Applied Clay Science 27 (2004) 229 234

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Influence of firing temperature on the ceramic properties of clays

from Campos dos Goytacazes, Brazil
S.N. Monteiro, C.M.F. Vieira *
Advanced Materials Laboratory-LAMAV, State University of the North Fluminense-UENF, Av. Alberto Lamego 2000, 28013-602,
Campos dos Goytacazes-RJ, Brazil
Received 6 December 2002; received in revised form 9 December 2003; accepted 19 March 2004
Available online 19 May 2004

Abstract
The characteristics of two clays used for red ceramic production in Campos dos Goytacazes, southeast of Brazil, were
investigated. Characterization was performed by X-ray diffraction, chemical analysis, as well as granulometric and plasticity
measurements. Technological properties related to water absorption, linear shrinkage and flexural strength were obtained from
specific tests. Samples were prepared by pressing clay bodies at 20 MPa, which were then fired at temperatures from 850 to
1200 jC. The results showed that both clays from three deposits are highly plastic due to the elevated percentage of kaolinitic
clay minerals. The samples richer in clay minerals present higher linear shrinkage as well as a decrease in water absorption in
comparison to the others. The effectiveness of these clays for red ceramic production has been discussed in terms of the Winkler
diagram.
D 2004 Elsevier B.V. All rights reserved.
Keywords: Clays; Characterization; Firing; Winkler diagram; Red ceramic; Campos dos Goytacazes

1. Introduction
In the municipal area of Campos dos Goytacazes,
located in the north of the State of Rio de Janeiro,
southeast of Brazil, there is a large production of red
ceramics. Nowadays more than 100 small to large
ceramic industries produce mainly low-cost bricks for
civil construction. The present production of bricks in
the region is estimated to be of the order of 1 billion
pieces per year. A smaller annual production of 14
million roofing tiles and 120,000 extruded floor tiles
also exists.
* Corresponding author. Fax: +55-222-726-1533.
E-mail address: vieira@uenf.br (C.M.F. Vieira).
0169-1317/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2004.03.002

Geographically, almost 70% of the municipal area

is a low plain with a maximum of 17 m above sea
level (Pinto, 1987). This plain was formed by the
Paraba river as its deltoid mouth extended into the
Atlantic Ocean, through an alluvium sediment deposition process, during the quaternary period (Lamego,
1974). Today, the quaternary sediments existing in the
Campos plain correspond to three kinds: river, marine
and lagoon deposits. The lagoon and river sediments
rich in clayed deposits are largely explored by the
ceramic industries. Different types of clays may be
found in the same area or microregion in Campos
depending on the layers of sediments that have been
deposited in the past. In a recent publication, four
clays from distinct layers in the same deposit were

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S.N. Monteiro, C.M.F. Vieira / Applied Clay Science 27 (2004) 229234

characterized (Monteiro and Vieira, 2002). These

clays were denoted by their natural colours in the
deposit: yellow, grayish yellow, gray and black.
The common industrial practice in Campos is to
prepare ceramic bodies by mixing the two main types
of clays found in the region. These types are locally
called weak, with a yellowish colour and strong,
with a grayish yellow colour (Vieira et al., 2000,
2001). Usually, the mined deposits present an upper
layer of weak clay and a lower layer of strong
clay, possibly followed by other types such as gray
and black clays, extending to a maximum depth of 3
m. Below that, the level of the groundwater bed is
reached. The coexistence of both types of weak and
strong clays in the same deposit makes it easy to
operate the fabrication practice referred to above.
Many ceramic industries still use wood as the easiest
and most economic fuel for their majority type Hoffmann furnaces.
The objective of this work therefore was to characterize the two most used clays, weak and
strong, from the three different deposits in Campos
and to study the influence of the firing temperature on
their technological properties. It is expected that the
present investigation will help to improve the knowledge on the main clays as well as to contribute to a
correct exploration of the deposits and to facilitate an
optimization of red ceramic fabrication.

