Accepted Manuscript

Title: Effects of high temperature treatment on

physical-thermal properties of clay

Authors: Jishi Geng, Qiang Sun

PII: S0040-6031(18)30450-7
DOI: https://doi.org/10.1016/j.tca.2018.06.018
Reference: TCA 78031

To appear in: Thermochimica Acta

Received date: 7-3-2018

Revised date: 25-6-2018
Accepted date: 27-6-2018

Please cite this article as: Geng J, Sun Q, Effects of high temperature
treatment on physical-thermal properties of clay, Thermochimica Acta (2018),
https://doi.org/10.1016/j.tca.2018.06.018

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Manuscript Title:

Effects of High Temperature Treatment on Physical-thermal Properties of Clay

Authors’ names:

Jishi Geng*, Qiang Sun*

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School of Resources and Geosciences, China University of Mining and Technology, Xuzhou,
Jiangsu Province 221116, P.R. China

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*
Corresponding author:
Dr. Jishi Geng

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School of Resources and Geosciences, China University of Mining and Technology, Xuzhou,
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Jiangsu Province 221116, P.R. China
Tel: +86-18252432178
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E-mail: gengjishi@cumt.edu.cn
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Dr. Qiang Sun

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School of Resources and Geosciences, China University of Mining and Technology, Xuzhou,
Jiangsu Province 221116, P.R. China
Tel: +86-15162139571
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E-mail: sunqiang04@cumt.edu.cn
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Highlights:
 The effect of high temperature on the thermophysical properties of clay is studied.
 The change of color and cracks of clay depends on its composition and temperature.
 The reactions that lead to the change of clay properties are analyzed.
 These changes are mainly the result of the thermally-induced degradation of clay.

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Abstract:
High temperature changes the internal microstructure of clay and consequently affects its

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physical and thermal properties. In this paper, the influence of firing temperature (up to 900C) on

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the thermo-physical properties of clay is analyzed through laboratory tests and the relationship

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between thermal conductivity and density is revealed. Furthermore, the variation of surface
characteristics including clay color and cracking is reported. The results obtained indicate that the

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thermal conductivity and diffusivity as well as the bulk density of clay decrease rapidly as the
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temperature increases from room temperature to 200C, and then become approximately constant.
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From the Thermogravimetric Analysis (TG) and Differential Thermal Analysis (DTA) tests it is also
shown that there are two significant stages for the clay exposed to high temperature: 25-200°C and
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400-700°C. The evaporation of adhered water and bound water are proved to be the main reason for
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the first stage of clay mass loss at 25-200°C, while the decomposition of minerals is considered as
the second stage of mass loss in the temperature range of 400-700°C. In addition, the combustion of
organic matter in clay is the main reason for its darkening at 300-400°C.
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Keywords: high temperature, clay, thermal parameter, physical property

1. Introduction
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Clay is one of the most commonly used materials and has a wide range of applications in the
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fields of civil, geological, environmental and geotechnical engineering such as building materials
[1,2], principal media for geothermal energy piles and underground power cables [3,4], landfill liners
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[5,6] and cushions for nuclear waste disposals [7,8]. It is generally believed that clay deposits are a
complex mixture of several different types of minerals. They may contain feldspars, quartz, micas,
chlorites, smectites, etc., with exchangeable ions such as iron- alkaline- and alkaline earth- ions
located in the internal structures or interlayers of clay minerals [9-11].
Clay materials may be exposed to high temperature in geotechnical engineering issues such as
the energy of terrestrial heat and underground water, the emerging areas of energy storage in
geotechnical structures, the underground storage of high-level radioactive waste and the temperature
variation of soil around the structure induced by fire [12,13]. High temperature can influence the
physical and mechanical properties (e.g., colour, density, porosity, permeability, wave velocity,
strength and compactness, elastic modulus), thermal properties, structure and appearance of clay
[14-17].
A number of researchers have studied the effects of high temperature treatment on the properties

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of clay. Miheiro et al. [14] investigated the densification of red Brazilian kaolinitic clay exposed to

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high temperature and pointed out that the densification is associate with a series of phase

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transformations during firing. Laloui and Cekerevac [18] studied the thermo-mechanical behavior of

