Case Studies in Construction Materials 7 (2017) 144–153

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Case Studies in Construction Materials

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Case study

Complete characterization of Berrechid clays (Morocco) and

T
manufacturing of new ceramic using minimal amounts of feldspars:
Economic implication
Ahmed Mannia, Abdelilah Elhaddarb, Abdeslam El Bouaria,
⁎
Iz-Eddine El Amrani El Hassanic, Chaouki Sadika,
a
Laboratory of Physical Chemistry of Applied Materials (LPCMA), Department of Chemistry, Faculty of Sciences Ben Msik, Hassan II University,
Casablanca, Morocco
b
Laboratory of Applied Geosciences, Faculty of Sciences, University of Mohammed 1, Oujda, Morocco
c
Department of Earth Sciences, Scientific Institute, University Mohammed V, Rabat, Morocco

AR TI CLE I NF O AB S T R A CT

Keywords: This work proposes the mixing of two varieties of Moroccan clay (C1 and C2) with silica sand in
Clays order to minimize the amount of the feldspar used. The raw materials were previously char-
Mineralogy acterized in terms of their composition and thermal behavior. Two formulations noted M1 and
Geochemistry M2 were elaborated according to the experimental protocol and they were evaluated in terms of
Ceramic properties
their mechanical and thermal characteristics. The addition of C2 clay in the formulation allows a
Morocco
reduction in the amounts of feldspar of the order of 5%, while improving the technological
characteristics of this new ceramic (M2) compared to that obtained by the conventional for-
mulation. Indeed, the obtained ceramic (M2) shows the following characteristics: porosity
(11.65%); density (2.71 g/cm3); shrinkage (4.91%); flexural strength (30.05 N mm−2) and
thermal conductivity (2.73 W/mK). Results of this study permit a reduction in the amount of the
feldspar used, a relatively expensive raw material, and consequently reduces the cost of ceramics.

1. Introduction

Ceramic tiles are materials produced by a fast firing process of clay, silica sand, calcite, pyrophyllite and feldspar mixtures. This
building material, generally used in flooring and also as wall covering and ventilated facades, is endowed with high technological
properties such as low thermal conductivity, high mechanical strength and excellent chemical and abrasion resistance [1–7]. These
properties mean that ceramic tiling was actually the material with the highest increase in production and sales over all other ceramic
building materials.
The ceramic tile industry is a dynamic sector whose technological innovation and market trends have drawn a complex picture of
products and processes. Raw materials have been deeply involved in such an evolution: the flexibility of current manufacturing cycles
enables the use of a very wide range of clays, whose chemical and mineralogical composition, particle size distribution and ceramic
properties were reappraised. Currently, an industry-oriented, technological classification of clay raw materials is proposed on the
basis of chemical (Fe2O3 content) and mineralogical parameters (amount of phyllosilicates and carbonates) together with particle size
(fractions < 2 μm and > 63 μm) and plasticity. It firstly discriminates light firing and dark-firing clays according to an iron oxide
threshold of 3%. Light-firing clays are distinguished by the amount of kaolinite group minerals and plasticity in “kaolins” (high-

⁎
Corresponding author.
E-mail address: schawki37@gmail.com (C. Sadik).

http://dx.doi.org/10.1016/j.cscm.2017.07.001
Received 19 January 2017; Received in revised form 17 April 2017; Accepted 5 July 2017
Available online 13 July 2017
2214-5095/ © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
A. Manni et al. Case Studies in Construction Materials 7 (2017) 144–153

