Thermochimica Acta 581 (2014) 100–109

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

The effect of temper on the thermal conductivity of traditional

ceramics: Nature, percentage and granulometry
Ignazio Allegretta a,∗ , Giacomo Eramo a , Daniela Pinto a , Anno Hein b
a
Dipartimento di Scienze della Terra e Geoambientali, Università degli Studi di Bari “Aldo Moro”, Via Orabona 4, 70125 Bari, Italy
b
Department of Materials Science, N.C.S.R. “Demokritos”, Aghia Paraskevi, 15310 Athens, Greece

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

Article history: Traditional ceramics were commonly produced using a mixture of clay and temper materials, which were
Received 31 October 2013 added in different percentage according to the craftsman purposes. The present study aims to examine up
Received in revised form 21 February 2014 to which extent some technological parameters (nature, granulometry and percentage of the temper and
Accepted 22 February 2014
firing temperature) affect the thermal conductivity of traditional ceramics. With this purpose a kaolinitic
Available online 2 March 2014
clay was tempered either with quartz or limestone belonging to two different granulometric distributions
in percentage of 5%, 15% and 25%, and fired at 500, 750 and 1000 ◦ C. Moreover the dependence on firing
Keywords:
temperature was studied. Thermal conductivity was measured with a modified Lee’s disks apparatus in a
Thermal conductivity
Traditional ceramics
temperature range from 120 to 370 ◦ C. It was found that quartz-tempered ceramics are more conductive
Quartz than the fired non-tempered clay, while limestone-tempered sample are less conductive. Mineralogical
Limestone and microstructural data are also provided and the influence of the ˛–ˇ quartz-phase transition on the
Firing temperature thermal conductivity of ceramics is discussed.
Microstructure © 2014 Elsevier B.V. All rights reserved.

1. Introduction
Ceramics were at the base of the economic and social life of
ancient society, as utilitarian and as artistic artefacts. Among util-
itarian ceramics, Rice [1] distinguishes three functional categories
for domestic pottery: storage, transport and processing. Ceramic
vessels for processing (or transformation) played a specific role, as
they were used as tools in various production cycles, apart from
food preparation also for example as crucibles, tuyeres, moulds,
etc. To fulfil its function, an artefact should have specific physical
properties which depend on the raw materials, the shape of the
object and the production cycle.
As to raw materials, ancient potters could use calcareous or non-
calcareous clay to produce respectively high or low porous ceramics
[2]. They could, also, modify the natural clay by refining or tem-
pering [1,3,4]. Both these actions affect the plasticity and, hence,
the workability of the clay paste: the removal of coarse particles
results in an increase in kneading plasticity, while the addition of
non-plastic materials (like quartz, limestone, grog, sand, shells, etc.)
makes the clay less sticky and plastic. Moreover, temper was added
∗ Corresponding author. Tel.: +39 0805442608; fax: +39 0805442625.
E-mail addresses: ignazio.allegretta@uniba.it, ignazio.allegretta@libero.it
(I. Allegretta), giacomo.eramo@uniba.it (G. Eramo), daniela.pinto@uniba.it
(D. Pinto), hein@ims.demokritos.gr (A. Hein).
to the clay mixture to reduce the drying time and the shrinkage with
consequent reduction of cracks and flaws in the artefact [1]. In this
way, potters obtained more durable fired products. The addition of
temper, in fact, influences the mechanical properties of ceramics
decreasing their strength but increasing their toughness [5,6].
The fabrication of a vessel with a specific shape facilitates its
use in a particular environment. For example, jars are more suit-
able than bowls in pouring liquids, while a spherical shape is more
appropriate than a cylindrical one to produce cooking pots because
in this way a larger surface is put in contact with the flame [1].
The methods used to mould the clay or to finish the artefacts
gave it certain characteristics. A technique called burnish, which
consists in rubbing the surface of the body with a hard tool, was
employed on the unfired object to reduce its permeability to liquids
[3]. Clay lumps mixed with very few amount of water were beaten
with hammers for the production of glass crucibles in order to avoid
a great shrinkage and the consequent formation of cracks which
could affect their performances.
Among all the physical properties, the one which plays a
determinant role in the heat transfer process, especially in trans-
formation ceramics, is the thermal conductivity [1]. It depends on
mineral phases, microstructures and porosity developed in ceram-
ics during processing and firing of raw materials [7–9]. In this sense,
the choice of raw materials is a critical step in the production of
suitable ceramics for a specific function. For example, technical
ceramics like smelting crucibles, which have an internal heating

http://dx.doi.org/10.1016/j.tca.2014.02.024
0040-6031/© 2014 Elsevier B.V. All rights reserved.
 I. Allegretta et al. / Thermochimica Acta 581 (2014) 100–109 101

source, should be insulating to reduce the heat loss through the

walls. To do this, craftsmen created wares rich in pores or increased
the thickness of the container [10–12]. In contrast to these, techni-
cal ceramics which are heated from the outside, like cooking pots
or glass melting crucibles, should have been rather conductive in

