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Thermal evolution of the mechanical properties of calcareous earthenware

Article in Ceramics International · January 2014

DOI: 10.1016/j.ceramint.2013.07.067

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CERAMICS
INTERNATIONAL
Ceramics International 40 (2014) 1709–1716
www.elsevier.com/locate/ceramint

Thermal evolution of the mechanical properties

of calcareous earthenware
María Florencia Serraa, María Florencia Acebedoa, María Susana Conconia, Gustavo Suareza,b,
Esteban F. Agliettia,b, Nicolás M. Rendtorffa,b,n
a
Centro de Tecnología de Recursos Minerales y Cerámica (CETMIC): (CIC-CONICET-CCT La Plata), Camino Centenario y 506, C.C.49 (B1897ZCA) M.B.
Gonnet, Buenos Aires, Argentina
b
Dpto. De Química, Facultad de Ciencias Exactas – Universidad Nacional de La Plata, UNLP, Argentina
Received 12 June 2013; accepted 12 July 2013
Available online 21 July 2013

Abstract

Calcareous earthenware is used very frequently for tableware, and fired twice between 980 1C and 1040 1C. Before firing it mostly consists in a
kaolinitic clay accompanied by quartz and ≈7 wt% of carbonates (Ca and Mg) as fluxing fraction. In this article the firing temperature correlation
with the textural, structural and mechanical properties was established in the 700–1100 1C firing range. Materials fired between 800 and 1050 1C
presented an interesting correlation between the processing variable (temperature) and the evaluated properties. The porosity in this range was almost
constant however the properties evolved exponentially with the temperature. A parallel behavior between flexural strength, diametral compression
resistance and dynamic elastic modulus was observed. Furthermore within the technological temperature range the correlation was linear.
Finally the incorporation of the porosimetric analysis performed permitted to understand that the firing processes of calcareous earthenware
below 1050 1C is not strictly a sintering process with a gradual densification and loss of porosity: it should be considered as a series of complex
chemical processes accompanied by a textural evolution of pore size increase with no important porosity decrease. Only for higher temperature
treatments (which exceed the technological ones) the porosity diminishes abruptly. When this reduction takes place, it is accompanied by an
increment in the mechanical properties figures and a loss in the dimensional stability.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: C. Mechanical properties; Clay based ceramics; Earthenware; Processing

1. Introduction clay has little amount of feldspar in its starting mineralogic

composition, and the fluxing part is formed by calcite (CaCO3)
The mechanical properties of porcelain bodies have been studied and dolomite (CaMg(CO3)2) hence it is wrong to assume this
extensively for almost a century. During this period three theories kind of material as an under fired triaxial ceramic [6,7].
have been presented to explain the strength of porcelains. These are The firing temperature is one of the most important
the “mullite hypothesis”, the “dispersion strengthening hypothesis” processing variables in the manufacture of ceramic pieces.
and the “matrix reinforcement hypothesis” [1–5]. In fact, in some cases, it defines the final product cost.
But in earthenware there are not a clear level of theoretical Accurate measurement, prediction and predetermination of
advances. In fact earthenware can be assumed to be an under material properties are important for its posterior use, and
fired porcelain, but this is only the case when strictly tri-axial undoubtedly the properties depends on both the phase (crystal-
(clay–quartz–feldspar) mixtures are being studied. Calcareous line and non-crystalline) composition and microstructure of the
final ceramic material [8–20].
n
Corresponding author at: Centro de Tecnología de Recursos Minerales y Ceramic clays are one of the most complicated ceramic
Cerámica (CETMIC): (CIC-CONICET-CCT La Plata), Camino Centenario y systems because of the non-simple relationship between the
506, C.C.49 (B1897ZCA) M.B. Gonnet, Buenos Aires, Argentina.
Tel.: +54 221 4840247; fax: +54 221 4710075.
behavior of minerals during the ceramic processing and the
E-mail addresses: rendtorff@cetmic.unlp.edu.ar, transformations during heating. These new crystalline phases
rendtorff@hotmail.com (N.M. Rendtorff). are sometimes grouped as neo-minerals [6]. A major challenge

0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.07.067
 Author's personal copy

