Applied Clay Science 101 (2014) 619–622

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Applied Clay Science

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Note

Ceramic behaviour of some clay deposits from Guayas province, Ecuador:

Preliminary study
M.M. Jordán a,⁎, F. Pardo b, T. Sanfeliu b, S. Meseguer b
a
Department of Agrochemistry and Environment, Miguel Hernández University of Elche, Avda. de la Universidad s/n, 03202 Elche Alicante, Spain
b
Unit of Applied Mineralogy, Department of Agrarian Sciences and Environment, University Jaume I, Campus de Riu Sec s/n, 12080 Castellón, Spain

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

Article history: This note is a preliminary study from mineralogical and chemical points of view about the possibility of using
Received 30 April 2014 local clays from Ecuador in industrial ceramics. The chemical and mineralogical composition of clays was deter-
Received in revised form 15 September 2014 mined by X-ray fluorescence (XRF) and X-ray diffraction (XRD). Also, the plasticity index (PI) was measured for
Accepted 19 September 2014
each sample. Test samples were prepared by pressing and firing at different temperatures. Linear contraction
Available online 7 October 2014
(LC), water absorption capacity (WAC), and bending strength were performed to characterise the fired clays.
Keywords:
The clay deposits studied were plastic raw materials with very high contents of quartz. The raw material in
Guayas traditional ceramics in Ecuador is clay with approximate levels of silica at 60%, alumina 15%, low alkalis and
Ecuador carbonates, and high iron levels. The sample mineralogy indicates quartz as a primary mineral, followed by
Clay deposits plagioclases, with hematite to a lesser extent in all the samples. Kaolinite, illite, and chlorite are the main clay min-
Mineralogy erals in the raw material samples. All the studied clays seem to be easily adaptable to a correct dry pressing ceramic
Ceramics process. The studied clays are an excellent raw material for the formulation of low porosity ceramic stoneware.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
In order to research the ceramic sector in Ecuador, certain basic
information is necessary, such as the number of industries involved in
the sector (Table 1), the raw material used (Table 2), and the products
made (Cárdenas et al., 2003). Ceramic industries were also arranged
by province, determining that the greatest percentage is based in the
provinces of Azuay (37%) and Pichinga (21%). Guayas province (13%)
is third overall, and the largest among Ecuador's coastal areas. Smaller
producers include the provinces of Loja (10%), Chimborazo and Cañar
(5%), Manabí, Tungurahua, and Imbabura (3%).
In Ecuador, only the traditional ceramic industry has been
developed, and within this segment, the highest percentage corre-
sponds to white and red ceramics (Cárdenas et al., 2003).
In order to determine which types of products the white and red ce-
ramic industries manufacture, the industries were consulted directly.
The results from this research indicate that the country produces roof
tiles, clay bricks and blocks, stoneware tiles, floor and wall tiles, sanitary
porcelain, and porcelain.
This study was focused on the properties of ceramic clays from
Guayas province (Ecuador), an area with an important local traditional
ceramic industry. Six deposits with industrial applications were studied.
The clays come from Samborondon, Marcabeli, and San Roque Piñas, in
Guayas province. The clays used for manufacturing traditional ceramic
⁎ Corresponding author. Tel.: +34 966658416; fax: +34 966658340.
E-mail address: manuel.jordan@umh.es (M.M. Jordán).
handicrafts come from nearby savannas at depths of 25–30 cm. These
clay deposits are Quaternary materials deposited during different epi-
sodes by the Guayas River.
The relationship between the mineralogical composition of the raw
materials and phase changes taking place during their sintering under
different conditions has been studied by different authors (Daskshama
et al., 1992; Jordan et al., 1999, 2009, among others). A sintering process
consists in the compaction of aggregated particles. This process is not
complete so the ceramic tile bodies are still quite porous. Towards
1000 °C, the larger pores are seen to increase (between 1 and 10 μm).
This phenomenon coincides with the destruction of clay minerals and
their re-crystallisation (Jordan et al., 2008).
The raw material in traditional ceramics in Ecuador is clay with ap-
proximate levels of silica at 60%, alumina 15%, low alkalis and carbon-
ates, and high iron levels (Cárdenas et al., 2003).
This study results from the necessity of the Ecuadorian ceramic in-
dustry to locate clays of high plasticity that additionally possess a high
degree of cohesion upon drying and wide vitrification ranges; therefore,
there is great interest in their ceramic behaviour.
Previous studies do not exist about these non-exploited clay de-
posits in Guayas province. This is the first time that the applicability of
these clays as a raw material for the ceramic industry has been tested.
New research and better characterisation of clay deposits were needed
for obtaining new ceramic processes and formulations. The main objec-
tive of this paper was to study the chemical–mineralogical composition
and technological behaviour that allows the evaluation of the applicabil-
ity of the clay deposits studied in manufacturing new ceramic products.

