incorporation of DWTS in
the body of clay brick decreased the ignition loss to be lower than the
maximum value that was recommended for traditional brick (15%)
(Weng et al., 2003). Clay bricks without the addition of DWTS show
high linear shrinkage, which could cause tension and breakage of fired
bricks (Perez-Villarejo et al., 2012). Incorporation of DWTS in the body
of clay bricks decreased the linear shrinkage to be lower than the max-
imum value that was recommended for traditional bricks (8%) (Weng et
al., 2003). Water absorption (Fig. 11) decreases with firing temperature.
As the firing temperature increases, clay minerals dehydrate
transforming to amorphous vitreous ceramic minerals which close
some of the open pores (Eliche-Quesada et al., 2011). Water absorption
decreases with DWTS content at firing temperatures below 850 °C be-
cause addition of DWTS decreases linear shrinkage (Fig. 10). Water ab-
sorption increases with DWTS content at firing temperatures above
850 °C because DWTS increases the apparent porosity (Fig. 12) as a re-
sult of macropore connection (Eliche-Quesada et al., 2011). The addition

A1

A2

A3

A4

Fig. 14. Visual inspection of unfired clay bricks fired at 850°C.

 M.A. Tantawy, R.S.A. Mohamed / Applied Clay Science 138 (2017) 114–124 121

Q
(a) Mt
(b)
H
Q Al Al
o Al Mt Q Q
C 700 C Mt
A2 700oC

Relative Intensity, %
Relative Intensity, % Q Mt Q

Mt
Q Al Al Al
Mt Q Mt Q Q Q Q
Q
C 850oC A2 850oC Q
Q
Q
Al Q
Q
Q Q Al Q
Al Q
Al Q H H
Al Al o H Q Q
C 1000oC A2 1000 C

10 20 30 40 50 60 10 20 30 40 50 60
2 2
Q

(c)
Q Al Al
A1 850oC Q Q Q Q Q
Relative Intensity, %

Al
Q Q Q Q Q
Q
A2 850oC Q

Q
H
Cr Al Cr
H
H
A4 850oC Q Cr Q

10 20 30 40 50 60
2

Fig. 15. XRD patterns of bricks, (a) C fired at 700–1000°C, (b) A2 fired at 700–1000°C and (c) A1, A2 and A4 fired at 850°C (Al albite, C calcite, Cr crystobalite, H hematite, Mt.
montmorillonite and Q quartz).

of DWTS facilitates the passage of water, hence water absorption in- behavior of clay previously illustrated in DTA of clay (Fig. 9). At 900–
creases (Othman et al., 2003). Incorporation of DWTS in the body of 1000 °C clay undergoes major structural reorganization due to the
clay bricks slightly increased the water absorption of bricks that were transformation of clay into ceramic minerals as proved by the formation
fired above 850 °C to be lower than the maximum value that was rec- of the Al\\Si spinel phase (Basta et al., 1982). Detailed explanation also
ommended for traditional bricks (20%) (Weng et al., 2003). Large was provided in FTIR results (Fig. 16a).
water absorption capacity may adversely affect the durability of the The bulk density of clay bricks that contain DWTS are in the normal
fired brick and its resistance to natural conditions (Matori et al., range that is recommended for traditional bricks (between 1.8 and
2012). Apparent porosity (Fig. 12) decreases whereas bulk density in- 2 g/cm3) (Weng et al., 2003). Much reduction in bulk density of fired
creases with firing temperature because clay minerals dehydrate to bricks could lead to structural and mechanical defects. Although, there
amorphous vitreous ceramic minerals that close some of the open is no fixed maximal porosity for clay bricks, a very high porosity value
pores. Apparent porosity decreases and bulk density increases with could be problematic since the material would be very fragile (Bories et
DWTS content at firing temperatures below 850 °C because addition al., 2014). Compressive strength (Fig. 13) decreases with DWTS content
of DWTS enhances compaction of brick matrix and closing some of the because it replaces clay which dehydrate to amorphous vitreous phases
open pores. Apparent porosity increases and bulk density decreases that bind the components of brick matrix. Compressive strength increases
with DWTS content at firing temperatures above 850 °C due to in- with firing temperature up to 850 °C then it decreases above 850 °C. The
creased number of pores created by the dissociation of clay minerals compressive strength of the brick samples that were made with 15–
and DWTS and decomposition of carbonaceous matter as well as com- 30 wt% DWTS are closer to that of bricks that were made from clay
bustion of the organic matter (Othman et al., 2003; Bories et al., only. The compressive strength of bricks that contain DWTS is higher
2014). The origin of organic matter of the clay is the remains of plant than the minimum value that is recommended for traditional bricks
matter. The origin of carbonates of the DWTS waste are dissolved (100 kg/cm2) (Weng et al., 2003). Brick samples of all mix compositions
CaCO3 and MgCO3 content of hard water from which DWTS waste pre- are characterized with smooth surfaces without appearance of cracks as
cipitates. The change in the trend of physical properties (water absorp- illustrated in the visual inspection of unfired clay bricks and that were
tion, apparent porosity and bulk density) at a temperature of 1000 °C fired at 850 °C (Fig. 14). The reddish color observed in fired bricks
with the addition of DWTS could be explained according to the thermal might be due to the presence of hematite which is one of the most intense
122 M.A. Tantawy, R.S.A. Mohamed / Applied Clay Science 138 (2017) 114–124