1710 M.F. Serra et al. / Ceramics International 40 (2014) 1709–1716

is to predict the phase transformations in silicate ceramics, forming and dried to constant weight in an oven at 100 1C.
since non-simple relationships occur between the structural They were then fired at different temperatures between 700
characteristics of the fired products and the physical properties. and 1100 1C with a heating (and cooling) rate of 10 1C/min,
Upon firing, the minerals in the clay bodies undergo and a 15 min soaking time was applied. The selected tempera-
chemical and structural modifications deeply transforming ture range was chosen because the earthenware is usually fired
the original materials. The high temperature, low-pressure at 980 1C (Orton standard cone 06) in the first firing usually
mineral transformations are mainly influenced by the chemical known as biscuit fire, and the second glazing firing is usually
and mineralogical composition of the original clay, its grain- carried out in the 1020–1040 1C range (cone 05).
size distribution, the maximum heating temperature, heating Chemical analysis of a dried clay sample (clay) is shown in
rate, duration of firing and kiln redox atmosphere [1]. Table 1. In the same table, some properties of the unfired
Firing transformation inside traditional ceramic kilns was materials are shown: these values are typical for the kind of
extensively reported in the literature, but usually this kind of materials used in the local ceramic industry. It can be pointed
evaluation is carried out qualitatively and not quantitatively. out that the material present a high proportion of silica and that
During ceramic process, once the crystalline structures of the alumina content is low. Furthermore the fluxing fraction is
minerals exceed their stability limits, they are partially (or principally composed by calcium, magnesium and with small
completely) decomposed while simultaneously others are being amounts of potassium and sodium. Finally, the iron content
formed. The destruction of the pre-existing structure does not occur is 0.66%.
instantly, the processes are governed by the system′s thermody-
namic and kinetic properties. Moreover these transformations 2.2. Textural properties of the calcareous earthenware
determine the final properties of the ceramic products [1–5].
The objective of this article is to elucidate the effect of the firing Fig. 1 shows the textural properties evolution with the firing
treatment in the mechanical properties: flexural strength, diametral temperature (porosity: P, water absorption: WA, and density:
compression and dynamic elastic modulus and to correlate them D). As a first glance P, WA and D remained stable up to
with the textural and structural properties of different ceramics 1000 1C; a slight variation after 900 1C could be detected,
processed from an important ceramic body fired in a wide range of showing that before this temperature some mineralization
temperatures that include the industrial employed conditions. started. Another remarkable result is the observed stability of
A second objective is to establish the temperature range the properties in this wide temperature range which make them
where the studied mechanical properties are parallel. unsuitable for quality control parameters. Instead, a mechanical
The material studied in this work is a ceramic paste (body) for characterization is suggested.
commercial white earthenware (“Pasta blanca lisa”, earthenware The dilatometric behavior of the material was presented and
commercial formula from Argentina) and was previously studied in discussed in the mentioned previous work [6], but the most
other aspects by the same group of authors. This kind of material is important result contraction started only at 1050 1C and was
frequently used for tableware, and other small ceramic objects, abrupt, up to 1100 1C (the end of the experiment).
usually fired at low temperatures in electric or gas kilns [21].
The present study complements the results obtained in a
recent article [6]. In that work, the textural and crystalline 2.3. Phase evolution, XRD-Rietveld analysis
thermal evolution of the calcareous clay were established by a
complete thermal analysis (DTA-TG and dylatometric study Fig. 2 shows the thermal evolution in the crystalline phase
accompanied by an XRD-Rietveld characterization of the of the original material. The material consists in a mixture of
samples fired in a wide range of temperatures (800–1100 1C). quartz, clays (caolinite and illite) and carbonates (calcite and
In order to understand this paper, some of the results are dolomite) accompanied with a small amount of feldspars.
transcribed in the materials and methods of this paper in Table 1
Sections 2.1–2.3. Furthermore in Section 2.4 we present the Chemical composition and properties of the calcareous earthenware (unfired).
Hg porosimetry performed for this article, that complement the
Archimedes textural characterization carried out in the former As received dried clay (%wt)
article. In Section 2.5 we present the mechanical characteriza-
SiO2 70.85
tion carried out. In Section 3 we present the results and Al2O3 12.81
discussion, finally we present the conclusions in Section 4. Fe2O3 0.61
TiO2 0.53
2. Materials and methods CaO 3.62
MgO 1.65
Na2O 0.15
2.1. Materials processing K2O 2.00
LOI 7.80
In a recent article the firing transformations of this material Total 100
were presented [6]. The same material was employed for the Properties
Green density (gr/cm3) 1.94
mechanical characterization carried out in this article. Pris-
Green porosity (%) 28.3
matic specimens of 8
8
70 mm3 were elaborated by plastic
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M.F. Serra et al. / Ceramics International 40 (2014) 1709–1716 1711

[29] with high refractoriness being stable up to much higher

temperatures (o 1600 1C), however this first mullite has low
crystallinity and was well described before [29].