grade, low-grade, and raw kaolins, kaolinitic loams) and “plastic clays” (ball clays, pyrophyllitic clays, white bentonites). Dark-firing
clays are classified according to their coarse-grained fraction and the amount of carbonates in carbonate-rich types (marly and
carbonatic clays), red loams and red clays; these latter are further differentiated by the relative abundance of clay minerals. Such a
classification is essential to draw the guidelines for body formulation and to explain the criteria followed in the industrial practice for
each category of ceramic tiles [8].
The ceramic industry in Morocco dates from the 1970s only. A real growth began during the 1990s, especially with the launch of
an important national project of construction. The Moroccan ceramic industry includes floor and wall tiles, stoneware, brick and
porcelain. Morocco has become known all across North Africa and Europe for its pottery and ceramics. Fes, Meknes, Sale and
especially Safi are the main pottery centers of the country, producing about 80% of Morocco’s production [9–13].
Clays, materials of prime importance to the ceramic industry, are extremely variable materials made up of different minerals,
generally of a silicate nature, sedimented in the form of platelets, fibers, belts etc., and are, for the most part, associated with other
minerals of detrital origin that often play a key role [14–19]. Worldwide, clays are the main raw materials exploited in the fabrication
of diversified ceramic products, and have been extensively studied, beside feldspar, talc and pyrophyllite whose reserves are less
significant and whose costs are very high. Morocco shows an extreme geological and structural diversity of clay minerals. Vermiculite
concentrations are mainly found in two locations in Morocco: in the western Rif and Upper Moulouya. The illitic clays are abundant
and show a wide distribution. The smectitic clays are also abundant in Morocco and can be divided into three main varieties: marls of
the Southern Rif basin; bentonite of the Eastern Rif and ghassoul of the Missour region. Interesting concentrations of talc are known in
two regions of Morocco: the High Atlas and the Anti-Atlas. Some centimeter thick levels of halloysite exist in the volcanic region of
Nador-Melilla (North-Eastern Rif). Moroccan soil does not contain kaolin deposits except in some small concentrations which are
associated with magmatic acidic rocks (Oulmes and Beni Snassen pluton). Different deposits of pyrophyllite exist in Morocco and are
almost entirely situated in the Precambrian area of the Anti-Atlas, regions of Aït Baha, Aït Azegrouz, N’Kob, El Grara and Ougnat.
Finally, Interesting indexes of fibrous clays are described in two regions of Morocco (Souk El Arbaa Gharb and Ouarzazate) [14].
The demand for feldspar as a raw material for the ceramic and glass industries is continuously increasing [20]. In Morocco, the
traditional sources of feldspar ores are rare (Jebel Zerhoun which is located at 25 km north of Meknes), this implies a great im-
portation of this raw material. Feldspathic materials are used extensively wherever manufacturers intend to achieve a high degree of
vitrification: for example, in porcelain tiles and light colored low porosity products 25 to 55% is used. In vitreous-china sanitary ware
and porcelain, feldspathic materials are introduced in quantities ranging from 20 to 30% and from 17 to 37% respectively. Producers
select potassium or sodium feldspar according to the desired specifications of the final product [21].
The present paper aims at investigating a particular application of local raw materials (clays and silica sand) to evaluate their
potential for the manufacture of semi-porous red paste (class BIIb) ceramic production and try to minimize the quantity of the
feldspars used, of which the whole raw material is imported, which will cause an important financial charge. Our methodological
approach includes three phases:

1. Preparation and characterization of the raw material (granulometric analysis, XRF, BET, CEC, PI).
2. Composition of mixtures and firing.
3. Characterization of the elaborated ceramics (porosity, density, shrinkage, thermal conductivity, Flexural strength).

2. Materials and experimental procedures

2.1. Raw materials

Raw materials used in the present investigation were: two varieties of natural clay (C1 and C2), silica sand, and industrial
feldspar.