Fraction content (%)

order to transfer as much heat as possible to their content. In this
case heat barriers like pores should be avoided using, for example,
less shrinking clay pastes. It is evident that the modification of the
clay mix by tempering is the most used method for enhancing or
reducing the thermal conductivity of the final product.
The two most common tempers used by ancient potters were
limestone and quartz [3,13,14]. According to firing temperature,
carbonates and quartz face different phase changes which modify
the texture of the ceramic body and, hence, its thermal properties.
While the effect of tempering on the strength and toughness of
ceramics was studied in depth [5,6,15,16], not the same attention
was paid to its effect on thermal conductivity. In the last years some
works concerning the effect of quartz or volcanic rock fragments on
Fig. 1. Granulometric distributions of the temper used for the production of the
thermal conductivity of traditional ceramic have been published samples (the fraction content in weight percentage vs. temper grain size is plotted).
[17]. As to limestone-tempered ceramics, even if some works have
been found [18], they do not consider the effect of temperature on
considered, which is that soaking temperature maintained for 1 h,
this kind of materials which is a crucial point [19]. Moreover no
producing a particular mineral content and microstructure [27].
attention has been paid to the granulometry of the temper which,
The name of the samples has the following structure: temper
as it is known, could affect mechanical properties [15,20]. For these
percentage (5, 15, 25), temper granulometry (C for coarse and F
reasons, this work analyzes the relation existing between the ther-
for fine sand), temper nature (L for limestone and Q for quartz)
mal conductivity of the ceramic body and the nature, percentage,
and firing temperature. Non-tempered samples are identified by
granulometry of temper used and the firing temperature employed.
the abbreviation NT. All the sample characteristics and names are
Finally, the use of temper with a given grain size distribution, rather
reported in Table 1.
than a single grain size class, was useful to test its effect other than
One month has been waited before testing the material in order
the relative amount of temper. This information could be used to
to enable the hydration reaction of CaO in limestone-tempered
better understand the criteria used by ancient craftsman to choose
specimens. Subsequently the porosity was estimated by water
raw materials and to deepen the development of ceramic technol-
immersion [28]. The microstructure of the ceramic tests was
ogy through the centuries.
observed by scanning electron microscopy (SEM) (50XVP LEO,
operated at 15 kV), while the mineralogical content was investi-
gated using a X-ray powder diffractometer PANalytical X’Pert pro
MDS, using CuK␣ radiation (40 kV; 40 mA) in step scan mode (0.02◦
2. Experimental procedure
2), with each step measured for 11 s. The incident beam passed
through a 0.04 rad, Soller slit, a 1/2◦ divergence slit, a 15 mm fixed
A total of 126 test pieces were prepared using a kaolinitic clay
mask and a 1/2◦ fixed anti-scatter slit.
(kaolinite = 58%, illite = 18%, smectite = 2%, quartz = 22%, rutile and
To determine thermal conductivity (k) a modified Lee’s disk
anatase in traces) [21]. Both limestone and quartz were chosen
apparatus was employed, a stationary method, which has proved to
as temper. Differently from literature [17] two different granu-
be suitable for the measuring of this parameter in insulating mate-
lometric distributions were chosen to reproduce in the best way
rials [17]. The setup consists of a brass disk of 70 mm of diameter,
the archaeological data. In fact, archaeological evidence suggests
acting as heat source at a stabilized and freely chosen temperature,
that the temper added to a clay mixture does not belong to a
of the sample disk placed on this heat source and of another brass
specific grain size but it belongs to a granulometric distribution
disk (detector) of the same dimension placed on top of the sam-
[13,14,22–24]. With this purpose two granulometric distributions
ple. The temperatures of the two brass disks were recorded with
per type of temper were prepared (Fig. 1): a fine sand with a mode at
thermocouples connected to a data logger. Thermal conductivity
125 ␮m (positive-skewed curve) and a coarse sand having a mode
of each sample was investigated in the range from 120 to 370 ◦ C.
at 1 mm (negative-skewed curve).
The setup was left for heating up until the thermal equilibrium was
The clay was mixed with 5, 15 and 25 vol% of temper, adding
reached. On the basis of the temperature difference between the
5 vol% of water and pressing the mixture in a mould of 70 mm of
brass disks thermal conductivity was calculated in the following
diameter and 10 mm of height. Although some procedures to hin-
way:
der lime spalling in limestone-tempered ceramic bodies are known
[4,25,26], in this research it was planned to process in the same way x
k(T ) = q̇loss (T )
all the test pieces, without any pre- or post-firing treatment, which A(T1 − T2 )
could have introduced further variables in the samples. A pressure where x and A are respectively the thickness of the specimen and
of 25 MPa was chosen in order to reduce the number of large pores the surface area in contact with the brass disk and T1 and T2 are
which greatly affects thermal conductivity [7]. After 1 day of drying the temperatures recorded on the heating and detector disk. The
at 100 ◦ C, samples were fired at 500, 750 and 1000 ◦ C with a rate of heat loss of the detector disk was determined using the following
150 ◦ C/h and a soaking time of 1 h. This soaking time was chosen relation:
to be a normalizing firing condition to compare the fabric of the
ceramic tests with that of similar archaeological ceramics, since in dT
q̇loss (T ) = mbrass Cp,brass
this latter case their fabric was a combination of unknown firing dt
conditions (i.e. T/t evolution and firing atmosphere). Thus, instead where mbrass and cp,brass are the mass and the heat capacity of the
of maximum firing temperature an equivalent firing temperature is brass disk. The mass of the brass disk was 173.9 g and its heat
102 I. Allegretta et al. / Thermochimica Acta 581 (2014) 100–109