2.4. Hg porosimetry

Although a wide range of temperatures was studied, open

porosity was almost constant (30%) up to 1050 1C (Fig. 1).
The materials fired at 1100 1C presented a smaller porosity
(≈15%). Mercury intrusion tests were performed by using a
Fig. 1. Porosity, water absorption and density of the earthenware (P, WA and Pascal Porosimeter 140 Thermo Fisher and pressures ranging
D) as a function of firing temperature [6]. from 1 to 2000 kg/cm2 (sizes equivalent radius of pores in the
range of 37–75,000 Å). These results are complementary to the
Archimedes analysis.

2.5. Mechanical properties characterization procedures

Three mechanical properties were chosen for this analysis:

the dynamic elastic modulus (E), the flexural strength (sf) and
the diametral compression resistance of short cylinders (sd).
Fracture strength is one of the most common and widely used
mechanical properties for structural ceramics because it is the
most simple and important material reliability parameter.
A number of methodologies and techniques have been devel-
oped for this purpose. Most of these techniques equate fracture
Fig. 2. Crystalline phase composition of the earthenware evaluated by the strength to maximum stress (tensile, compressive or mixed) at
Rietveld method as function of the firing temperature. fracture. Consequently, in order for a particular load and
specimen geometry to be useful for determination of fracture
A complete identification and quantification was shown in a strength stress distribution must be well established. Due to
previous work [6,22–24]. advantages including simple geometry, low cost specimen
The complexity of the system from this perspective was fabrication flexural tests are the most widely used for measur-
clearly demonstrated. A group of clay minerals decomposed ing ceramic materials strength.
partially before 800 1C and completely before 900 1C. The diametral compression test, also known as “splitting
The amorphous phases grouped in Fig. 2 are principally test” or “Brazilian Test”, has usually been employed in the
metakaolin, product of the thermal decomposition of the mechanical evaluation due to several advantages: simpler piece
kaolinitic clay. In fact, this metakaolin is not strictly amor- preparation, simple geometry and quickness of testing, inde-
phous and can be understood as a low crystallinity phase [1,5]. pendent data with regard to surface finish and no edge effects
The flux components (carbonates) also decomposed at [30–32].
around 800 1C, moreover dolomite (a Mg–Ca carbonate) The elastic modulus (E) is a measurement of the material
resulted into a Ca carbonate at this temperature, and decom- stiffness, and is the slope of the stress strain plot. There are
posed only at after higher thermal treatments [25–27]. The some dynamic methods for evaluating E; the impulse excita-
product of the decomposition is not crystalline and accom- tion technique is usually employed for ceramic materials
panies the metakaolin in Fig. 2 in the amorphous or low [33,34]. When the object under test is subjected to an initial
crystalline group. deformation by means of a light mechanical impulse, the
A little amount of feldspars were present in the starting object will immediately act as a spring-mass system and
composition, the amount detected can be neglected [6]. On the produce a transient mechanical vibration. The frequency of
other hand feldspars, particularly plagioclase and gehelenite, this vibration depends on the mass of the object and its
crystallized after 900–1000 1C thermal treatments becoming stiffness, which is determined by its shape and dimensions and
the first minerals that mineralize within the calcareous clay. the modulus of elasticity of the material. The great advantage
However, after higher treatments they will decompose; gehle- of this technique is the low operative cost, high repetitivity and
nite first (1000 1C) and plagioclase after higher (and out of the fact that it is nondestructive [33].
range) temperatures (1150 1C) [28]. But a fring temperature of
1150 1C exceeds the one employed for these materials and is 2.5.1. Dynamic elastic modulus (E)
not observed in the performed tests. The dynamic elastic modulus E of the composites were
The most important neo-mineral of triaxial ceramics is measured by the excitation technique with a GrindoSonic,
mullite, that starts its formation between 900 and 1000 1C MK5 “Industrial” Model [34]. In each case the test was carried
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1712 M.F. Serra et al. / Ceramics International 40 (2014) 1709–1716

out in prismatic bars. The actual expression of the dynamic

elastic modulus can be found in literature [33].