2.1.1. Natural clay (C1 and C2)

The region of Berrechid, belonging to the Western Moroccan Meseta, contains a large number of quarries of clay exploited by the
numerous industrial units (cementers, brickyard and ceramists) of the region. The main clay quarries are located in the SE of the
commune of Ejemaa of Rhyah, located about 22 km northeast of Berrechid (Fig. 1) and accessible by the main road N° 11 linking
Berrechid and Khouribga. In terms of geomorphology, it is a flat field consisting of a succession of hills of low altitude (300–500 m)
shaped by erosion. Four geological units are distinguished in the region and are from the base to the top:

1. A Paleozoic base composed of schists and pelites of Silurian to Devonian age (-435 to −350 Ma) transformed into gray-green to
purplish clay;
2. Triassic red clay (−245 Ma) of shape in the form of deposits of metric thickness and which contains intercalations of green
basaltic flows and locally evaporite levels (rock salt and gypsum);
3. A tabular layer composed of limestone and marls of Upper Cretaceous age (−96 Ma) and;
4. A terminal layer of quaternary age (−1.8 Ma) composed of red clay, often very stony. Our study was carried out on two facies,
which are the most exploited in the region: the C1 facie corresponding to the red-purplish Silurian – Devonian clays and the C2
facie corresponding to the Triassic red clays.

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Fig. 1. (a) Geographic localization of clay careers in the Berrechid region (b) outcrops of the clays (C1 and C2) used in this study.

2.1.2. Silica sand (SabM)

Several deposits of silica sand exist in Morocco. Silica sand used in this study (SabM) comes from an artisanal quarry, located 3 km
SE of the Mechraa Hammadi Dam, on the road ranging from Nador to Oujda via Layoune (in the North-Eastern part of Morocco;
Rifain Domain). The sands appear as a thin layer (20 to 40 cm) of a white-pink and friable rock intercalated in a limestone-marl series
of the upper Jurassic (130 Ma). The sand is composed mainly of globular grain shape and smooth and shiny surface of quartz whose
grain size ranges from 0.1 to 0.5 mm. The content of silica in the sand is very high (SiO2 = 96%), however its iron levels
(Fe2O3 = 0.51%) remain high enough for the use in glassware (Table 2) [22].

2.1.3. Feldspar
Feldspar deposits remains rare in Morocco thus several varieties of rocks rich in albite and orthose (albitites, rhyolites and
pegmatite) are often used by ceramists as alternative sources of Na-feldspar and K-feldspar. However, the Na and K content in these
rocks remains low (2–3%) and their effect as a fluxing agent is limited. In order to have pure feldspars with high Na and K contents (8
to 10%) it is necessary to use imported feldspars which are necessarily more expensive. The industrial feldspar used is provided by
Company ESEI S.A. Morocco. It corresponds, according to its Na2O and K2O contents (respectively 7.5% and 4.37%), to the com-
position of sodium-riche albite.

2.2. Experimental procedures

We prepared tens of mixtures from the Moroccan geomaterials described above. Among these mixtures, we retained the mixture
M1 (78% C1 + 9% Feldspar + 13% Silica sand) that allowed obtaining ceramics resisting to a temperature exceeding 1100 °C. To
improve the technical quality of this formula and to reduce the amount of the feldspar used, a second formula (M2) will be tested
(68% C1 + 11% C2 + 4% Feldspar + 17% Silica sand).
The raw material (clay, sand, feldspar) underwent crushing operations and wet grinding. The slip was placed in an oven for 24 h
at 110 °C until complete desiccation. The product obtained was dry milled, sieved and we retained the fraction size less than 63 μm.
This latter was moistened using a sprayer in the limits of 4 and 6% of water. The moistened powder was pressed into moulds of
10 × 5 × 2 cm3 using a hydraulic press of 80 MPa. The specimens in the form of briquettes were dried in an oven (110 °C, 24 h) and
then heated to a firing temperature up to 1100 °C in an experimental furnace CWF 1300 [2].
Granulometric analysis of clays was carried out by wet sieving. The percentages of the various classes of particle-size are given in
Table 1. The chemical compositions of the raw materials, performed by X-Ray Fluorescence (XRF), are shown in Table 2. As the major
properties of the ceramic materials are intimately connected to their mineralogical composition, the samples (C1 and C2) were finely

Table 1
Granulometric analysis of clay C1 and C2.