Table 1
Characteristics of the analyzed samples. The letters Q and L refer to ceramics temper with quartz or limestone, while C and F indicate the granulometry of the temper
(respectively coarse and fine). Finely, for non-tempered ceramics the prefix NT is used.

Sample Temper Temperature (◦ C)

Quantity (vol. %) Nature Granulometry (mm)

NT500 500
NT750 750
NT1000 1000

5CQ500 5 Quartz 1.000 500

15CQ500 15 Quartz 1.000 500
25CQ500 25 Quartz 1.000 500
5FQ500 5 Quartz 0.125 500
15FQ500 15 Quartz 0.125 500
25FQ500 25 Quartz 0.125 500
5CL500 5 Limestone 1.000 500
15CL500 15 Limestone 1.000 500
25CL500 25 Limestone 1.000 500
5FL500 5 Limestone 0.125 500
15FL500 15 Limestone 0.125 500
25FL500 25 Limestone 0.125 500

5CQ750 5 Quartz 1.000 750

15CQ750 15 Quartz 1.000 750
25CQ750 25 Quartz 1.000 750
5FQ750 5 Quartz 0.125 750
15FQ750 15 Quartz 0.125 750
25FQ750 25 Quartz 0.125 750
5CL750 5 Limestone 1.000 750
15CL750 15 Limestone 1.000 750
25CL750 25 Limestone 1.000 750
5FL750 5 Limestone 0.125 750
15FL750 15 Limestone 0.125 750
25FL750 25 Limestone 0.125 750

5CQ1000 5 Quartz 1.000 1000

15CQ1000 15 Quartz 1.000 1000
25CQ1000 25 Quartz 1.000 1000
5FQ1000 5 Quartz 0.125 1000
15FQ1000 15 Quartz 0.125 1000
25FQ1000 25 Quartz 0.125 1000
5CL1000 5 Limestone 1.000 1000
15CL1000 15 Limestone 1.000 1000
25CL1000 25 Limestone 1.000 1000
5FL1000 5 Limestone 0.125 1000
15FL1000 15 Limestone 0.125 1000
25FL1000 25 Limestone 0.125 1000

capacity was 0.38 kJ/(kg K). dT/dt was estimated as the slope of the
temperature vs time curve of the brass disk when it was left for
cooling (Fig. 2).
Moreover, the experimental results of thermal conductivity of
the ceramic tests are compared with computed data. The thermal
conductivity of the matrix (kmat ) was calculated using the equation
suggested by Litovsky [29]:
1/4
ku.c. (T ) − pu.c. kpor
kmat (T ) =
(1 − pu.c. )3/2
where ku.c. and pu.c. are the thermal conductivity and the porosity
(from 0 to 1) of the untempered ceramic fired at a certain temper-
ature and kpor is the thermal conductivity of air.
In order to calculate the thermal conductivity (ks ) of the solidus
part in tempered material, Maxwell eqaution was used [19]:
1 + 2vd (1 − kmat /kd )/(2kmat /kd + 1)
ks = kmat
1 − vd (1 − kmat /kd )/(kmat /kd + 1)
where kd and vd are the thermal conductivity and the volume frac-
tion of the disperse phase (in this case the temper).
Finally, the computed thermal conductivity of a porous tem-
pered ceramic (kcomp ) was determined as follow:
kcomp = ks (1 − p)3/2 + p1/4 kpor
where p is the porosity of the tempered sample measured by water
immersion. Considering the thermal conductivity of quartz and
pores respectively equal to 1.7 and 0.024 W m−1 K−1 [30], a the-
oretical thermal conductivity could be calculated.
This comparison has been proposed only for quartz-tempered
ceramics because contrary to limestone, quartz does not react in
these temperature ranges.
3. Results and discussion
One month after the firing, 15% – fine-limestone and, 25% –
coarse-limestone-tempered ceramics fired at 750 ◦ C, as well as all
the specimens tempered with coarse limestone fired at 1000 ◦ C, has
deteriorated due to lime spalling.
3.1. Mineralogical content
Semi-quantitative results of XRPD investigations are reported
in Table 2. They show that the mineral content of the samples is
related to the kind of mixture (i.e. limestone or quartz temper) and
the firing temperature. The mineral content of quartz-tempered
ceramics is qualitatively the same as that of non-tempered clay
fired at the same temperature (i.e. 500, 750 and 1000 ◦ C). For
limestone-tempered samples fired at 500 ◦ C, the same evidence can
also be observed, with the exception of calcite added as temper. On
 I. Allegretta et al. / Thermochimica Acta 581 (2014) 100–109 103

A B

Heat Flux in J/s

T (°C)
exo

Cooling time (s) T (°C)

Fig. 2. Cooling curve of the brass disk at 25 ◦ C represented as temperature in function of cooling time (A) and the heat flux corresponding to the measured temperature (B).