http://dx.doi.org/10.1016/j.clay.2014.09.028
0169-1317/© 2014 Elsevier B.V. All rights reserved.
620 M.M. Jordán et al. / Applied Clay Science 101 (2014) 619–622

Table 1 The water absorption capacity (WAC) was determined in fired

Number and percentage of ceramic and related industries in Ecuador. clay pieces following the EN ISO-10545-3 (AENOR, 1997) standard.
Industry Number of companies % The bending strength tests were conducted at 1120 °C in a Gabbrielli
White clays 15 35
Crab 424 instrument with a digital control system according to the
Red clays 15 35 EN ISO 10545-4 standard (AENOR, 2012). The temperature was se-
Cement⁎ 8 19 lected following the standards for ceramic materials used for floor
Glass 4 9 coverings. The values obtained show a high level of deviation,
Refractary 1 2
which made carrying out a high number of determinations (between
⁎ Limestone is used as a raw material in the ceramic and cement industries. 15 and 20) for each test necessary.

2. Materials and methods 3. Results and discussion

Six deposits of clays were selected in the Samborondon (series EC-1,
EC-2, EC-3, and EC-4), Marcabeli (series EC-5), and San Rafael Piñas
(series EC-6), located in the Guayas province of Ecuador.
Twenty samples of each clay deposit were collected. Samples were
taken according to standardised sampling procedures (Sanfeliu and
Jordan, 2009). They were oven-dried at 110 °C until reaching a constant
mass and then ground with a hammer mill to pass through a 630 μm
sieve following normal ceramic laboratory practices (Meseguer et al.,
2009a). Ten selected samples from each deposit were analysed for the
mineralogical and chemical composition (average values are discussed).
A representative sample of each deposit was selected for ceramic tests.
Mixtures of samples from the same deposit were prepared in a propor-
tion of 65% solid and 35% water with a 1% deflocculating agent (sodium
pyrophosphate).
Mineralogical analysis was carried out by X-ray diffraction (XRD)
using a Siemens D-5000 diffractometer, CuKα radiation, both on pow-
der (bulk samples) and oriented aggregates (natural and reacted with
ethylene glycol and heated to 550 °C for 2 h) of the clay fraction were
obtained following the criteria expressed by Moore and Reynolds
(1997). A semi-quantitative analysis was carried out following the
Jordan et al. (1999) methodology. The chemical analysis was based on
X-ray fluorescence measurements (Bruker S4 Pioneer) using conven-
tional techniques (Meseguer et al., 2009b).
The plasticity index (PI) was determined with the Pfefferkon meth-
od (ten determinations per sample). Samples were moistened by hand,
mixed sufficiently, and sieved (1 mm) until homogeneous agglomerates
with 5% water were obtained. They were left to rest for 2 days and then
pressed (0.3 MPa, 80 × 40 × 5 mm) using a laboratory press. The pieces
were finally heated to 830, 880, 925, 980, 1025, 1080, 1120, and
1165 °C, maintaining at the maximum temperature for 2 h. These tem-
peratures were arbitrarily chosen but correspond to temperatures used
during the firing of industrial ceramic tiles. The linear contraction (LC)
was measured following conventional techniques. The linear contrac-
tion is calculated as follows:
3.1. Mineralogical composition
Some authors (Dondi et al., 1998; Jordan et al., 1999; Jordan et al.,
2001; Dondi et al., 2014; among others) point out that mineralogical dif-