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soils and presented a new thermo-plastic mechanism of clay for isotropic thermo-mechanical paths
including thermal hardening. Certini [19] analyzed the influence of high temperature on the physical,

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chemical, mineralogical and biological properties of forest soils and his results indicated that the
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mineralogical assemblage is not changed to any great extent below 500C because the first step of
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disruption in the dehydroxylation of most minerals occurs at temperatures over 500°C. Chen et al.
[12] proved that the volume change of clay was mainly due to the discharge of water and steam from
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the sample, the movement of particles induced by steam pressure, and the physical and chemical
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reactions such as solid particle breakage and decomposition of organic matter. Sun et al. [15]
analyzed the variations of uniaxial compressive strength, resistivity and thermal parameters of high
temperature treated clay, and the thermal parameters showed the similar variation to those from Han
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et al. [17]. Table 1 summaries the literatures on the effect of high temperature on the microstructural,
physical and mechanical properties of clay. However, there is still insufficient knowledge of the
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thermo-physical properties of clay exposed to high temperature (above 200°C) and the relationship
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between thermo-physical-chemical parameters.

Therefore, in this paper, the physical and thermal properties of clay under high temperature (up
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to 900°C) and the relationship between thermal parameters and density are studied via a combination
of techniques such as Transient Plane Source (TPS) technique and DTA/TG. Moreover, the reasons
for the variations of physical and thermal properties of clay are discussed. The study of the thermal
properties of clay is essential to study the behavior of clay at elevated temperature.
2. Materials and test methods
2.1 Experimental materials
In this study, the experimental clay is obtained from Xuzhou of Jiangsu Province, China, with
its basic physical and mechanical properties shown in Table 2 and its particle size distribution shown
in Figure 1. Its chemical composition indicates the presence of silica (55.34%) and alumina (34.64%)
as major constituents, along with traces of sodium (0.16%), potassium (1.31%), iron (1.92%),
magnesium (0.31%) and calcium (0.22%) oxides as impurities, and its Loss On Ignition (LOI) value
is 6.1% as presented in Table 3. In addition, the X-ray Diffraction (XRD) pattern of the clay (Figure

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2) shows sharp peaks at d = 7.15, 4.45, 3.85, 3.57, and 2.38 Å due to kaolinite and at d = 4.25, 3.34,

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and 2.45 Å due to quartz, indicating that the later is the major contaminant of the clay.

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The clay samples are formed into a cylindrical shape of Φ50 ×100 mm. During their production

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process, the samples are manually compacted in the mold with a hammer of 1.0 kg. The drop height
of the hammer is 29 cm and the number of frontal and reverse strikes is 100 times and 50 times,

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respectively. Under the same proportioning conditions, the mass of the mixture (clay and water) in
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each mold is the same, so that each sample has the same volume and density, thereby reducing the
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test error. After compaction, the samples are first cured naturally in the mold for 24 hours and then
demoulded. Next, the samples are weighed and kept in the sealing bags at an ambient temperature of
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about 25C, which is essentially constant. The samples are brown at room temperature with no
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visible texture.
2.2 Experimental method
The samples are heat-treated at different temperatures of 25C, 100C, 200C, 300C, 400C,
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500C, 600C, 800C, and 900C. A digital electrical oven is used to heat the samples up to 200C
and a digital muffle furnace is used to heat the samples up to 900C. Four samples are heated to each
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target temperature at a heating rate of 5C/min. Then, the samples are cooled down to room
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temperature naturally after maintaining the holding temperature for 2 hours to ensure that the
samples have been sufficiently heated by thermal loading.
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These samples are observed before and after thermal treatment. Their surface features as well as
their physical and thermal parameters such as mass loss (), bulk density (), thermal conductivity ()
and diffusivity () are analyzed in later sections. The material density of the samples is determined
by measuring weight and volume (dimensions). The thermal conductivity is tested before and after
heating using a DRE-2C thermal constant analyzer based on the TPS technique, as shown in Figure 3.
The thermal decomposition mechanism of clay is studied through Thermogravimeric Analysis (TG)
and Differential Thermal Analysis (DTA). The TG/DTA is performed at a heating rate of 10°C/min
from room temperature to 1000°C by using corundum (α-Al2O3) as an inert substance and the HCT-4
apparatus (as shown in Figure 4).
3 Results and analysis
3.1 Surface features
The variation of color and surface features of the clay after high temperature treatment is shown

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in Figure 5. For all the clay exposed to 200C, its color does not change while its color becomes
black, dark grey, yellowish and brick-red for the clay exposed to 300C, 400C, 600C, and 900C,

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respectively. When the temperature is above 600C, brick-red samples are obtained. The color of the

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clay samples turns black because of the combustion of organic matter and the color turns to brick-red
as a result of the formation of hematite (Fe2O3) during firing under oxidizing conditions.