Table 2
Semi-quantitative mineral data.

Sample Mineral phases

Kln Ilt Sme Ant Rt Qz Cal Lm Prt Gh Ca-Ol An Wo Mul Spl-type

Clay xxxx xx x tr tr xx
NT500 xxx xx x tr tr xx
NT750 xx x tr tr xx
NT1000 tr tr xx tr xxx

5CQ500 xxx xx x tr tr xx
15CQ500 xxx xx x tr tr xxx
25CQ500 xxx xx x tr tr xxxx
5FQ500 xxx xx x tr tr xx
15FQ500 xxx xx x tr tr xxx
25FQ500 xxx xx x tr tr xxxx
5CL500 xxx xx x tr tr xx x
15CL500 xxx xx x tr tr xx xx
25CL500 xxx xx x tr tr xx xxx
5FL500 xxx xx x tr tr xx x
15FL500 xxx xx x tr tr xx xx
25FL500 xxx xx x tr tr xx xxx

5CQ750 xx x tr tr xx
15CQ750 xx x tr tr xxx
25CQ750 xx x tr tr xxxx
5FQ750 xx x tr tr xx
15FQ750 xx x tr tr xxx
25FQ750 xx x tr tr xxxx
5CL750 xx x tr tr xx x
15CL750 xx x tr tr xx xx
25CL750 xx x tr tr xx xx x
5FL750 xx x tr tr xx x tr
15FL750 xx x tr tr xx x x
25FL750 xx x tr tr xx xxx tr

5CQ1000 tr tr xx tr xxx
15CQ1000 tr tr xxx tr xxx
25CQ1000 tr tr xxxx tr xxx
5FQ1000 tr tr xx tr xxx
15FQ1000 tr tr xxx tr xxx
25FQ1000 tr tr xxxx tr xxx
5CL1000 tr tr xx tr tr xxx
15CL1000 tr tr xx x x tr tr xxx
25CL1000 tr tr xx xx x tr tr tr xxx
5FL1000 tr tr xx tr tr tr tr xxx
15FL1000 tr tr xx x tr tr tr xxx
25FL1000 tr tr xx tr xx x tr tr tr tr xxx

The following mineral phases are detected: quartz (Qz), anatase (Ant), illite (Ilt), kaolinite (Kln), smectite (Sme), calcite (Cal), rutile (Rt), portlandite (Prt), lime (Lm), gehlenite
(Gh), calcio-olivine (Ca-Ol), mullite (Mul), spinel-type phase (Spl-type), wollastonite (Wo). Mineral abbreviations after Whitney and Evans [41].

the contrary, the mineral assemblage in the limestone-tempered
bodies fired at 750 and 1000 ◦ C, differs from that of the non-
tempered clay fired at the same temperatures, as consequence
of the reaction between calcite and the clay matrix. According to
XRPD data the original kaolinite of the clay is completely trans-
formed into metakaolinite [31–33] in samples fired at 750 ◦ C, while
relicts of illite/mica and smectite structures are still present at this
temperature. The principal newly formed phase in limestone-
tempered samples fired at 750 ◦ C is portlandite (which forms
by lime hydration after firing); the major concentration of this
mineral phase was detected in the two samples which cracked
after the firing (25CL750 and 15FL750). Traces of gehlenite
occur only in the 25% – fine-limestone-tempered sample fired at
750 ◦ C. In limestone-tempered samples fired at 1000 ◦ C, lime and
104 I. Allegretta et al. / Thermochimica Acta 581 (2014) 100–109

Coarse Tempered fired at 500 °C Fine Tempered fired at 500 °C

k (W/mK)

k (W/mK)
T (°C) T (°C)

Coarse Tempered fired at 750 °C Fine Tempered fired at 750 °C

k (W/mK)
k (W/mK)

T (°C) T (°C)

Coarse Tempered fired at 1000 °C Fine Tempered fired at 1000 °C

.
k (W/mK)

k (W/mK)

T (°C) T (°C)

Fig. 3. Thermal conductivity of ceramic samples vs. test temperature. Circles, triangles and squares respectively represent 5%, 15% and 25% – tempered ceramics. Quartz-
tempered ceramics are represented with solid symbols while limestone-tempered bodies with hollow ones. Non-tempered samples are shown with a star.