2.5.2. Flexural Strength (sf)

The flexural strength (sf) was measured on 10 samples by a
three points test on the bars with a 40 mm span and a
displacing speed of 0.1 mm/min. Universal testing machine
(Instron 4483). Ten samples were measured for each sample
fired at different conditions.
The flexural strength was calculated from the following
equation:
3Ll
sf ¼ ð1Þ Fig. 3. Hg porosimetry curves of the earthenware fired at different tempera-
2wh2
tures. The mean pore diameter as a function of the firing temperature is shown
where L is the final maximum load of samples, l is the distance as a inset.
between the support points of the three point test, w is the
width of the samples and h is the height of the prisms.

2.5.3. Diametral compression (sd)

The diametral compression of cylinders was performed in
ten samples of 15.0 mm diameter (d) and 7.0 mm of thickness
(t) with the same Universal testing mechanical machine, with
the same load speed. In this case MoS2 lubricant paste was
applied on the platen surfaces in contact with the disk to
reduce the effect of friction; white and carbon papers were
placed together between each platen and the disk for load
distribution (padding material). L was employed for the final
maximum load of samples.
For this method the mechanical strength can be calculated
with the following equation (Eq. 2) effects [30–32].
2L Fig. 4. Dynamic elastic modulus (E) of the calcareous earthenware as a
sd ¼ ð2Þ function of the firing temperature (materials with ≈30% of porosity in squares
πdt and the material with 15% of porosity as a circle); the exponential growth
fitting is shown as well.

3. Results and discussion

it is a complex chemical processes described in Section 2.3
accompanied by a textural evolution of pore size increase.
3.1. Hg porosimetry

Pore size distributions (Hg intrusion) are shown in Fig. 3. 3.2. Dynamic elastic modulus (E) of the calcareous
Accumulative pore size curves are not similar for group of earthenware
materials studied, showing an important change when achiev-
ing 1100 1C. The starting asymptote of the materials behavior The obtained values are comparable to the ones that can be
is concordant with the Archimedes results (Fig. 1), the under found in literature [21]. The dispersion values are low for this
fired samples present higher and constant value. And the property. Fig. 4 shows the evolution of the dynamic elastic
sample fired at 1100 1C presented the lowest value. modulus of the material as a function of the maximum firing
However same difference could be evaluated: small pores temperature employed in the 700–1100 1C range. The results
(between 50 and 100 nm) proportion in the samples fired at were grouped in two groups in terms of the porosity evaluated
low temperature (800–900 1C) are important and null for the by the Archimedes method (Fig. 1), materials fired between
samples fired at 1000 and 1100 1C. 700 and 1050 1C presented porosities near to 30% and the
Finally, the mean pore diameter was plotted as a function of material fired at 1100 1C presented a 15% porosity value.
the firing temperature, inset in Fig. 3. The average pore size is An exponential growth is evident in the first group
clearly correlated with the firing. Remembering that the (squares); in the graph the exponential growth fitting results
porosity was constant and ≈30% for samples fired below are also shown. The fitting results (measured in the value of
1050 1C, the evaluated progression is remarkable. Showing R2) are adequate. This exponential growth has been reported
that the firing processes of earthenware below 1050 1C is not for different ceramic materials. And is usually related to the
strictly a sintering process with a gradual densification instead sintering (densification and decrease in the porosity) of the
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M.F. Serra et al. / Ceramics International 40 (2014) 1709–1716 1713

Fig. 5. Flexural strength (sf) of the calcareous earthenware as a function of the Fig. 6. Diametral compression resistance (sd) of the calcareous earthenware as
firing temperature (materials with ≈30% of porosity in squares and the material a function of the firing temperature; the exponential growth fitting is shown
with 15% of porosity as a circle); the exponential growth fitting is shown as well.
as well.

ceramic material. As described in former sections this is not

the case in the present earthenware, but the increase is still
exponential. In this case the behavior occurs with nearly
constant porosity and might be related with the pore size that
grows with the firing temperature as shown in Fig. 3, instead of
pore fraction in the 700–1050 1C range. Finally, for the
material fired at 1100 1C the abrupt increase is related to the
important porosity difference.