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During the heat treatment at different temperatures, cracks become obvious from visual
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inspection (Figure 6), which is the result of increased porosity and internal deterioration. When the
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temperature is less than 200C, a small number of cracks appear on the clay surface. At the heating
temperature increases above 300C, the number of cracks and crack apertures gradually increase,
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forming a crack network. Moreover, the depth of the cracks also increases continuously. As the
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temperature increases further, new cracks form and propagate towards each other, while the cracks
develop slowly at this later stage. It has been found that the color change and the formation of cracks
are associated with the chemical and physical changes of the clay after exposure to high temperature
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[15, 30-33].
3.2 Mass loss and density
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The mass loss ratio after exposure to elevated temperature, defined as the lost mass divided by
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the original mass, is calculated by Equation (1).

m1  m 2
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 =  100% (1)
m1

where  is the mass loss ratio (%), m1 is the mass of the clay before high temperature treatment, m2 is
the mass of the clay after high temperature treatment.
As Figure 7 shows, the variation of mass loss and density can be divided into three phases:
room temperature to 200C, 200C-500C and 500C-900C. Most of the mass loss and the rapid
decrease of density occur when the temperature rises from room temperature to 200C. Then the
change decreases gradually from 200C to 500C and eventually tends to be stable in the temperature
range of 500C-900C. This is mainly because of the evaporation of water (absorbed water, bounded
water, and mineral water) in the clay during the high temperature process. The adsorbed and
interlayer water usually evaporates at temperatures from 100°C to 200°C. The variation of density is
mainly due to the evaporation of structural water at 300C or above. When the temperature is
between 300 and 700°C, the decrease of density is mainly due to dihydroxylation. Meanwhile, the

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chemical changes of minerals such as pyrite, ankerite and kaolin also take place in the temperature

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range of 400-600C [16, 34].

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3.3 Thermal conductivity

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In this section, the evolution of the thermal conductivity of clay during heating is analyzed
according to the mineralogical nature of clay. The thermal conductivity () of clay refers to the

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amount of heat transferred in the cross sectional area of clay for unit temperature gradient in the
direction of heat flow. It can be determined from the Fourier heat flow as expressed by Equation (2).
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Q
A
= (2)
A  T d
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where  is the thermal conductivity (Wm-1K-1), Q is the heat flow (Watt), A is the cross sectional
area (m2), T is the temperature difference across the sample (K), and d is the sample thickness (m).
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The thermal conductivities of the clay samples after high temperature treatment are presented in
Figure 8. These values are the average of five repeated measurements. As shown in Figure 8, the
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thermal conductivity of the samples is about 1.75 Wm-1K-1 at room temperature, and it decreases
monotonically with the increase of the temperature. Moreover, the thermal conductivity of clay
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changes significantly in the temperature range of 25-300C, and at high temperatures (400-900C) it
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becomes stable, close to a constant value of about 0.4 Wm-1K-1. This flat trend of thermal
conductivity at high temperatures is similar to the results measured by Han et al. [17] and Sun et al.
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[16] The relationship between thermal conductivity and temperature is approximately exponential
(Figure 8), and the fitting equation (Equation (3)) is given as follows.

 = 0 .3 3 4 + 1 .7 6 e x p   0 .0 1 2 T   0 .9 5 2
2
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where  is the thermal conductivity and T is the temperature.

The variation of the thermal conductivity of the samples with density is shown in Figure 9. It
can be considered that this is the effect of moisture on the thermal conductivity since these values are
closely related. With the decrease of the density, the thermal conductivity decreases gradually. The
decrease in density is due to the loss of water through evaporation during the heating process. When
the density decreases owing to water loss, the air quantity in pores and cracks increases, resulting in
increased porosity and decreased thermal conductivity, as shown in Figure 10.
3.4 Thermal diffusivity
The thermal diffusivity indicates that the temperature of each part of the clay tends to be

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uniform when the clay heated or cooled, which can be expressed by Equation (4). In the process of

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stable heat transfer, the thermal diffusivity of clay can be calculated by heat capacity, density, and

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thermal conductivity, as shown in Equation (5).