gehlenite occur in coarse- and fine-tempered ceramics, respec-
tively, in addition to portlandite. All these samples contains also
an amorphous phase testified by a broad hump in the background
in the range 15–30◦ 2, a spinel-type phase [31,32,34–37] and
traces of a weakly crystallized mullite, occurring as reaction prod-
uct of the decomposition of metakaolinite [32,33,35,36,38,39]. A
more detailed discussion of the mineralogical composition of the
samples, including quantitative and microstructural data as well
as discussions about reactions taking place on them, is presented
by Allegretta [40] and will be the subject of an upcoming paper.
According to Allegretta and coauthors [40], the percentage of amor-
phous phases in samples fired at 1000 ◦ C ranges from 18 to 40 wt.%,
the spinel-type phase varies between 25 and 35 wt.% and mullite
ranges from 4 to 8 wt.%. Spinel-type phase has been identified as a
␥-Al2 O3 or at least a Si-poor Al-spinel [40]. Lime and portlandite
range from 0 to 10 wt.% and from 1 to 10 wt.%, respectively, in
 I. Allegretta et al. / Thermochimica Acta 581 (2014) 100–109 105

Fig. 4. BSE micrographs of limestone-tempered ceramics fired at 500 ◦ C (A and B), 750 ◦ C (C and D) and 1000 ◦ C (E and F). Cracks parallel to the surface are signed with a
white arrow. The magnification in macrograph F, puts in evidence the reaction rim around fine limestone grains.

coarse-limestone tempered samples, from 0 to 1 wt.% and from 1
to 14 wt.%, respectively, in fine-tempered samples. The percentage
of gehlenite is directly related to the amount of the temper and
its granulometry. It ranges from 0 to 1 wt.% in coarse-limestone
tempered samples and from 1 to 4 wt.% in fine tempered.
Traces of a probable Ca-olivine phase were detected in sam-
ple 25CL1000 and in all fine tempered samples, whereas traces of
anorthite and wollastonite were only detected in sample 25FL1000
[40].
3.2. Thermal conductivity
3.2.1. The effect of temper
A first distinction about the effect produced by the addition
of either limestone or quartz could be done. In fact, the addition
of quartz increases the thermal conductivity of the ceramic body,
whereas the addition of limestone always produces a reduction of k
(Fig. 3). Both calcite and quartz are more conductive than the fired
clay [30,42] and therefore the addition of either quartz or limestone
(kQz = 7.7 W m−1 K−1 and kCal = 3.6 W m−1 K−1 at 30 ◦ C) should pro-
duce a positive effect on the thermal conductivity of the ceramic
[19]. Taking into account a reduction of the thermal conductivity
with the temperature increase [30], kQz and kCal are respectively 1.7
and 1.6 W m−1 K−1 and hence greater than the thermal conductiv-
ity of the non-tempered ceramic body. This difference in thermal
behaviour between quartz and limestone-tempered ceramic could
not be explained only on the basis of the difference in thermal con-
ductivity of the two tempers. Another factor should be considered:
these two thermal conductivity values are relative to crystal phases
and not to rocks. In particular, as the limestone used for the fabrica-
tion is a micritic one, the presence of discontinuities in the temper
itself (Fig. 4A and B) lowers the thermal conductivity of the temper
and consequently the thermal conductivity of the ceramic.
As regards quartz-tempered samples, Fig. 3 shows that while in
samples fired at 500 ◦ C k increases with quartz content, in samples
fired at 750 and 1000 ◦ C the highest thermal conductivity is reached
with the 15% of quartz temper. At the same time, 15% – tempered
ceramics are less porous than 25% – tempered ones. In fact, in coarse
and fine-tempered bodies fired at 750 ◦ C, porosity (Table 3) moves
respectively from 44% to 45% and from 43% to 44% tempering with
15% and 25% of quartz. The porosity difference between 15% and
25% – tempered ceramics increases when firing temperature is set
at 1000 ◦ C. In this case, using both coarse and fine quartz, porosity
moves from 39% (15CQ1000 and 15FQ1000) to 42% (25CQ1000 and
25FQ1000). This could be explained taking into account the ˛–ˇ
quartz phase change. In fact, this phenomenon occurs at 573 ◦ C and
106 I. Allegretta et al. / Thermochimica Acta 581 (2014) 100–109

Table 3
Open porosity of ceramic samples determined by water immersion. For 1000 ◦ C-fired bodies tempered with coarse limestone, porosity is not determined (ND) because of
ceramic breaking.

Sample p  Sample p  Sample p 

NT500 43 4 NT750 47 1 NT1000 40 1

5CQ500 39 1 5CQ750 46 <1 5CQ1000 40 1
15CQ500 37 <1 15CQ750 44 <1 15CQ1000 39 1
25CQ500 35 4 25CQ750 45 1 25CQ1000 42 <1
5FQ500 41 2 5FQ750 47 <1 5FQ1000 40 <1
15FQ500 37 1 15FQ750 43 <1 15FQ1000 39 <1
25FQ500 33 <1 25FQ750 44 <1 25FQ1000 42 <1
5CL500 41 1 5CL750 47 2 5CL1000 ND ND
15CL500 39 <1 15CL750 45 2 15CL1000 ND ND
25CL500 38 3 25CL750 41 2 25CL1000 ND ND
5FL500 46 2 5FL750 49 4 5FL1000 42 3
15FL500 43 3 15FL750 42 2 15FL1000 38 2
25FL500 44 4 25FL750 40 1 25FL1000 39 4