Size in μm Different percentages size fractions (%)

C1 C2

> 60 (sand) 4.5 5.6

60-2 (silt) 55.8 58.1
< 2 (clay) 39.7 36.3

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Table 2
Chemical analysis by X-Ray Fluorescence of raw materials used in this study (wt%).

Oxides (mass%) SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O TiO2 P2O5 LOI Total

C1 54.85 18.25 8.51 1.52 1.07 1.05 2.93 1.49 0.85 9.02 100.54
C2 52.56 24.02 6.78 0.71 1.08 1.07 2.49 1.01 0.22 10.10 100.04
Silica sand 96.06 2.22 0.51 0.09 0.17 0.06 0.20 0.15 0.02 0.49 99.97
Feldspar 66.01 16.18 0.09 0.67 1.40 7.50 4.37 0.04 0.00 4.12 100.38

crushed and analyzed by X-ray diffraction. The different phases were identified using the XPERT DATA COLLECTER software.
Infrared (IR) spectroscopy is a method frequently used to show vibration of chemical bonds. Samples were prepared by the KBr pellet
technique and analyzed by FT-IR in transmission mode. The pellet manufacture was done by pressuring the KBr containing 1% of clay
powder whose main grain size was less than 125 μm. The microstructures of surfaces of the sintered specimens (M1 and M2) were
observed with a field emission scanning electron microscope (Detector Type: SUTW-Sapphire).
Thermal conductivity measurements were employed at room temperature (30 °C) by a hot-wire method using the Quick Thermal
Conductivity Meter (QTM500, Kyoto Electronics). A thermo-gravimetric analysis (TGA) study was performed using a thermo-balance
of the Versa-Therm type under atmospheric air and α-Al2O3 as reference. The temperature was increased from room temperature to
800 °C at a rate of 10 °C/min. Brunauer–Emmett–Teller (BET) specific surface areas of clay samples were determined from the
77 K N2 adsorption–desorption isotherms in a Quantachrome Autosorb Automated Gas Sorption System.
The determination of the cation exchange capacity (CEC) is an important test in the evaluation of the quality of clays. The
determination of CEC followed the Standard Test Method for the Methylene Blue Index of clay, according to the ASTM C 837-81 [23].
A simple and reliable method for the evaluation of the plasticity of clay materials is based on measurement of the Atterberg Limits.
The plasticity index was calculated basing on the arithmetic difference of the liquid limit (LL) and plastic limit (PL) of the studied
clays. Liquid limit and plastic limit tests were carried out with a Casagrande apparatus. The term deflocculant refers to a substance
which, when added to an aqueous suspension of dispersed colloidal powders, causes greater fluidity of the suspension, diminishing its
apparent viscosity. Deflocculant is a synonym for fluidizer and merely correlates the deflocculation process with a decrease in
viscosity, neglecting its function as a dispersant and a preventer of the rapid aggregation that would cause precipitation of the solid
particles suspended in water. Deflocculants are compounds which impede flocculation by way of a higher zeta potential and a relative
increase in the repelling forces between the particles. A good dispersion action creates very high zeta potentials, thus giving minimum
viscosity. In a slip composed of mixture M2 and 200 ml of water, increasing quantities of deflocculant (tripolyphosphate silicate
‘TPPS' and sodium silicate ‘NaS') were gradually added. After agitation during 15 min, the slip viscosity was measured.
The reduction in the weight of each sample (M1 and M2 samples fired at 1100 °C) between drying and the temperature of firing is
given by the following formula:

Loss in weight% = 100 × [(m110 − mt)/m110]

where m110 is mass of sample at 110 °C, mt mass of fired sample at the temperature t.
Fired products were characterized for mechanical properties like flexural strengths with three-point bending. This test was carried
out at ambient temperature. The loading procedure consisted of applying a preliminary load (0.05 kN) at a rate of 0.5 mm/min to
eliminate positioning defects of the specimens. The distance between bottom supports was 80 mm. Three bricks were tested and the
average value was taken. The determination of the value of shrinkage was done by the study of the variation of the average lengths of
the lines recorded on briquettes between drying at 110 °C and firing at 1100 °C. The following formula allows the calculation of the
firing shrinkage:

Shrinkage (%) = (L110 − Lt/L110) × 100

where Lt is the length after firing, and L110 the length after drying at 110 °C.
The water absorption, bulk density and apparent porosity were measured according to ASTM C373-88 [24], which involves
drying the test specimens to constant mass (D), boiling in distilled water for 5 h and soaking for an additional 24 h at ambient
temperature. After impregnation, the mass (S) of each specimen while suspended in water and their saturated mass (M) is de-
termined. The test was carried out on four representative specimens.
Water absorption, WA (%), expresses the relationship of the mass of water absorbed to the mass of the dry specimen as follows:

M− D
WA = × 100
D

The bulk density, B (g/cm3), is calculated as follows:

D
B=
V

where V (cm3) is the exterior volume (V = M − S).

The open porosity, P (%), expresses the relationship of the volume of open pores to the exterior volume of the specimen and is
calculated as follows:

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M− D
P= × 100
V

3. Results and discussion

3.1. Granulometric analyses

The percentage of the elements whose diameter was between 60 and 2 μm (silt) was significant: approximately 55.8% for C1 and
58.1% for C2. The percentage of the elements whose diameter was lower than 2 μm (clays) was high: 39.7% for C1 and 36.3% for C2.
The granulometry of the studied samples was excellent for use in ceramics. The problem of the elements whose diameter was hgreater
than 2 μm can be corrected by simple crushing and sieving.

3.2. Chemical and mineralogical analysis

The most abundant oxides in the studied clays were SiO2, Al2O3, Fe2O3 and K2O (Table 2). Both clays were siliceous
(SiO2 = 55–53%). The clay C2 was more aluminous than clay C1 (Al2O3 = 23 vs 18%) which explains the good mechanical prop-
erties at high temperature. The amount of quartz and alumina has a decisive influence on the refractoriness and mechanical resistance
of the final products [22]. The relatively high amount of Fe2O3 gives a red color after firing. However, Fe2O3 is not the only factor
responsible for the coloration of ceramic wares, because there are also other components such as CaO, MgO and TiO2. This oxide
(Fe2O3) is present in form of goethite. Another important component of the studied clays was the alkali and alkaline oxides, because
these fluxing agents can induce early vitrification and increase the firing shrinkage, and decrease the firing temperature, with a
corresponding energy saving [18]. The K2O content is high; which is probably related to the presence of the illites. On the basis of
their CaO and MgO content, these clays contain significant levels of dolomite. Feldspar is distinguished by its sodi-potassic character.
The results in Table 3 show the predominance of illite, kaolinite, dolomite and goethite, presenting favorable properties for
ceramic use. The content of quartz is very tolerable since it can be easily digested by vitreous flow during firing. The feldspar sample
consisted of orthoclase (22%), albite (65%) and quartz (10%). The silica sand consisted mainly of quartz and microcline as a minor
phase.
Infrared spectroscopy is adapted to spectral measurements in the region of 4000 cm−1 to 400 cm−1. The IR spectra of the raw
clays are shown in Fig. 2. They show the presence of kaolinite characterized by the following bands: 3423 cm−1 OeH valence
vibration; 1000 cm−1 valence vibration of SieO; 539 cm−1 strain Vibration of AleOeSi. The Band located at 472 cm−1 is attributed
to deformation vibration of SieOeMg. A band at 3621 cm−1 was attributed to the vibrations of AlAleOH. Bands located at 800 and
1437 cm−1, corresponded to the CeO bond vibration in carbonates [19].