3.3. Flexural strength (sf) of the calcareous earthenware

Only after 1000 1C treatments the mechanical properties

achieved were adequate for the application [21] the actual Fig. 7. Mechanical properties of the studied materials (log graph).
industrial cycles are of 1040 1C. Fig. 5 shows the evolution of
the flexural strength (sf) with the firing temperature. The same accomplished in the whole range (700–1100 1C). The fact that
aggrupation was carried out (Section 3.2). In the first group the standard deviation values are much smaller than the ones
(porosity ≈30%) the exponential growth can be observed. As obtained for the flexural strength, together with the higher
expected the relative error is higher for sf than E. The result of values shows the benefits of this technique for this kind of
the mean square fitting is also shown in Fig. 5 and adequate. materials. When the material is plastic the employed disc
The achieved values are comparable to the one reported shapes can be easily obtained by extrusion (Fig. 6).
[1,7,21] for similar materials. The value for the over fired
material with lower porosity is relatively lower than the one 3.5. Comparison of the three mechanical properties studied
achieved for E, the flexural strength value depends on the
weakest defects and the elastic modulus is more related to the The three mechanical properties chosen present an expo-
bulk property. Again the observed exponential behavior is nential growth. The logarithms of the three properties are
remarkable taking into account that the firing processes are not plotted as a function of the firing temperature in Fig. 7. Instead
a strict sintering process in the 700–1050 1C temperature of E, E/1000 is plotted in order to compare easily. Evidently
range. For a nearly constant porosity group of ceramics the the three properties grow in a parallel way. Nevertheless in a
mechanical property obtained was not constant. more accurate analysis the exponential parameter follows the
E o sf o sd progression. And the pre-exponential parameter
3.4. Diametral compression (sd) of the calcareous follows the same progression.
earthenware
3.6. Linear temperature dependence range
The evolution of the diametral compression resistance can
be observed in Fig. 5, the achieved values are greater than the For a technological propose a linear range was seeked.
flexural strength (almost doubles). The exponential behavior Fig. 8 shows the linear evolution of E and sf in the 900–
was corroborated by the mean square fitting. The results are 1050 1C range. This range includes both technological tem-
shown in Fig. 5 also. The exponential behavior was peratures (980 1C and 1040 1C). Also in this range a linear fit
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1714 M.F. Serra et al. / Ceramics International 40 (2014) 1709–1716

Fig. 8. Dynamic elastic modulus (E) and flexural strength (sf) as a function of Fig. 9. Dynamic elastic modulus (E) and flexural strength (sf) of the
the firing temperature (intermediate range). The results of the linear fitting are earthenware as a function of the porosity.
shown. The vertical lines represent the manufacturing temperatures.

was carried out satisfactorily showing that the E slope is five times
the flexural strength slope. An interesting result is that within this
temperature range both technological properties are bonded. This
fact could represent an important operative saving in production
control (E¼ 4.1+4.86sf) and (sf ¼  0.84+0.206E).