agglomerates. Finally, the clays were classified to

particles smaller than 840 Am using a 20-mesh sieve.
The clays were characterized by X-ray diffraction
(XRD), chemical analysis, particle size distribution
and plasticity measurements. The XRD of sample
powders was performed in a Sheifert model URD
65 diffractometer operating with Cu-Ka radiation for
2h angle ranging from 5j to 50j. The chemical
compositions were obtained by wet analytical methods and the particle size distribution by wet sieving
and sedimentation method, according to the norm
(ABNT, 1984a). The plasticity was measured by the
Atterberg indices: lower plastic limit (LPL), upper
plastic limit (UPL) and plastic index (PI), according to
the norms (ABNT, 1984b,c).
In order to determine the technological properties,
114.3  25.4  10 mm specimens were made using a
stainless steel matrix by applying a 20-MPa uniaxial
pressure. These specimens, initially with 6.5% moisture, were dried at 110 jC until constant weight was
achieved. Firing was then carried out at temperatures
in the range from 850 to 1200 jC. During firing the
heating and cooling rates were kept at 10 jC/min and
the specimens were maintained at the maximum
temperature for 60 min. The technological properties
determined were linear shrinkage, water absorption
and flexural strength. Flexural strength was obtained
by the three points bend test performed in a universal
machine, according to the norm (ASTM, 1977).

2. Materials and methods

3. Results and discussion
The two types of clays, weak and strong,
used in this work came, for statistical purposes, from
three separate micro regions. These regions, denoted
as 1, 2 and 3, correspond respectively to the localities
of Visconde, Limao and Saturnino Braga in the
district area of Campos. Therefore, six different clays
samples were, accordingly, investigated: W1
weak clay from the upper layer from Visconde;
S1strong clay from the lower layer from Visconde; W2weak clay from the upper layer from
Limao; S2strong clay from the lower layer from
Limao; W3weak clay from the upper layer from
Saturnino Braga; S3strong clay from the lower
layer from Saturnino Braga.
After extraction, the clays were initially dried at
110 jC and then manually crushed to reduce large size

Fig. 1 presents the XRD pattern for the two types

of clays, S and W, from the three different regions.
According to Fig. 1, the clays have similar mineralogical compositions with the predominance of kaolinite. Other secondary mineral phases found in all
clays were quartz, mica and gibbsite. The XRD
pattern of the clay S2 also shows the presence of
gypsum (calcium sulfate hydrate).
Table 1 shows the chemical compositions in terms
of oxide contents, as well the loss of ignition and
organic carbon for the clays. The following characteristics can be highlighted relative to what would be
expected in other conventional clays. All the clays
from Campos have high loss of ignition, low SiO2,
high alumina and low alkaline and earth-alkaline

S.N. Monteiro, C.M.F. Vieira / Applied Clay Science 27 (2004) 229234

231

Fig. 2. Particle size distribution of the weak clays.

Fig. 1. X-ray diffraction pattern of the clays. M: Mica; K: kaolinite;

Gi: gibbsite; Q: quartz; Gp: gypsum.

oxides. The high loss of ignition associated with low

SiO2 and high Al2O3 is due to the significant level of
clay minerals. The low content of alkaline oxides
(K2O and Na2O) is a consequence of kaolinitic clays
that naturally have a low percentage of flux minerals.
The low earth-alkaline oxides (CaO and MgO) content indicates absence of carbonates. The high Fe2O3
content confers the typical reddish color to products
such as bricks and roofing tiles.
It can also be observed in Table 1 that the weak
clays from regions 1 and 3 show a higher SiO2/Al2O3
ratio than the strong clays. These ratios are 1.48
and 1.41 for the weak clays and 1.33 and 1.35 for
the strong clays. This indicates that the weak

clays from these two regions have relatively more

quartz and less clay minerals than the strong clays.
The two types of clays from region 2 do not present
the same situation, because the strong clay has a
higher SiO2/Al2O3 ratio (1.40) than the weak clay
(1.34). More importantly, weak clays have significantly higher iron oxides than the strong clays.
Figs. 2 and 3 present the curves of particle size
distribution for the clays investigated. In these curves
a clear separation can be observed between the curves
corresponding to weak and strong clays from
both regions 1 and 3. The strong clays from regions
1 and 3 contain about 70% of fine particles ( < 2 Am),
associated with the clay minerals, whereas the fraction
( < 2 Am) in the weak clay makes up to 45% of the
sample from region 1 and 51% of the sample from