3.3. Thermal analysis

The DTA results for the Berrechid clay are shown in Table 4. The endothermic peak around 130 °C was due to the release of
adsorbed water. The exothermic peak in the temperature region 380–390 °C is due to the combustion of organic materials present in
the clay samples. The endothermic peaks at 610–620 °C, are due to the dehydroxylation of minerals clays. The small endotherm close
to 560 °C corresponds to the conversion of α-quartz to β-quartz. The TG curves show a slight mass loss below 130 °C, associated with
the loss of loosely adsorbed water. A small mass loss was observed between 380 − 390 °C, and a slight mass loss (1.56–1.77%) was
observed between 610 and 620 °C, followed by a major mass loss (4.15–4.96%) event between 650 and 700 °C corresponding to illite
dehydroxylation [13].

3.4. BET and CEC

Table 5 presents BET surface area and cation exchange capacity (CEC) of the clays. It is noted that the values of the specific
surface area for both clays C1 and C2 were of the same order of magnitude. It should be noted that the measurement of the specific
surface area by the BET method does not allow the determination of the external surface of the clay particle. The CEC values of both
C1 and C2 clays were substantially equal.

3.5. Plasticity test

The plasticity of a clayey raw material is controlled by several factors such as the relative abundances of the granulometric

Table 3
Potential mineralogical composition of clays C1 and C2 (wt%).

Illite Kaolinite Dolomite Quartz Calcite Smectite Goethite

C1 36 28 5 20 1 4 6
C2 31 35 3 20 1 5 5

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Fig. 2. FT-IR patterns: (a) clay C1 and (b) clay C2.

Table 4
The mass losses (%) registered on TG curves.

Samples Endothermic Peak (95–150 °C) Exothermic peak (380–390 °C) Endothermic peak Endothermic peak

C1 0.69 0.91 1.56 4.15

C2 0.58 1.88 1.77 4.96

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Table 5
BET and CEC of clays.

Parameter C1 C2

2
BET surface area (m /g) 35 38
CEC (meq/100 g) 22.3 23.1

fractions, the amounts of expandable clay minerals (smectite, vermiculite and mixed layer clays) and the presence of organic matter.
The plasticity limit (PL) corresponds to the amount of water necessary for the clay to reach a plastic consistency, which makes it
possible for it to be formed by extrusion. The plasticity index PI, is associated with the range between plastic and sludge consistency.
Table 6 indicates that Berrechid clays are characterized by a high plasticity.