is associated with an increasing of 2% of volume [43–46]. When the
temperature drops to room temperature, the phase change ˇ–˛
occurs producing a detachment zone around quartz grains as can
be clearly observed in Fig. 5. These voids behave as thermal bar-
riers and are closely connected with the quartz content and the
firing temperature. In fact, in 500 ◦ C-fired samples, in which the
˛–ˇ phase transition did not occur, the highest thermal conductiv-
ity is reached with 25% of quartz. This phase transition could explain
why in 25% – quartz tempered material the porosity is higher than
in 15% – tempered tests fired at 750 and 1000 ◦ C.
As shown in Fig. 6, the computed keff of 25% – quartz-tempered
ceramics is equal to or minor than keff of 15% – tempered samples.
In fact, even if the quartz content increases, the phenomenon of
heating conduction is influenced more by the less conductive phase
[19] (pores) which is higher in 25% – tempered ceramics (Table 3).
Regarding limestone-tempered samples, differences in thermal
conductivity are due to the development of secondary porosity and
fractures in the samples. At 500 ◦ C, increasing in limestone content
produces a reduction in porosity which moves from 41% to 38% (in
coarse-tempered ceramics) and from 46% to 44% (in fine-tempered
bodies). This reduction in porosity should lead to an increase in
thermal conductivity. However, 25CL500 and 25FL500 are less con-
ductive than the other limestone-tempered ceramics. In this case,
the problem is the geometry of the pores. In fact, as shown in
Fig. 4B, the porosity of 25% – tempered samples is characterized
by fractures parallel to the sample surface which affected thermal
conductivity more than dispersed porosity [10,12].
At 750 ◦ C the loss of some samples due to lime hydration does
not allow to analyze clearly the effect of progressive limestone
addition on thermal conductivity. However, while for ceramics
tempered with fine limestone this thermal behaviour could be
explained on the base of the porosity (25FL750 are less porous
and more conductive than 5FL750), for coarse-tempered bodies the
problem is the shape of the pore. In fact, even if 5CL750 is more
porous than 15% – tempered, these last one have a porosity charac-
terized by fractures perpendicular to the heat flux (Fig. 4C and D). At
1000 ◦ C only fine tempered samples survived because of hydration
of the lime. The progressive addition of limestone decreases the
thermal conductivity. This is due to the formation of big fracture
perpendicular to heat flux because of the lime hydration (Fig. 4E
and F). A further contribution to the reduction of thermal conduc-
tivity could be given by gehlenite which is less conductive than
calcite (kGh = 1.5 W/m K at 30 ◦ C) and forms in limestone-tempered
bodies fired at 1000 ◦ C (estimated from 1 to 4 wt.%) [40].
Finally, analyzing the influence of the granulometric distribu-
tion of the temper it is possible to see that 500 ◦ C-fired samples
tempered with fine quartz have a lower thermal conductivity than
those tempered with coarse quartz. In quartz-tempered samples
fired at higher temperature no significant differences could be
observed between the trends of thermal conductivity of the ceramic
pastes with different granulometry. The comparison among the
experimental thermal conductivity value of ceramic pastes tem-
pered with quartz and fired at 1000 ◦ C (Fig. 6) shows that the k
values of fine- and coarse-tempered samples converge at 15%, but
invert at 5% and 25%. Such inversion is consequence of the higher
rim porosity around coarse quartz grains at 120 ◦ C, which decreases
at 370 ◦ C because of the thermal expansion of quartz grains.
In limestone-tempered ceramics no difference could be
detected between coarse and fine-tempered materials. At 750 ◦ C
the effect of the granulometry is negligible in comparison with the
effect due to porosity and the data could not be put in relation
because some sample went destroyed because of the hydration of
CaO to form portlandite (Table 2). For the same reason, the effect
of granulometry in limestone-tempered samples fired at 1000 ◦ C
could not be analyzed.
3.2.2. The effect of firing temperature
Regarding to the effect of firing temperature, a sensible reduc-
tion of thermal conductivity is recorded at 750 ◦ C due to the
increase in porosity (as shown in Table 3 porosity goes from 40% of
NT500 to 47% of NT750) in samples fired at this temperature and
the dehydroxylation of kaolinite proved by the absence of kaolin-
ite peak at d = 7 Å. Only in samples 15FL750 and 25FL750 porosity
decreases and this is due to the fine size of the limestone inclusions.
The stresses caused by the dilatation of coarse grains are greater
than that produced by fine ones. Such dilatation occurs during the
sintering of the clay matrix, which undergoes a plastic deforma-
tion when heats up and rests fixed when cools down, opening up
rim pores around the limestone inclusions. Limestone inclusions
have of course the same thermal expansion coefficient, which has
a lower mismatch with the sintered matrix compared to that of
quartz [4]. Some authors [47] suggest either to finely crush or to
preheat the limestone in order to counteract the formation of cracks
around the particles. Moreover, portlandite (which is the respon-
sible of the destruction of 25CL750 and 15FL750) does not form in
25FL750 and traces of gehlenite are detected (Table 2), which can
create a connection between fine limestone grains and the matrix.
At 1000 ◦ C, k increases again, due to: (1) the reduction of the poros-
ity of the body (it returns to 40%), (2) the formation of amorphous
phases, and (3) the weakly crystallization of mullite and spinel-
type phase. The formation of mullite combined with the decrease
in porosity is the key steps for the increase in thermal conductiv-
ity of ceramics. In fact, as reported in literature [9], at higher firing
temperature, k change sensibly reaching up to 3 W m−1 K−1 . More-
over the spinel phase could improve the thermal conductivity of a
ceramic (kSpl = 9.5 W m−1 K−1 at 30 ◦ C) [42].
As far as the influence of the firing temperature on the poros-
ity, at 500 ◦ C the porosity is due to moulding, drying and the
 I. Allegretta et al. / Thermochimica Acta 581 (2014) 100–109 107