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T  T
2

= / (4)
 L
2

where  is the thermal diffusivity of clay (mm2s-1),

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
= (5)
c
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where  is the thermal conductivity (Wm-1K-1),  is the density (gcm-3), c is the heat capacity
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(Jg-1K-1).
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The thermal diffusivity of the clay samples after high temperature treatment is presented in
Figure 11. It can be seen that the thermal diffusivity of clay is about 1.6 mm2s-1 at room temperature.
Furthermore, the thermal diffusivity decreases rapidly as the temperature increases in the temperature
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range of 25-300C, and then it approaches a constant value when the temperature is above 800C.
The average value of the measured thermal diffusivity is 0.2 mm2s-1 at 900°C, which is about 12.5%
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compared to that at 25°C. In addition, the relationship between thermal diffusivity and temperature is
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approximately exponential (Figure 11), and the fitting equation (Equation (6)) is given as follows.

 = 0 .1 3 4 + 1 .6 8 e x p (  0 .0 0 4 5 T ) 2
 0 .9 8 (6)
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where  is the thermal diffusivity and T is the temperature.

4 Discussion
After high temperature treatment, clay experiences a series of physical and chemical changes
including loss of water, changes in mass and density, and decomposition of mineral composition,
which results in destruction of clay structure. The corresponding endothermic- or exothermic peaks
shown in the DTA curves are very useful to establish transformations with or without mass loss and
have been used as one of the major tools for qualitative clay characterization. For example, the
release of interlayer water from clay as a result of heating is referred to as dehydroxylation and this
phenomenon can be observed with TG and DTA. These thermal analyses are often used to identify
thermal stability temperature ranges of clay minerals and are analogous to the temperature stepped
combustion approach [35].

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The TG and DTA curves (Figure 12) show four endothermic peaks for the clay. The exothermic

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peak at 100C represents the evaporation of absorbed and exchangeable cation-coordinated water.

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The dual endothermic peaks at 475C and 747C are due to desorption of structural water, i.e.,

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dehydroxylation of Kaolinite and illite [36]. The exothermic peak at 573C corresponds to the /
quartz transition.

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Because of the dehydration, dehydroxylation, and amorphization during the heating process,
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there are two significant stages for the clay with the temperature interval and mass loss percentage of
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25–200C and 7.1%, 400–700C and 2.9%, respectively, as observed from the DTA and TG curves.
At 25-200C, the loss of mass is mainly attributed to the rapid desorption of interparticle water,
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adsorbed water and interlayer water in the clay surface and interlayer space. Therefore, lots of pores
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and cracks are produced owing to the loss of water, resulting in a rapid decrease of density (as shown
in Figure 7). In the temperature range of 400-700C, the mass loss is mainly due to the combustion
of organic matter and the dissipation of structural water (structural OH groups). The structural water
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begins to lose when the temperature is above 300C, and the organic matter begins to turn into char
residue obviously in the range of 300-700C (especially 400-500C) [15,17]. The combustion of
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organic matter causes the color of the sample to turn black, as shown in Figure 5. When the
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temperature reaches 700-900C, the clay mass remains unchanged.

After high temperature treatment, the mineralogical composition of clay will change (for
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instance, the dehydroxylation of minerals), resulting in the variation of physical and thermal
properties. During heating, Kaolinite will be transformed into mullite and cristobalite through several
steps of endothermic and exothermic reactions [37-40]. The dehydroxylation of kaolinite takes place
in the temperature range of 400-800°C, which is shown in Equation (7) and (8). Above this
temperature, the loss of water is accompanied by a slight change in the dimensions of the structure.
In addition, a series of quartz phase transformations will occur at high temperature, i.e., -quartz will
be transformed into -quartz at 573°C and then converted into -tridymite at about 870°C [41,42], as
shown in Equation (9). Moreover, several minerals of clay will decompose at high temperature,
which is summarized in Table 4. Generally, these reactions will result in significant damage to the
mineral crystal lattice, eventually leading to increased clay defects.