3.6. Characterization of ceramic samples M1 and M2

The technological characteristic of the fired clays and the two formulations (M1 and M2) fired at 1100 °C are given in Table 7. The
flexural strength increased from 26.81 to 30.05 N mm−2. The amorphous silica liberated during the clay decomposition or the
impurities contained in the raw materials could also contribute to liquid phase formation which improves the mechanical properties.
This increase in strength lead to a decrease of the porosity of 32% and an increase of the density of 13%. The addition of silica sand
lead to an increase of the thermal conductivity. It ranged on average from 1.185 to 2.675 W/mK.
Several efforts have been made by various researchers to improve the properties of semi-porous ceramic tiles. Technological
evaluation and industrial applications of clay deposits from Tunisia were studied by several research teams. Geotechnical char-
acterization was carried out on the three representative mixtures of Triassic clay samples from South-Eastern Tunisia [25]. Each
mixture was fired at three different temperatures 850, 900 and 950 °C. Firing characteristics (shrinkage: 0.6–3.3%; water absorption:
9.5–14%; and mechanical resistance to the inflection: 10–25 Nmm−2) were obtained. At the end of the study, the authors affirmed
that these clays had the qualities necessary for the manufacture of porous ceramics. The potential use of Tithonian–Barremian detrital
deposits from central Tunisia as raw materials for ceramic tiles and pigments was studied by Hajjaji et al. [26]. The technological
properties were assessed in pressed ceramic tiles after firing at different temperatures. Lab-scale tests involved determinations of
water absorption: 4–21%; bending strength: 18–29 MPa; linear shrinkage: 2–8%; and the results were compared with those of
commercial tiles from Tunisia and Italy.
The densification behaviour of a red firing Brazilian kaolinitic clay was studied by F.A.C. Milheiro et al. [27]. The red clay
presented a refractory behaviour during firing due the high amount of kaolinite clay mineral, high loss on ignition, and the presence
of gibbsite, which impairs sintering, resulting in greater porosity of the specimens. The material showed the following characteristics:
shrinkage: 11%; water absorption: 12.5% and compressive strength: 9 MPa. Clay materials for ceramic tiles from the Sassuolo District
(Italy) were studied by Dondi [28]. The characteristics obtained were compatible with those of this work. shrinkage: 3–9%; water
absorption: 4–15%; Flexural strength 30–42 N mm−2. The general characteristics and technological properties of ceramic clays used
in the Spanish ceramic cluster have been investigated by Meseguer et al. [29]. Red clays for ceramic wall tiles and floor tiles are
mainly extracted in the Valencian Community. Clays were analyzed by X-ray diffraction, chemical composition, particle size dis-
tribution, thermal analysis and plasticity index. Ceramic bodies were fired at temperatures varying from 850 to 1150 °C to determine
the linear shrinkage, water absorption and flexural rupture strength.
The effect of pyrophyllite incorporation in ceramic compositions on mechanical properties was studied by Mukhopadhyay et al.
[30]. China clay (Kaolin) and quartz in the ratio of 1:2 was progressively replaced by pyrophyllite in a conventional porcelain mix.
Addition of 15% pyrophyllite as a replacement of a combination of china clay and quartz decreased the linear shrinkage by 5.03%
while fired strength was improved by about 31.5% compared to that of the conventional body fired at 1300 °C. The material without
addition of pyrophyllite showed the following characteristics at 1150 °C: Flexural strength: 30 N mm−2; linear shrinkage: 4%; por-
osity: 28%; density: 2 g cm−3.
Fig. 3 shows SEM observations on polished surfaces of the M2 ceramic sample fired at different temperatures in the 1000–1150 °C
range. SEM micrographs show the progression of enhanced densification with increasing temperature. The SEM of the sample sur-
faces reveals the presences of microscopic pores and voids at 1000 °C. A sintering process takes place, which consists of the aggregate
compaction of particles. The higher porosity is connected with dense zones, resulting from carbonate decomposition with the evo-
lution of CO2. At 700 °C, CaCO3 present in the clay mixture (dolomite), begins to decompose to CaO, this decomposition during firing
is often accompanied by the evolution of CO2 outside the structure of the fired samples which tends to create a more porous structure.
The free CaO reacts with the amorphous phase derived from decomposition of illite and kaolinite, which diminishes at increasing

Table 6
Plasticity index of the studied clays.

Plasticity limit (%) Liquidity limit (%) Plasticity index

C1 20 47 27
C2 23 52 29

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Table 7
Evaluation of technological parameters of clays (C1; C2) and formulations (M1; M2) fired at 1100 °C.
M2: (68% C1 + 11% C2 + 4% Feldspar + 17% Silica sand).

Open porosity (%) Water absorption (%) Shrinkage (%) Density (g cm−3) Flexural strength LOI (%) Thermal conductivity (W/
(N mm−2) m K−1)

C1 22.74 17.35 7.12 2.98 14.37 11.41 1.13

C2 21.57 16.25 8.62 2.81 14.66 10.25 1.24
M1 15.37 9.23 5.61 2.36 26.81 8.23 2.62
M2 11.65 7.50 4.91 2.71 30.05 6.61 2.73

M1: (78% C1 + 9% Feldspar + 13% Silica sand);

M2: (68% C1 + 11% C2 + 4% Feldspar + 17% Silica sand).