A
k of coarse-tempered ceramics
k of fine-tempered ceramics
kcomp

Fig. 5. Evolution of the detachment zone around quartz grains. The zone (white
arrows) is absent in samples fired at 500 ◦ C (A), but it is evident at 750 (B) and
1000 ◦ C (C).

shrinkage during firing. If on the one hand the pressing enables

the reduction of both the amount of primary pores and their
dimension [7], on the other hand the addition of coarse quartz
grains could increase the amount of large pores in the green body
[20,48]. During drying, because of the difference in water absorp-
tion between quartz and clay, a stressed area could form around
temper particles. This leads to the formation of surface-parallel
cracks. At 750 ◦ C these stressed areas are the weakest points of Fig. 6. Comparison between the experimental and the computed thermal conduc-
tivity (kcomp ) of quartz-tempered ceramics fired at 1000 ◦ C and tested at 120 (A), 220
quartz-tempered fabrics, where cracks could also form because of
(B) and 370 ◦ C (C). Both k of fine- and coarse-tempered ceramics are plotted.
the thermal expansion mismatches between quartz and the matrix
and the ˛–ˇ quartz inversion. As it has been modelled [49] the
greater the volume of non-plastic inclusion the larger the damaged
zone, i.e. the volume of pores. Moreover the ˇ–˛ quartz transition
108 I. Allegretta et al. / Thermochimica Acta 581 (2014) 100–109
at 573 ◦ C produce fractures in quartz particles which contribute
to the porosity of the system. In fact, SEM micrographs (Fig. 5)
shows a detachment zone and fractures around quartz grains and
fractures just around them in sample fired at this 750 ◦ C. Further-
more the kaolinite–metakaolinite transformation, could contribute
to the lowering of the thermal conductivity of the materials.
An overall decrease in porosity is observed in ceramics fired
at 1000 ◦ C, where cracks parallel to the surface disappeared, the
detachment zone and cracks increase around quartz grains.
3.3. Technological and functional implications
The thermal, mineralogical and microstructural results shown
above, suggest some considerations on the ceramic test charac-
teristics and their functional implications. Such discussion may
only deal with the etic approach (i.e. absolute, measurable), but
it is worth to note that the reasons to adopt a given material
or processing are not always technological [4,50]. In other terms,
a given ceramic should have some necessary physical properties
for a specific efficient use(s), which could be assessed and tested,
whereas possible uses due to cultural learning should be proved by
an ethnographic study [51].
Temper addition produces different effects on thermal conduc-
tivity: while quartz improves the conductivity of the ceramic body,
limestone always lowers it. The maximum thermal conductivity
was determined for the ceramic tests tempered with 15% of quartz
and fired at 750 and 1000 ◦ C, while at 500 ◦ C the thermal conduc-
tivity increases with quartz content. Moreover coarse quartz makes
the ceramic more conductive than fine quartz while in limestone-
tempered bodies the grain size of the temper does not influence
the thermal conductivity.
Firing temperature affects thermal conductivity because it influ-
ences the sintering of the material and hence its porosity. For this
reason samples fired at 1000 ◦ C are more conductive than those
fired at 750 ◦ C.
Since the ceramic tests were prepared taking into account a
series of combinations between composition and firing temper-
ature, reproducing some possible fabrics of traditional ceramics,
these results could be used to understand which technological
choices could be suitable for the preparation of ceramics for a spe-
cific function.
Because of their thermal properties, ceramics fired at 750 and
1000 ◦ C tempered with 15% of quartz are the most suitable mate-
rials to be used for the production of cooking pots. In fact, the
higher thermal conductivity enables the heating of pot content and
improves the thermal shock resistance [6], which is really impor-
tant in ceramic which should withstand a temperature difference
of about 700 ◦ C. Moreover, from a mechanical point of view, 15%
– tempered materials are collocated in the range (10–20%) where
there is the best compromise between strength and toughness [5].
In this way, a pot could withstand loads and in case of stresses
it could break gradually without immediately crash [6]. However,
if crack formation starts, the presence of temper in these per-
centages improves the resistance to crack propagation [6]. Both
fine and coarse quartz could be used because no difference in
thermal conductivity and porosity were observed. At these temper-
atures, tempering with 25% of quartz is not reasonable, because no
improvement of thermal conductivity could be seen and this is due
to the increase of porosity and the formation of cracks parallel to the
surface. Moreover, these cracks weaken the ceramic [5] reducing