470520C 1 3
A l 2 O 3  2 S iO 2  2 H 2 O     A l 2 O 3  2 S iO 2  H 2O + H 2O (7)
2 2

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1 540C 1
A l 2 O 3  2 S iO 2  H 2 O    A l 2 O 3  2 S iO 2 + H 2O (8)
2 2

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573C 870C
 -q u a rtz     -q u a rtz     -trid ym ite (9)

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In addition to physical and chemical reactions, the thermal properties of clay are closely related
to the solid-liquid-gas phase. Because the thermal conductivities of water (0.519 Wm-1K-1), air

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(0.021 Wm-1K-1) and minerals (0.05-2.428 Wm-1K-1) are different, the fillers in pores and micro
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cracks have an important effect on the thermal properties of clay. When the pores are filled with
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water, the contact between water and grain (grain-water-grain) is tight owing to the surface tension of
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water. The heat can be easily transferred from one grain to another compared to the model of
grain-air-grain (Figure 13). Therefore, the thermal properties decrease with the water loss at high
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temperature, and cracking may create contact resistance between mineral grains as the thermal
expansivity increases with the increase of the temperature, thus leading to a decrease in thermal
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properties owing to increased temperature.

5 Conclusion
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This paper investigates the variations of mass, density, surface features and thermal properties
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of clay in the temperature range from room temperature to 900 °C. The reasons for the change of
physical and thermal properties of clay with temperature are analyzed in detail. Based on the results
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obtained, the following conclusion can be reached:

(1) The surface color of the clay treated with high temperature changes from brown at room
temperature to black at about 300-400°C, and then becomes brick-red above 600 °C, which is related
to the changes in physical and chemical properties. These changes are mainly manifested in three
aspects: the dissipation of water, the decomposition of minerals, and the combustion of organic
matter.
(2) The thermal conductivity and diffusivity of clay vary significantly with temperature. They
decrease rapidly as the temperature increases from room temperature to 200°C, and then tends to be
stable in the temperature range of 300-900°C.
(3) The thermal conductivity of clay shows good linearity with density after heating, and an
increase in mass loss (including loss of water and organic matter as well as the decomposition of
minerals) and porosity is very important for the change of the thermo-physical properties of the clay.

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However, owing to the differences in formation conditions, mineral composition, structure, and

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texture of clay, the thermal properties of clay vary significantly. Therefore, measurement of various

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mineral contents, detailed lithologic interpretation and chemical analysis should be thoroughly
carried out in future studies.

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Acknowledgements
This research was supported by ‘‘the Fundamental Research Funds for the Central Universities”
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(2017BSCXA27) and “Postgraduate Research & Practice Innovation Program of Jiangsu Province”
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(KYCX17_1524). The authors thank the Priority Academic Program Development of Jiangsu Higher
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Education Institutions. They would also like to thank the technicians who helped them during the
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experiment and the anonymous reviewer for the constructive comments.

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application of clays from the Gabes region in South Tunisia, Appl. Clay Sci. 135 (2017)
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215–225.
[29] I. Štubňa, T. Húlan, T. Kaljuvee, L. Vozár, Investigation of dynamic mechanical properties of
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Estonian clay Arumetsa during firing, Appl. Clay Sci. 153 (2018) 23–28.
[30] D.W. Hu, F. Zhang, J.F. Shao, Experimental study of poromechanical behavior of saturated
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claystone under triaxial compression, Acta Geotech. 9 (2014) 207–214.

[31] W.H. Somerton, G.D. Boozer, A method of measuring thermal diffusivities of rocks at elevated
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temperatures, Aiche J. 7 (1961) 87–90.