3.7. Correlation between the mechanical properties. And

different important properties of the calcareous earthenware

3.7.1. Porosity and density correlation

There are several empirical or semi empirical models for the
relationship between the mechanical properties and the poros-
ity of ceramic materials [35–37]. All of them can be grouped in
exponential (or hyperbolic) decreases of the mechanical
properties as a function of the porous fraction P. Fig. 8 shows
the relation between the porosity, the dynamic modulus (E) Fig. 10. Mechanical properties of the studied calcareous earthenware as a
and the flexural strength (sf). The behavior is far away from function of the neominerals content (sum of all the crystalline phases).
the exponential decay generally observed in ceramic materials
[35–37]. Undoubtedly this fact is related with the crystalline
transformations that occur in parallel with the sintering modulus. It is important to point out that these correlations
processes during the thermal treatments. All the empirical occur in the range that includes the evaluated porosity step
models are based in stable materials that only differ in the (30–15%) (Fig. 1).
porosity.
Particularly, the behavior can be described as following. 3.7.3. Mullite correlation
Presenting two ranges, one dependent range (900–1100 1C) Fig. 11 shows the correlation of the three mechanical
and one independent range (700–900 1C). For E, the decrease properties studied and the mullite content in the final materials
is gradual (almost linear) with porosity in 30–10%. The evaluated by the Rietveld method. The mechanical properties
decrease in the 1100–900 1C is not linear, in fact it is abrupt increase with the mullite content. The mullite hypothesis is
in the 900–1050 1C range. These ranges correspond to the ones corroborated to this group of materials. It can be clearly shown
observed in the sintering processes (Fig. 1). although the mullite reinforcement method is not the only
acting mechanism that undoubtedly this mechanism contri-
3.7.2. Crystalline phases correlation butes to the increment in the mechanical properties. It is
Once the porosity correlation is discarded, the crystal- difficult to separate the mullite contribution to the other
lographic correlation is proposed. Fig. 9 shows the value of crystalline phases contribution (Section 3.7.2).
the mechanical properties as a function of the amount of
neominerals that crystalized in the ceramic material (Fig. 2). 3.7.4. Mean pore size correlation
Fig. 10 shows the correlation between the amount of Finally Fig. 12 shows the values of the three mechanical
crystalized minerals (neominerals) and the three mechanical properties studied as function of the mean pore size evaluated
properties studied in the 800–1100 1C firing temperature range. by porosimetry (Section 3.1). In the above sections the
While the correlation is linear for the flexural and diametral mechanical properties porosity relation could not be observed
compression strength it is exponential for the dynamic elastic moreover the porosity was almost constant between 800 and
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M.F. Serra et al. / Ceramics International 40 (2014) 1709–1716 1715

after 1000 1C treatments the mechanical properties achieved

were adequate for the application.
In fact, in this temperature range (800–1050 1C) the
mechanical properties increase with the crystallization of the
neominerals product of the described chemical processes.
These neominerals are feldspars (plagioclase and gehelenite)
and the spinel-type pre-mullite alumino silicate. Also during
this range the pore sized increased exponentially with no
densification.
The parallel growth of these mechanical properties was
established. Moreover it was shown to be exponential in the
wide range (700–1050 1C) and linear in a more technological
Fig. 11. Mechanical properties (flexural strength, diametral compression and range (900–1050 1C).
dynamic elastic modulus) of the calcareous earthenware as a function of the Finally the performed porosimetric analysis permitted to
mullite content. understand that the firing process of calcareous earthenware
below 1050 1C is not strictly a sintering process with a gradual
densification and loss of porosity instead it is a complex
chemical processes accompanied by a textural evolution of
pore size increase with no important porosity decrease. Only
for higher temperature treatments (exceeding the technological
ones) the porosity diminishes abruptly. This fact is accom-
panied by an increase in the mechanical properties figures and
a loss in the dimensional stability.

Acknowledgments

The authors wish to express their gratitude for the help in

Fig. 12. Mechanical properties (flexural strength, diametral compression and
porosimetry experiments and mechanical tests to Mr. Lucas
dynamic elastic modulus) of the calcareous earthenware as a function of the Huck and Mr. Martiniano Piccico respectively.
mean pore diameter.