ferences in raw materials have great influence on the behaviour of ce-
ramic pastes with respect to their rheological and thermal properties,
as well as the porous structure of the fired products.
The mineralogical compositions of the samples differed considerably
(Table 3). Bulk samples from deposit EC-1 consisted mainly of quartz,
plagioclase, and hematite, and contained illite in minor amounts.
Quartz, illite/muscovite, and kaolinite were the dominant phases in
clay fraction EC-1. Another component found in a lower quantity in
this fraction was chlorite. Quartz and plagioclase were the dominant
phases in bulk samples from deposit EC-2, while hematites, illite/
muscovite, and chlorite were present in lower quantities. In clay fraction
EC-2, the mineral phases found were quartz, illite/muscovite, and chlo-
rite as the dominant phases, and the kaolinite content was minor. The
main phases found in bulk EC-3 samples were quartz, plagioclase, chlo-
rite, hematites, and kaolinite. The main phases in clay fraction EC-3
were kaolinite, quartz, and illite/muscovite. In this fraction, chlorite
was found in trace amounts. The mineral composition of EC-4 samples
in bulk rock consisted of quartz, plagioclase, kaolinite, chlorite, and he-
matites, with a small amount of illite/muscovite. In clay fraction EC-4,
the mineral phases found were kaolinite and chlorite, with the dominant
phases quartz and illite/muscovite. The mineral composition of EC-5
samples in bulk rock consisted of quartz, plagioclase, feldspars, and he-
matites, with a small amount of talc and illite/muscovite. In clay fraction
EC-5, the mineral phases found were quartz as dominant phase, feldspar,
illite/muscovite, kaolinite, and traces of chlorite. Finally, the mineral
composition of EC-6 samples in bulk rock consisted of quartz, hematites,
plagioclase, illite/muscovite, kaolinite, and talc. In clay fraction EC-6, the
mineral phases found were quartz, the dominant phase, kaolinite, and
illite/muscovite. Another component found in a lower content in this
fraction was chlorite.

Li −L f
LC ¼  100
Li 3.2. Chemical composition

where:
The chemical composition (Table 4) of most samples showed a
high iron content (7.3–5.1% Fe2O3), responsible for the reddish col-
LC linear contraction (%)
our developing at firing, except for samples from the EC-5 deposit
Li initial length of the ceramic body
with a 0.6% Fe2O3 content. EC-5 C clays showed the highest relative
Lf final length of the ceramic body.
amounts of alkalis (Na2O + K2O), explaining why this sample ma-
tures at relatively low temperatures. The CaO content was relatively
low in samples EC-1, EC-2, EC-3, EC-4 (3.6–1.7%), and very low in
samples EC-5 and EC-6 (0.1%). The CaO control is important because
Table 2
decarbonation is a strongly endothermic reaction that generates a
Number of quarries for each raw material in Ecuador.
high volume of gas, leading to expansive reactions (Cultrone et al.,
Raw material Number of quarries 2004). A higher loss on ignition was observed for the EC-2, EC-4,
Limestone 24 and EC-6 samples due to the presence of organic matter. Samples
Clays/kaolin 17 EC-1, EC-3, and EC-5 showed low values for ignition loss. Finally,
Silica 8 the SiO 2 content was up to 60% in all studied samples, with Al2O 3
Gypsum 6
values between 14 and 18%.
 M.M. Jordán et al. / Applied Clay Science 101 (2014) 619–622 621

Table 3
Mineralogical composition of clays.