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[32] E.T. Stępkowska, S.A. Jefferis, Influence of microstructure on firing colour of clays, Appl. Clay
Sci. 6 (1992) 319-342.
A

[33] H. Tian, T. Kempka, N.X. Xu, M. Ziegler, Physical properties of sandstones after high
temperature treatment, Rock Mech. Rock Eng. 45 (2012) 1113–1117.
[34] R. Stuart, Thermal characterization of the clay binder of heritage syendy sandstones, J. Therm.
Anal. Calorim. 92 (2008) 97-100.
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 An example from western Taiwan, Quat. Geochronol. 34 (2016) 24-32.
[36] K. Heide, M. Földvari, High temperature mass spectrometric gas-release studies of kaolinite
Al2[Si2O5(OH)4] decomposition, Thermochimica Acta. 446 (2006) 106-112.
[37] A.H. De-Aza, X. Turrillas, M.A. Rodriguez, T. Duran, P. Pena, Time-resolved powder neutron
diffraction study of the phase transformation sequence of kaolinite to mullite, J. Eur. Ceram. Soc.
34 (2014) 1409–1421.
[38] M. Hajpál, Changes in sandstone of historical monuments exposed to fire or high temperature,

T
Fire Technol. 38 (2002) 373-382.

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[39] S. Lee, Y.J. Kim, H.S. Moon, Phase transformation sequence from kaolinite to mullite

R
investigated by an energy-filtering transmission electron microscope, J. Am. Ceram. Soc. 82

SC
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Bull. Chin. Ceram. Soc. 6 (1993) 37–41.
U
[41] M. Fukuhara, A. Sampei, Effects on high-temperature-elastic properties on -/β-quartz phase
N
transition of fused quartz, J. Mater. Sci. Lett. 18 (1999) 751–753.
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[42] I. Ohno, K. Harada, C Yoshitomi, Temperature variation of elastic constants of quartz across the
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alpha-beta transition, Phys. Chem. Miner. 33 (2006) 1–9.

[43] T. Zhang, G. Cai, S. Liu, A.J. Puppala, Investigation on the thermal characteristics and
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prediction models of soils, Int. J. Heat Mass Tran., 106 (2017) 1074-1086.
E PT
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Figure 1 Grading curve of experimental clay

100

80
Percent passing (%)

T
60

IP
40

R
SC
20

0
0.001 0.01 U 0.1 1
N
Size distribution (um)
A
M
ED
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Figure 2 X-ray powder diffractograms of experimental clay

5000 K: Kaolinite
Q: Quartz
Ms: Muscovite Q
4000
Intensity (a.u.)

3000

T
IP
2000

R
K
1000 Q K

SC
Ms
Ms KQ K K
0

0 10 20 U 30 40
N
2 (degree)
A
M
ED
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Figure 3 DRE-2C thermal constant analyzer testing system

T
RIP
SC
U
N
A
M
ED
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A
Figure 4 HCT-4 comprehensive thermal analyzer

T
IP
R
SC
U
N
A
M
ED
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Figure 5 Variation of color and surface features of clay samples after high temperature treatment

T
R IP
SC
U
N
A
M
ED
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Figure 6 Surface cracks of clay samples after heat treatment at different temperatures

T
IP
(a) 200C (b) 300C (c) 400C

R
SC
U
N
A

(d) 500C (e) 600C (f) 800C

M
ED
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Figure 7 Effect of temperature on mass loss and density of clay samples

2.1 35

30
2.0
25
Density (gcm-3)

Mass loss (%)

1.9
20

T
IP
1.8 15

R
1.7 10

SC
5
1.6
0
1.5
0 U
100 200 300 400 500 600 700 800 900 1000
N
Temperature(C)
A
M
ED
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Figure 8 Effect of high temperature on thermal conductivity of clay

2.0
1.8 Experimental data
Thermal conductivity (Wm-1K-1)

Fitting curve
1.6
1.4
1.2

T
1.0
 =0.334+1.76exp(-0.012T )

IP
0.8 R 2  0.952

R
0.6

SC
0.4
0.2

0 100 200 300 400 500

U
600 700 800 900 1000
N
Temperatrue (C)
A
M
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Figure 9 Variation of thermal conductivity of clay with density

1.6
Thermal conductivity (Wm-1K-1)

1.4

1.2

T
1.0

IP
0.8

R
0.6

SC
0.4

0.2
1.40 1.45 1.50 1.55 1.60
U
1.65 1.70 1.75 1.80 1.85
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Density (gcm-3)
A
M
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Figure 10 Variation of thermal conductivity and porosity of clay with temperature

1.6 Thermal conductivity

26
Porosity
Thermal conductivity (Wm-1K-1)

1.4

1.2 24

T Porosity (%)
IP
1.0
22
0.8

R
SC
0.6 20

0.4

0.2 U 18
N
0 100 200 300 400 500 600 700 800 900 1000
Temperature (C)
A
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Figure 11 Effect of high temperature on thermal diffusivity of clay