Table 1
Chemical analyses and SiO2/Al2O3 ratio of the clays (in wt.%)
Determinations

Clays
W1

S1

W2

S2

W3

S3

SiO2
Al2O3
TiO2
Fe2O3
CaO
MgO
Na2O
K2O
Loss of ignition
Organic carbon
SiO2/Al2O3

41.08
27.76
0.82
9.94
0.07
0.44
0.38
1.16
15.67
0.55
1.48

41.42
31.22
0.80
6.43
0.05
0.22
0.22
0.80
17.12
0.58
1.33

40.66
30.30
0.83
8.41
0.06
0.31
0.30
1.10
16.01
0.40
1.34

42.27
30.14
0.77
6.42
0.06
0.27
0.32
1.16
15.06
0.78
1.40

39.25
27.82
0.85
9.92
0.14
0.44
0.32
1.16
16.13
0.51
1.41

40.63
30.17
0.79
5.10
0.15
0.36
0.56
0.84
18.65
0.70
1.35

Fig. 3. Particle size distribution of the strong clays.

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S.N. Monteiro, C.M.F. Vieira / Applied Clay Science 27 (2004) 229234

Fig. 5. Gresification diagram of the weak clays.

Fig. 4. Winkler diagram.

region 3. In contrast, both weak and strong clays from

region 2 present similar particle size distribution with
fine particles ( < 2 Am) making about 56% of the
samples.
In Fig. 4 the six clays investigated were located on
a Winkler diagram. According to the Winkler diagram
in this figure, only the weak clay from region 1 is
adequate to be processed as an extruded ceramic
product (field I).
Any mixture made only with these clays would fall
inside the dashed line delimited by clays W1, S1, W2,
S2, W3 and S3, in Fig. 4, outside field III, adequate
for bricks. This fact indicates the need to add nonplastic materials in order to weaken any ceramic
body for bricks made with the investigated clays.
Table 2 depicts the results of the plasticity tests,
given by the Atterberg limits. One may observe that all
clays present similar values of plasticity, which would
be considered relatively high by conventional standards. In fact, the elevated values of PI characterize them

as highly plastic. Both weak and strong clays also

show high values for the lower plastic limit (LPL). This
parameter has an important technological application,
since it indicates the minimum percentage of moisture
necessary to reach a plastic condition (Abajo, 2000).
With a high LPL there will be more difficulty in drying
the samples. On the other hand, the use of high plastic
clays contributes to a reduction in the wearing down of
the equipment for comminution and conformation
(extruder). Moreover, high plasticity is associated with
bodies with greater mechanical strength.
Figs. 5 and 6 show the temperature-dependence
curves for water absorption and linear shrinkage. This
type of curves is also known as a gresification diagram
and is associated with the efficiency of the sintering
process. In general, the curves in Figs. 5 and 6 display

Table 2
Plasticity parameters given by Atterberg indices (in wt.%)
Atterberg indices

LPL
UPL
PI

Clays
W1

S1

W2

S2

W3

S3

29
65
36

30
68
38

29
69
40

25
69
44

28
66
38

30
67
37

Fig. 6. Gresification diagram of the strong clays.