(a) C 700oC
1000 °C. This may explain why these bricks showed lower mechanical
properties at 1000 °C. Al\\Si spinel phase that has been detected in DTA
Relative transmittance, %

Q results proves that this phase is formed prior to mullite formation during
W W
1627 Q 691 firing of the examined clay (Oikonomopoulos et al., 2015). According to
3444
C 850oC 791 Q literature, the metakaolinite transforms to Al\\Si spinel at a temperature
471 around 980 °C (Sonuparlak et al., 1987), whereas the mullite phase usual-
L
1091 ly appears at a temperature around 1100 °C (Chen et al., 2000). Hematite
C 1000oC results due to the dehydroxylation of iron hydroxides (Basta et al., 1982)
or decomposition of the phyllosilicates (Escalera et al., 2014). In the XRD
patterns of A1, A2 and A4 fired at 850 °C (Fig. 15c), cristobalite (JCPDS 76-
0940) appears at the expense of quartz with increasing DWTS contents
due to the conversion of silica at higher temperatures (Tantawy et al.,
2014). In the FTIR spectra of fired bricks (Fig. 16), the main constituents
that were detected in C and A2 bricks fired at 700 °C are quartz (795,
4000 3600 3200 2800 2400 2000 1600 1200 800 400 695 and 470 cm−1), wollastonite (1085 cm−1) and hematite
(475 cm−1). While, orthoclase (635 cm−1) was detected in bricks that
Wavenumber, cm-1 were fired at 850 and 1000 °C. The absorption band at about 800 cm−1
(b) A2 700oC which is corresponding to Si\\O\\Al vibrations that is a characteristic of
the degree of disorder in metakaolin structure (Liew et al., 2012) overlaps
Q with the (Si\\O\\Si) stretching vibration band of quartz (Baltakys et al.,
W Q 691
W 1627
2007). Wollastonite would result from the reaction of SiO2 derived from
791
Relative Transmittance, %

3444 A2 850oC Q clay minerals decomposition with CaO from carbonates decomposition
471
when the temperature reaches 900 °C (Barilaro et al., 2008). The transfor-
L
mation of the clay minerals during heating is reflected in the 3800–
1091
3700 cm−1 and 1100–900 cm−1 regions. The main features are; disap-
A2 1000oC
pearance of the absorption bands at 3800–3700 cm−1 region and that
at 915 cm−1 (which is due to Al(OH) vibrations in octahedral sheet struc-
ture) as well as broadening and shifting of the Si\\O stretching band in
the 1100–1000 cm−1 region to a higher wavenumber. These changes
indicate the lose of crystalline hydroxyl groups of clay minerals and the
destruction of their layer structures, followed by a crystal frame-work col-
lapse and tetrahedral sheet disorder with raising heating temperature
4000 3600 3200 2800 2400 2000 1600 1200 800 400 (Prost et al., 1989). The broadening of absorption bands at 1100–
1000 cm−1 region and shifting to higher wavenumbers, with increasing
Wavenumber, cm-1 DWTS addition (Fig. 16c) indicates the persistence of a vitrified phase
that is formed during firing and thus may encourage the formation of
(c) A1 850oC
mullite at higher temperature (Padmaja et al., 2001) that contributes to
the durability of bricks (Viswabaskaran et al., 2003). The SEM micro-
W Q graphs of raw clay illustrate the wave-like and laminated microstructure
Relative Transmittance, %