References
1050 1C firing treatments. However the mechanical properties [1] W.M. Carty, U. Senapati, Porcelain-raw materials, processing, phase
are clearly correlated with the mean pore size in the sintering evolution and mechanical behaviour, Journal of the American Ceramic
temperature range studied, this correlation must be taken into Society 81 (1) (1998) 3–20.
account together with the crystalline phase (neominerals and [2] N.L.S. Lisiane, J.S. Bartolomeu, P.G. Wherllyson, M.C. Juliana, S.
L. Bruna, C.S. Renato, R.M. Romualdo, Influence of firing conditions on
mullite correlation) revealed in Sections 3.7.2 and 3.7.3.
properties of red ceramic, Materials Science Forum 727–728 (2012)
721–726.
[3] Y. Iqbal, W.E. Lee, Microstructural evolution in triaxial porcelain,
4. Conclusions Journal of the American Ceramic Society 83 (12) (2000) 3121–3127.
[4] A. De Noni, D. Hotza, V. Cantavella Soler, E. Sánchez Vilches, Influence
The effect of the firing temperature on the structural and of composition on mechanical behaviour of porcelain tile. Part III: effect
textural properties of calcareous clay body was established in a of the cooling rate of the firing cycle, Materials Science and Engineering
A 528 (9) (2011) 3330–3336.
previous work. This material is frequently employed for
[5] O. Castelein, B. Soulestin, J.P. Bonnet, P. Blanchart, The influence of
tableware, fired between 980 1C and 1040 1C. In this article heating rate on the thermal behaviour and mullite formation from a kaolin
the firing temperature correlation with the textural, structural raw material, Ceramics International 27 (5) (2001) 517–522.
and mechanical properties was established in the 700–1100 1C [6] M.F. Serra, M.S. Conconi, G. Suarez, E.F. Agietti, N.M. Rendtorff,
firing range. Materials fired between 800 1C and 1050 1C Firing transformations of an argentinean calcareous commercial clay,
presented an interesting correlation between the processing Cerâmica 59 (350) (2013) 254–261.
[7] M.J. Trindade, M.I. Dias, J. Coroado, F. Rocha, Mineralogical transfor-
variable (temperature) and the evaluated properties. The mations of calcareous rich clays with firing: a comparative study between
porosity in this range was almost constant however the calcite and dolomite rich clays from Algarve, Portugal, Applied Clay
properties evolved exponentially with the temperature. Science 42 (3–4) (2009) 345–355.
The three mechanical properties evaluated increased in a [8] M.M. Jordán, J.D. Martín-Martín, T. Sanfeliu, D. Gómez-Gras, C. de la
parallel way showing that in this temperature range, with the Fuente, Mineralogy and firing transformations of Permo-Triassic clays
used in the manufacturing of ceramic tile bodies, Applied Clay Science
accurate evaluation of one of them, the other two could be 44 (1–2) (2009) 173–177.
calculated. Furthermore a linear parallel correlation was found [9] M.M. Jordan, M.A. Montero, S. Meseguer, T. Sanfeliu, Influence of
in the technological temperature range (800–1050 1C). Only firing temperature and mineralogical composition on bending strength
 Author's personal copy