S.N. Monteiro, C.M.F. Vieira / Applied Clay Science 27 (2004) 229234

a decrease in the water absorption values and an

increase in linear shrinkage with increasing firing
temperatures for all clays. This is due to effective
formation of a liquid phase. The liquid surface tension
and capillarity help to bring particles close together
and to reduce porosity (Reed, 1976). Above 1000 jC,
the curves show a sudden change that is associated
with a more significant liquid phase formation. It can
also be observed that the strong clays present, at the
same temperature, greater densification than the
weak clays. This is a consequence of the larger
percentage of finer particles present in the strong
clays. None of the clays reached zero values for the
water absorption, even when fired at 1200 jC, in
accordance with the refractory behavior of kaolinitic
clays. Here it is worth mentioning that both clays, S
and W, from region 2 present a quite similar behavior
in terms of the water absorption and linear shrinkage as
a function of the firing temperature. This is due to the
closeness of their mineralogical compositions with
similar quantities of plastic and non-plastic materials,
as observed by the particle size distribution characteristics shown in Figs. 2 and 3.
Figs. 7 and 8 depict the variation with temperature of the flexural strength for the clays studied. The
relevant observation in these figures is the fact that
the flexural strengths for all weak clays are
similar and increase sharply with firing temperature
above 1000 jC. Strengths three to four times those
achieved at 1000 jC are reached at 1200 jC. As

Fig. 7. Flexural strength of the weak clays against the firing

temperature.

233

Fig. 8. Flexural strength of the strong clays against the firing

temperature.

mentioned before, liquid phase formation above

1000 jC reduces porosity, which hinders crack
formation and improves the mechanical strength.
This is an important limitation for practical purpose.
In fact, a structural limit for the strength of
ceramic products has been proposed (Dondi and
Fabbri, 1996), which varies according to the materials porosity.
The strong clay from region 2 (Fig. 8) has the
same behavior as the weak clays, namely, a sharp
increase in flexural strength above 1000 jC. This
should be expected since S2 in the diagram of Fig.
4 is comparatively close to W2.
Conversely, the strong clay specimens from
region 1 practically presented no variation on the
mechanical strength with firing temperature while
the specimens from region 3 presented a decreasing
mechanical strength from 1000 jC. These clays
showed microstructural cracks and dark spots associated with black core defects. The cracks are
a consequence of their elevated linear shrinkage
(Fig. 6). The black core defects are due to the
reaction of remaining carbon from incomplete organic matter combustion with hematite (Albero et
al., 1991). Although all the clays show a similar
amount of organic carbon, the higher amount of
clay mineral presented in the clays S1 and S3
probably contributed to a low permeability of the
specimens. This fact associated with the elevated
heating rate (10 jC/min) may cause the presence
of black core.

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S.N. Monteiro, C.M.F. Vieira / Applied Clay Science 27 (2004) 229234

4. Conclusions
The characteristics and the dependence of firing
temperature on the properties of the two main types of
clays from three different deposits in Campos dos
Goytacazes (Brazil) led to the following conclusions:
Although the clays analyzed have the same
kaolinitic predominance, different layers of sediments result in clays with individual characteristics. For example, in two regions (1 and 3), the
strong clays (grayish yellow) that came from
lower layers present a higher percentage of clay
minerals and less quartz than the weak clays
(yellowish) from the upper layers. This fact
contributes to a relatively finer granulometry and
higher loss of ignition for the strong clays from
these two regions. In the other region (2) the
strong and weak clays are very similar in
their characteristics and firing behavior. This latter
result indicates that difference in colour used in
the local industries to separate weak from
strong clay in the same deposit may not
correspond to significantly different characteristics
and properties.
All clays analyzed are too plastic for red ceramic
fabrication, which makes it necessary to correct the
particle size distribution according to the Winkler
diagram.
The gresification diagram revealed a refractory
behavior for all clays that is associated with the
difficulty of achieving a low level of porosity. This
is due to the kaolinitic predominance of clay
minerals and the low percentage of alkaline flux.
Due to the finer particles, the strong clays, from
regions 1 and 3, present a higher densification than
the weak clays. Therefore, these clays display a
higher linear shrinkage above 1000 jC.
In spite of their higher densification, the strong
clays from regions 1 and 3 do not attain a high
mechanical strength, because their very high linear
shrinkage and the presence of organic matter give

rise to the formation of microstructural cracks, dark

spots and black core defects.

Acknowledgements
The authors would like to express their thanks for
the financial support provided by the Fundacao de
Amparo a` Pesquisa do Estado do Rio de Janeiro
(FAPERJ), process number E-26/151.544/2001.

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