the maximum load withstood by the pot. Finally, this moderately
high thermal conductivity (in comparison with that developed in
high-fired kaolinitic clay [9]) could have been very useful in keep-
ing the pot content warm once the vessel was removed from the
fire.
Quartz-tempered ceramics fired at 750 and 1000 ◦ C could be
also used as storage vessel. In particular, 1000 ◦ C-fired bodies are
more suitable than those fired at 750 ◦ C to contain liquids because
of their lower porosity. However, samples fired at 1000 ◦ C are more
suitable than those fired at 750 ◦ C for the production of storage ves-
sels because their mechanical behaviour (and hence the capability
to withstand their content) improves with firing temperature [52].
Due to their very low thermal conductivity, limestone-tempered
ceramics fired at 1000 ◦ C could be suitable for the production of
wares where the heating source is set inside (e.g. smelting cru-
cibles). In this way the heat loss is reduced because of the presence
of large cracks parallel to the surface [12], due to lime hydration,
which increase with limestone content. Since no pre- or post-firing
processing was used to control the lime spalling, the functionality
of part of the test pieces is reduced. A similar behaviour should be
expected from kiln walls. Eramo et al. [13], in fact, found that in the
Late Roman site of S. Giusto (Foggia, Italy) potters used local clays
which contains limestone for the production of kilns while they
used a finer alluvial clay, poor in calcareous sand, to make cooking
pots. On the base of the results shown in this work, it could be
drawn the hypothesis that these potters could have had this kind
of knowledge which enabled them to chose the correct material for
different purposes.
The same use is suggested for the limestone-tempered ceramics
fired at 750 ◦ C but they could also be used as storage vessel because
they do not contain lime which, in contact with water, could
hydrate and break the ceramic. Moreover, at temperature below
that of carbonate decomposition, limestone-tempered ceramics
has a higher transverse rupture strength than those tempered with
grog or grit [16]. For this reason, they could be more suitable than
quartz-tempered materials for the production of storage and trans-
port vessels.
Ceramics fired at 500 ◦ C could be used as storage container even
if liquid should be avoided because of the presence of both kaolin-
ite and illite at this temperature. Such 500 ◦ C-fired bodies could
not be used for processing pots in contact with a flame. In fact the
flame temperature, in a small fireplace, ranges from 900 ◦ C in the
continuous flame region to 300 ◦ C at the flame tips [53] and this
could induce unwanted further microstructural and mineralogical
transformations during pottery.
4. Conclusions
In the present work the influence of temper and firing tempera-
ture on thermal conductivity of ceramic bodies has been studied. It
could be concluded that quartz-tempered ceramics are more con-
ductive than limestone-tempered ones. In particular, while adding
quartz to the clay mixture increases k, the addition of limestone
reduces the thermal conductivity of the non-tempered fired clay.
As regards the effect of quartz temper on the thermal properties of
the ceramic, the ˛–ˇ quartz phase transition has a key role in the
heat transfer process. In fact, while in samples fired under 573 ◦ C
the higher the quartz content the higher the thermal conductiv-
ity, in samples fired over this temperature the maximum value of
k is at 15% of quartz content. While the nature of the temper could
affect sensibly the thermal behaviour of the ceramic, no significant
change could be detected changing the temper granulometry in
terms of thermal conductivity range, except some inversions of k
values in quartz-tempered samples fired at 1000 ◦ C.
As to firing temperature at 750 ◦ C, thermal conductivity
decrease because of the great increase of porosity, but at 1000 ◦ C k
is quite the same of sample fired at 500 ◦ C.
Finally, from a technological point of view quartz-tempered
ceramics are very suitable for the production of cooking pots,
though a content of non-plastic inclusions over the 15% is
 I. Allegretta et al. / Thermochimica Acta 581 (2014) 100–109
useless for the improvement of thermal conductivity. On the con-
trary limestone-tempered ceramics could be used in environment
where heat loss should be reduced because of their lower thermal
conductivity.
Acknowledgements
The authors would like to thank Dr Saverio Fiore at the IMAA-
CNR of Tito Scalo (PT), who provided the kaolinitic clay. Dr. Sabrina
Gualtieri, Dr. Michele Dondi and Guia Guarini at the ISTEC CNR of
Faenza (RA) are kindly acknowledged for the moulding and firing
of the test pieces. This paper is part of a Ph.D. thesis made possible
by a fellowship of Apulia Region.
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