W 1627 Q 691
3444 o
A2 850 C 791 of kaolinite and montmorillonite minerals of raw clay samples respective-
Q
ly (Fig. 17a). The SEM micrographs of C and A2 that were fired at 700–
471
1000 °C illustrates that the compact matrix of clay diminishes as a result
L
1091 of shrinkage that accompanies dehydration of clay minerals leading to
o
A4 850 C formation of porous matrix in the case of brick that were fired at 850 °C
(Fig. 17b). The matrix was densified in the case of bricks that were fired
at 1000 °C due to the formation of amorphous vitreous phases. Bricks
that were made from clay alone have a densified matrix compared to
that containing DWTS. This is due to the former enriched with the
amorphous phase that resulted from dehydroxylation of clay minerals.
The SEM results show that the porosity of clay bricks enhances with incor-
poration of DWTS due to the increased number of pores created by the
4000 3600 3200 2800 2400 2000 1600 1200 800 400
decomposition of carbonaceous matter which DWTS contains (Fig. 17c).
Wavenumber, cm-1 The SEM micrographs of A1, A2 and A4 that were fired at 850 °C show
that the porosity of clay bricks decreases with DWTS content due to the
Fig. 16. FTIR spectra of bricks, (a) C fired at 700–1000°C, (b) A2 fired at 700–1000°C and formation of Al\\Si spinel vitrified phase (Fig. 17d).
(c) A1, A2 and A4 fired at 850°C (L wollastonite, Q quartz and W water ).
5. Conclusion

coloring material and only 1–1.5 wt% of hematite is enough to give a
reddish color to fired bricks (Schwertmann, 1993). In the XRD patterns
of C and A2 fired at 700–1000 °C (Fig. 15a and b), from 700 °C onwards,
dehydroxylation of kaolinite is accompanied with the appearance of an
amorphous phase which could be metakaolinite (Kakali et al., 2001).
Formation of amorphous phases, which in turn facilitates vitrification
and contributes to brick densification according to Nkayem et al., 2016,
enhances with firing temperature up to 850 °C then decreases at
This investigation studied the geological assessment of clay from the
Goset Abu Khashier area and the physico-ceramic properties as well as
the phase composition of bricks that were made from this particular
clay replaced with 15–60 wt% DWTS. Based on this investigation, the
main conclusions are:
1. The Qarara Formation deposits in the Goset Abu Khashier area
(Lat. 28° 28′ 48.6″ N, Long. 30° 57′ 20.7″ E) extend as separated
 M.A. Tantawy, R.S.A. Mohamed / Applied Clay Science 138 (2017) 114–124 123

(a)
Raw clay

(b)
C 700oC C 850oC C 1000oC

(c)
o o
A2 700 C A2 850 C A2 1000oC

(d)
o
o
A1 850 C A2 850 C A4 850oC

Fig. 17. SEM micrographs of (a) raw clay, (b) C fired at 700–1000°C (c) A2 fired at 700–1000°C and (d) A1, A2 and A4 fired at 850°C.

hills and scarps containing several million tons of clay deposits. The
deposits compose of three units; shale containing clay, sand interca-
lated by green shale and limestone.
2. The investigated deposits consist of low-grade ferruginated clay
whereas DWTS could be added as a pore forming agent in clay bricks
manufacturing.
3. The crystalline phases that were detected in clay are kaolinite, mont-
morillonite, albite, hematite and quartz while in DWTS they are
quartz, albite and calcite.
4. Compressive strength increases with a firing temperature up to
850 °C then it decreases above 850 °C. The formation of amorphous
phases, which in turn facilitates vitrification and contributes to
brick densification enhances with firing temperatures up to 850 °C
then decreases at 1000 °C. This may explain the decrease of mechan-
ical properties of bricks fired at 1000 °C.
5. The incorporation of DWTS in the body of clay bricks moderate the
ceramic properties of fired bricks (ignition loss, linear shrinkage,
water absorption, bulk density and compressive strength) to be in
agreement with the limiting values that were recommended for
traditional bricks.
6. Replacement of examined clay by 15–30 wt% of DWTS is considered
as the appropriate percentage for building bricks production. Such
implementations would lead to lower production costs, and mini-
mizing environmental impacts due to DWTS disposal into water
bodies.
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