Bulk fraction Clay fraction

Sample Q FdK Plg Hem I/M K Cl Talc Q FdK I/M K Cl

EC-1 ++++ − ++ + (+) − − − +++ − + + (+)

EC-2 +++ − ++ + + − + − ++ − ++ + ++
EC-3 +++ − +++ + (+) + ++ − ++ − ++ ++ +
EC-4 +++ − +++ + + ++ ++ − ++ − ++ +++ +++
EC-5 ++++ ++ +++ + (+) − − + +++ + + + (+)
EC-6 ++++ − + ++ + + − + +++ − ++ ++ (+)

Legend: Q: Quartz, Fk: K-feldspar; Plg: Plagioclase (albite/oligoclase), Hem: Hematite; I/M: Illite/Muscovite; K: Kaolinite; Cl: Chlorite; T: Talc;; ++++ (N20%); +++ (N15%);
++ (N10%); + (N5%); (+) Present (5–2%); (.) (b2%);− not present.

Table 4
Chemical analysis (% by mass, air-dried). LOI: loss on ignition.

% EC-1 EC-2 EC-3 EC-4 EC-5 EC-6

SiO2 66.8 ±2.1 65.2 ±1.8 67.3 ±2.3 62.7 ±1.9 75.7 ±3.2 61.5 ±1.1
Al2O3 17.2 ±1.1 14.8 ±0.9 15.2 ±0.7 15.8 ±0.8 14.5 ±1.1 18.6 ±1.2
Na2O 2.6 ±0.2 2.4 ±0.1 3.0 ±0.2 1.9 ±0.3 3.3 ±0.2 0.2 ±0.07
K2O 1.0 ±0.2 0.9 ±0.1 1.1 ±0.1 0.7 ±0.05 3.8 ±0.2 2.5 ±0.3
CaO 2.5 ±0.3 1.7 ±0.2 3.6 ±0.2 1.7 ±0.1 0.1 ±0.07 0.1 ±0.06
MgO 2.1 ±0.8 1.6 ±0.4 2.1 ±0.2 1.8 ±0.2 0.1 ±0.04 1.1 ±0.05
Fe2O3 6.2 ±0.6 5.9 ±0.5 5.1 ±0.5 6.2 ±0.4 0.6 ±0.1 7.3 ±0.7
TiO2 0.7 ±0.1 0.7 ±0.1 0.5 ±0.1 0.7 ±0.2 – – 0.9 ±0.1
MnO 0.1 ±0.03 0.1 ±0.06 0.1 ±0.08 0.1 ±0.04 – – – –
P2O5 0.1 ±0.09 0.1 ±0.1 0.1 ±0.09 0.1 ±0.08 – – – –
Cl – – 0.3 ±0.1 – – 0.2 ±0.1 – – – –
SO3 0.3 ±0.08 0.4 ±0.06 – – 0.5 ±0.1 – – – –
L.O.I. 0.6 ±0.1 6.7 ±0.6 2.1 ±0.5 8.2 ±0.7 1.7 ±0.2 7.8 ±0.3