1716 M.F. Serra et al. / Ceramics International 40 (2014) 1709–1716

and porosity of ceramic tile bodies, Applied Clay Science 42 (1–2) (2008) [23] H.M. Rietveld, A profile refinement method for nuclear and magnetic
266–271. structures, Journal of Applied Crystallography 2 (1969) 65–71.
[10] B.C.A. Pinheiro, J.N.F. Holanda, Effect of the firing temperature on some [24] J. Rodríguez-Carbajal, Program FullProf. 98, version 0.2, 1998.
mechanical properties of red ceramic [Efeito da temperatura de queima [25] S. Maitra, A. Choudhury, H.S. Das, Ms.J. Pramanik, Effect of compac-
em algumas propriedades mecânicas de cerâmica vermelha], Ceramica 56 tion on the kinetics of thermal decomposition of dolomite under non-
(339) (2010) 237–243. isothermal condition, Journal of Materials Science 40 (18) (2005)
[11] M.M. Jordan, M.A. Montero, S. Meseguer, T. Sanfeliu, Influence of 4749–4751.
firing temperature and mineralogical composition on bending strength [26] É. Kristóf-Makó, A.Z. Juhász, In situ XRD study of the thermal
and porosity of ceramic tile bodies, Applied Clay Science 42 (1–2) (2008) decomposition of mechanically treated dolomite, Materials Science
266–271. Forum 321–324 (2000) 380–385.
[12] C.M.F. Vieira, S.S. Teixeira, S.N. Monteiro, Effect of the firing [27] E.D. Cater, P.R. Buseck, Mechanism of decomposition of dolomite,
temperature on the properties and microstructure of red ceramic incorpo- Ca0.5Mg0.5CO3, in the electron microscope, Ultramicroscopy 18 (1–4)
rated with grog [Efeito da temperatura de queima nas propriedades e (1985) 241–251.
microestrutura de cerâmica vermelha contendo chamote], Ceramica 55 [28] F. González-García, V. Romero-Acosta, G. García-Ramos, M. González-
(335) (2009) 332–336. Rodríguez, Firing transformations of mixtures of clays containing illite,
[13] F.A.C. Milheiro, M.N. Freire, A.G.P. Silva, J.N.F. Holanda, Densification kaolinite and calcium carbonate used by ornamental tile industries,
behaviour of a red firing Brazilian kaolinitic clay, Ceramics International Applied Clay Science 5 (4) (1990) 361–375.
31 (5) (2005) 757–763. [29] J. Sanz, A. Madani, J.M. Serratosa, J.S. Moya, S. Aza, Aluminum-27 and
[14] S.J.G. Sousa, J.N.F. Holanda, Characterization of non-calcareous thin red silicon-29 magic-angle spinning nuclear magnetic resonance study of the
clay from south-eastern Brazil: applicability in wall tile manufacture, kaolinite–mullite transformation, Journal of the American Ceramic
Ceramica 58 (345) (2012) 29–35. Society 71 (10) (1988) C418–C421.
[15] V. Das Kshama, B.V. Mohan, M. Lalithambika, C.G.R. Nair, Sintering [30] M.K. Fahad, Stresses and failure in the diametral compression test,
studies on plastic clays, Ceramics International 18 (6) (1992) 359–364. Journal of Materials Science 31 (14) (1996) 3723–3729.
[16] F. González-García, V. Romero-Acosta, G. García-Ramos, M. González- [31] C. Rocco, G.V. Guinea, J. Planas, M. Elices, Review of the splitting-test
Rodríguez, Firing transformations of mixtures of clays containing illite, standards from a fracture mechanics point of view, Cement and Concrete
kaolinite and calcium carbonate used by ornamental tile industries, Research 31 (1) (2001) 73–82.
Applied Clay Science 5 (4) (1990) 361–375. [32] M.L. Sandoval, M.A. Pucheu, M.H. Talou, A.G. Tomba Martinez, M.
[17] M.M. Jordán, A. Boix, T. Sanfeliu, C. De La Fuente, The mineralogy of A. Camerucci, Mechanical evaluation of cordierite precursor green bodies
Cretaceous clays in Castellon and their application in the ceramic obtained by starch thermogelling, Journal of the European Ceramic
industry, International Ceramics Journal 10 (1995) 25–29. Society 29 (16) (2009) 3307–3317.
[18] M.M. Jordán, A. Boix, T. Sanfeliu, C. De La Fuente, Firing transforma- [33] M. Radovic, E. Lara-Curzio, L. Riester, Comparison of different
tions of cretaceous clays used in the manufacturing of ceramic tiles, experimental techniques for determination of elastic properties of solids,
Applied Clay Science 14 (4) (1999) 225–234. Materials Science and Engineering A 368 (1–2) (2004) 56–70.
[19] M.M. Jordán, T. Sanfeliu, C. De La Fuente, Firing transformations of [34] N.M. Rendtorff, L.B. Garrido, E.F. Aglietti, Mechanical and fracture
Tertiary clays used in the manufacturing of ceramic tile bodies, Applied properties of zircon–mullite composites obtained by direct sintering,
Clay Science 20 (1–2) (2001) 87–95. Ceramics International 35 (7) (2009) 2907–2913.
[20] S. Meseguer, F. Pardo, M.M. Jordan, T. Sanfeliu, I. González, Ceramic [35] W. Pabst, E. Gregorová, G. Tichá, Elasticity of porous ceramics—a
behaviour of five Chilean clays which can be used in the manufacture of critical study of modulus porosity relations, Journal of the European
ceramic tile bodies, Applied Clay Science 47 (3–4) (2010) 372–377. Ceramic Society 26 (2006) 1085–1097.
[21] ASTM Designation C 242, Standard definition of terms related to ceramic [36] W. Pabst, E. Gregorová, G. Tichá, Effective properties of suspensions,
whiteware and related products, ASTM designation C 242, Annual Book composites and porous materials, Journal of the European Ceramic
of ASTM Standards, vol. 15.02, American Society for Testing and Society 27 (2007) 479–482.
Materials, Philadelphia, PA, 1996. [37] A.S. Wagh, J.P. Singh, R.B. Poeppel, Dependence of ceramic fracture
[22] D.L. Bish, J.E. Post, Quantitative mineralogical analysis using the properties on porosity, Journal of Materials Science 28 (13) (1993)
Rietveld full-pattern fitting method, American Mineralogist 78 (1993) 3589–3593.
932–940.

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