1.8
Experimental data
1.6 Fitting curve
Thermal diffusivity (mm2s-1)

1.4
1.2

T
 =0.134+1.68exp(-0.0045T )

IP
1.0
0.8 R 2  0.98

R
0.6

SC
0.4
0.2
0.0 U
N
0 100 200 300 400 500 600 700 800 900 1000
A
Temperature (C)
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ED
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Figure 12 TG and DTA curves for experimental clay

20
475
0 573
15
-2
 quartz transition 747 10

Exo 
-4 DTA
Mass change: -7.1% 5
TG (%)

T DTA(uV)
-6
Mass change: -2.9% 0

IP
-8 -5

R
Dehydration TG (%)

SC
-10 -10
Dehydroxylation
100
-12 -15
0 100 200 300 400 500
Temperature (C) U
600 700 800 900 1000
N
A
M
ED
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A
Figure 13 Conceptual diagram for a change of moisture content [43]

T
R IP
SC
U
N
A
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ED
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Table 1 Summary of the researches carried out on the effect of high temperature on clay properties

Clay type Ref. Temperature Main research contents

Characterizing and studying the evolution, phase formation

IC clay, EC clay [20] RT-1250C and microstructural changes of clay through DSC/TG, XRD
and SEM methods.
Studying the thermal treatment on particle size, water
Kaolinite, content, specific gravity, plasticity, activity index, swelling
[21] 100-600C
Bentonite and compression index and strength properties.

T
Studying the effects of heat treatment temperatures on the
plastic refractories, cold crushing strength and modulus of

IP
Flint clay [22] 110-1500C
rupture.
Studying the mineralogy, pore structure, and cation-exchange

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Bentonite [23] 100-1300C capacity as a function of thermal treatment.

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Studying the mechanical properties, resistance to high
Kaolinite clay [24] 450-800C temperature and chemical agents, as well as shrinkage of the
calcined geopolymer.
Studying the influence of high temperature on the thermal
Clay [17] 20-800C
and mass loss. U
properties and the relationship between thermal parameters
N
Studying the mineralogical changes of two clay materials
with different mineralogical composition during firing
A
Clay [25] RT-1000C
through XRD and HTXRD methods.
M

Studying the tensile strength and the compressive strength,

Clay [26] RT-1000C the elastic modulus, the stress and deformation properties and
the cracking behavior of the clay materials.
ED

Studying the AC conductivity performed on illitic clay during

Illitic clay [27] 30-1100C firing in order to reveal dominant conductivity mechanisms.
Studying the mineralogical, chemical, physical, and
Gabes clay [28] 25-1150C geotechnical of the clay materials.
PT

Studying the development of the phases and its influence on

Estonian clay [29] RT-1100C the elastic and inelastic mechanical properties of this clay
during the heating and cooling stages of the firing.
E
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Note: RT, room temperature.

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Table 2 Basic physical and mechanical properties of experimental clay

Density Water content Liquid limit Plastic limit Plasticity index

 (gcm )-3 w (%) WL (%) WP (%) IP (%)

1.83 22.3 55 20 35

T
R IP
SC
U
N
A
M
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Table 3 Chemical composition of experimental clay

Chemical analysis Al2O3 SiO2 Fe2O3 Na2O K2O CaO MgO LOI

Content (%) 34.64 55.34 1.92 0.16 1.31 0.22 0.31 6.1

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R IP
SC
U
N
A
M
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Table 4 Reactions of several minerals at different temperatures

Temperature (C) Mineral Reaction

25-220 Ca-Montmorillonite Desorption
25-220 Mg-Montmorillonite Desorption
400-695 Mg-lllite Decomposition
455-642 Kaolinte Decomposition
554-723 Ca-Montmorillonite Decomposition
573 Quartz α-β inversion
700-800 Calcium carbonate Decomposition

T
790-950 Mg-lllite Decomposition

IP
816-908 Ca-Montmorillonite Decomposition
300-500 Organic matter Oxidation and carbonization

R
400-800 Carbon Oxidation

SC
U
N
A
M
ED
E PT
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A