3.3. Plasticity behaviour
The plastic behaviour of the samples and their adaptability for
pressing were similar (Marsigli and Dondi, 1997). Samples were consid-
erably plastic raw materials (PI = 30–34) (Table 5), explaining their
excellent aptitude for working in the plastic state (Daskshama et al.,
1992; Galos, 2011).
3.4. Bending strength
The bending strength (Table 6) of the bodies fired at 1120 °C was be-
tween 16 and 25 MPa. The values were within the interval for materials
used for pavements and/or floor coverings (15–20 MPa) but were
somewhat inferior to the required specifications for earthenware
(34–35 MPa) (Jordan et al., 2008; Galos, 2011). The differences in the
measured values made it necessary to carry out a high number of deter-
minations in each test. The discrepancies were in large part due to errors
of the geometry of the pieces from surface micro-fissures and errors
related to the device used in the tests.
3.5. Firing behaviour
Table 7 shows the values for linear contraction (LC) and water
absorption capacity (WAC) for each clay deposit. The WAC decreased
Table 5
Plasticity index (IP) values for selected samples of deposits
EC-1, EC-2, EC-3, EC-4, EC-5, and EC-6.
gradually, with oscillations up to 1080 °C in all samples. Around
1120 °C, a considerable decrease in the WAC was observed, suggesting
the beginning of vitrification (Carretero et al., 2002; Jordan et al.,
2008). Above 1160 °C, high sintering levels were reached for some
pieces, indicated by the fast WAC decrease (b5%). The changes in the
water absorption capacity were mainly due to two factors with opposite
effects: The first factor was related to the reduction in the open porosity
of the pieces to increasing amounts of the liquid phase and the decreas-
ing viscosity. Besides reducing the porosity of the tile bodies, this effect
partially blocked the pre-existent capillary system (Amorós et al., 1992),
which reduces the WAC even more. The second factor was the conse-
quence of the micro-structural heterogeneity of the raw tile bodies,
which led to the elimination of the smaller pores at higher tempera-
tures. This brought about differential contractions among the different
micro-regions of the tile body, and as a result, the average pore size
diameter increased.
The chemical analysis of the fired samples indicated high values for
silica, alumina, and iron; however, the alkali values were low, and
those for the loss due to calcination were practically non-existent after
firing. At low temperatures, alkalis were present in the tile bodies. At
higher firing temperatures alkalis contribute to the formation of the
liquid phase, reducing the porosity of the tile bodies (Amorós et al.,
1992; Jordan et al., 1999). Linear contraction increased gradually with
temperature. However, this increment was inexistent for low tempera-
tures in deposits EC-5 and EC-6, low for EC-1, and high for the EC-2 and
EC-4 clay deposits. This behaviour in clays from the EC-2, EC-3, and EC-4
Table 6
Bending strength σ (MPa) for ceramic tile bodies.

Sample PI Sample Sintered 1120 °C

EC-1 31 ± 2 EC-1 18 ± 4
EC-2 34 ± 4 EC-2 19 ± 6
EC-3 34 ± 3 EC-3 16 ± 2
EC-4 33 ± 2 EC-4 20 ± 2
EC-5 32 ± 2 EC-5 22 ± 2
EC-6 30 ± 1 EC-6 25 ± 5
622 M.M. Jordán et al. / Applied Clay Science 101 (2014) 619–622

Table 7 4. Conclusions
Linear contraction (LC) and water absorption capacity (WAC) vs temperature for selected
samples of deposits EC-1, EC-2, EC-3, EC-4, EC-5, and EC-6.
The clay deposits studied correspond to highly plastic clays with
EC-1 LC WAC T (°C) very high contents of quartz. All the samples were considerably plastic
1 9.39 0.00 1165 raw materials explaining their excellent aptitude for pressing. The
2 10.80 0.48 1120 sample mineralogy indicates quartz as a primary mineral, followed by
3 5.38 8.90 1080 plagioclase, with hematite to a lesser extent in all the samples. Kaolinite,
4 2.37 14.93 1025
illite, and chlorite are the main clay minerals in the raw material
5 1.71 16.39 980
6 0.97 17.11 925 samples. From the point of view of the industrial application for these
7 0.64 17.78 880 clays, it can be stated that according to their origin, composition, and be-
8 0.37 16.69 830 haviour, they are an excellent raw material for the formulation of low
porosity ceramic stoneware (Dondi et al., 2014).
EC-2 LC WAC T (°C)
The positive results obtained in this set of preliminary tests lead us to
1 10.30 0.00 1165 envisage new research programmes in Guayas province focused on test-
2 9.03 4.73 1120
ing these and other raw materials on a semi-industrial scale, and
3 4.01 13.37 1080
4 2.48 16.17 1025 assessing the effective possibility of using them as ceramic raw mate-
5 2.27 16.62 980 rials in the local ceramic industry.
6 2.21 15.94 925
7 2.14 16.91 880 Acknowledgements
8 1.47 17.43 830

EC-3 LC WAC T (°C) The authors would like to express their gratitude to Dr. M. Montano,
researcher of the Instituto de Ciencias Químicas y Ambientales of the
1 2.37 0.00 1165
2 11.70 1.12 1120 Escuela Politécnica Superior del Litoral (Ecuador), for help in the discus-
3 2.40 17.92 1080 sion and additional comments.
4 0.07 23.24 1025
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6 0.07 21.57 925
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