Fig. 3. Microstructures of the M2 ceramic sintered at various temperatures.

firing temperatures.
Between 1000 and 1150 °C a considerable decrease in the porosity occurs, coinciding with the beginning of vitrification. The
densification behaviour of the ceramic mixture is influenced by the sources of flux materials such as K2O, Na2O and Fe2O3 (coming
from feldspar), which favour the formation of a vitreous phase [18]. At 1100 °C the porosity starts to reduce, when a liquid phase was
present. At 1150 °C, the bodies presented a homogenous structure. The porosity was absent, which could explain the good advance in
mechanical properties with decrease in the pore fraction.

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Table 8
Viscosity values versus deflocculant of M2 formulation.

% Deflocculant ‘TPPS' Viscosity (g cm−1 s−1) % Deflocculant ‘NaS’ Viscosity (g cm−1 s−1)

0.6 50 1.03 48
0.7 46 1.075 38
0.8 40 1.1 37
1 39 1.135 36
1.03 37 1.215 29
1.075 37 1.275 26
1.1 39 1.3 27
1.125 42 1.38 56
1.135 50 1.4 76

3.7. Viscosity

It was noted, that from 1.075 and 1.275% of the deflocculant contents, viscosity was minimal and stable for TPPS and NaS
respectively. The reduction in viscosity observed for both deflocculants is directly related to the increase in the intensity of the
repulsive electrostatic forces between the electrical double layers of the particles. This increase could be related to the adsorption of
the orthophosphate anion PO3−, resulting from the hydration of TPPS on the lateral surfaces of clays, at the sites (Al2[OH]4)2+ of the
octahedral layer. This allows a reversal of the positive charge of these sites and therefore an increase in absolute value of the zeta
potential. Cations (Ca2+, Mg2+, etc.) which are adsorbed in the Stern layer, reduce the thickness of the electrochemical double layer,
thus leading to flocculation of the slip. Deflocculation is also provided by adsorption in the diffuse layer of Na+ (from NaS). The large
ionic radius, promotes the increase of the electrochemical double layer and therefore the repulsive forces. The increase in viscosity
observed (beyond 1.075% by TPPS and 1.275 by NaS) is due to the increase of ionic strength associated with the dispersant (mainly
Na+ and unadsorbed anion P2O74− and PO3−) affecting the extension of the electrical double layers and consequently the reduction
of repulsive interactions between the particles [7] (Table 8).

4. Conclusions

The region of Berrechid, belonging to the Moroccan Western Meseta, contains important reserves of clays of various geological
ages and chemico-mineralogical compositions. These clays, which are heavily used by ceramists and brickworkers in the industrial
zone, are often used in an empirical manner. In this work, we have studied two main clay facies of the Berrechid region (C1: red-
purplish clay of Silurian-Devonian age and C2: Triassic red-clay) in order to clearly define their granulometry, plasticity, chemical-
mineralogical composition, thermal behavior, etc. The perfect control of these clays allowed us to develop a clay mixture (M2: 68%
C1 + 11% C2 + 17% siliceous sand and 4% Na-K-feldspar) whose firing at 1100 °C gave a new ceramic of good technical quality
(Porosity: 11.65%, bulk density: 2.71 g cm−3, shrinkage: 4.91%, flexural strength: 30.05 N mm−2 and thermal conductivity: 2.73 W/
m K−1). By these characteristics, this new semi-porous ceramic meets the standards of ceramic materials suitable for the manufacture
of wall tiles, flooring and sanitary fixtures. The advantage of this new ceramic is that it uses a smaller amount of feldspar (4%), almost
half the amount usually used by ceramists (8–10%). Also, this reduction in the quantity of feldspar, a relatively rare and expensive
raw material, will contribute, on an industrial scale, to lower the cost price of this new ceramic. This study confirms the fundamental
role that research and development (R & D) can play in national ceramics companies in improving quality and reducing the cost of
production of their finished products.

Acknowledgement

We are grateful to Pr. Michele Dondi for his constructive comments and for his help with the improvement of the manuscript.

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