Applied Clay Science 149 (2017) 8–12
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Applied Clay Science
journal homepage: www.elsevier.com/locate/clay
Research paper
Comparison of dehydration in kaolin and illite using DC conductivity
measurements
MARK
Marian Kublihaa, Viera Trnovcováb, Ján Ondruškab,⁎, Igor Štubňab, Ondrej Bošáka, Tiit Kaljuveec
a
b
c
Institute of Materials, Faculty of Materials Science and Technology, Slovak University of Technology, J. Bottu 25, 917 24 Trnava, Slovakia
Department of Physics, Faculty of Natural Sciences, Constantine the Philosopher University in Nitra, A. Hlinku 1, 949 74 Nitra, Slovakia
Laboratory of Inorganic Materials, Faculty of Chemical and Materials Science, Tallinn Technical University, Ehitajate 5, 190 86 Tallinn, Estonia
A R T I C L E I N F O
A B S T R A C T
Keywords:
Illite and kaolinite
DC conductivity
DTG
DSC
EGA
Dehydration
Temperature dependencies of the DC conductivity of kaolin and illite are measured from 20 °C up to 450 °C using
“as received” samples and samples after heating to 400 °C and 450 °C. Release of physically bound water (PBW)
from green kaolin shows two maxima, at 55 °C and 298 °C. Release of the PBW from green illite takes place in 3
steps at 72 °C, 186 °C, and 298 °C. Up to 200 °C, the dominant charge carriers are H+ and OH– ions in both
materials. At higher temperatures, alkali ions (both Na+ and K+ in kaolin, prevalently K+ in illite) are the
dominant charge carriers with the conduction activation energy of 1.19 ± 0.02 eV in kaolin and of
1.12 ± 0.02 eV in illite. Above 400 °C, dehydroxylation runs in illite. Due to this process, the DC conductivity of
illite increases; in partly dehydroxylated illite, higher conduction activation energy (1.22 eV) indicates that
alkali metal ions are moving in a more disordered structure. In kaolin, dehydroxylation starts only above 450 °C.
1. Introduction
Kaolinite and illite are common plastic components in traditional
ceramics. They determine various processes which occur during heating
of green ceramic bodies (Ferrari and Gualtieri, 2006). The structure of
kaolinite consists of a repetition of tetrahedron-octahedron (T-O) sheets
in one layer. The layers are tightly laid on top of each other, and no
space for alkali metal cations or H2O molecules exists between them
(Grim, 1962) (Fig. 1a). The illite structure consists of a repetition of
tetrahedron-octahedron-tetrahedron (T-O-T) sheets in one layer. The
interlayer space is occupied by K+ ions (Grim, 1962) and likely also
with water molecules (Carroll et al., 2005; Drits and McCarty, 2007;
Ferrari et al., 2006; Gualtieri et al., 2008; Viczian, 1997) (Fig. 1b).
During heating up to 300 °C, kaolin and illitic clay lose physically
bound water. Above 450 °C, dehydroxylation starts and kaolinite and
illite lose chemically bound water. An addition of illite to kaolin increases the content of the glassy phase due to a fluxing action of K2O
and decreasing the firing temperature (Ferrari and Gualtieri, 2006;
Wattanasiriwech and Wattanasiriwech, 2011).
Many methods of thermal analyses are used for a study of the processes that run in kaolin and illite during their heating. Measurement of
temperature dependencies of their electrical conductivity (so called
thermoconductometry) is a convenient method to detect the release of
both physically (PBW) and chemically (ChBW) bound water (Kriaa
⁎
et al., 2014). Electrical properties of kaolin (MacKenzie, 1969; Maiti
and Freund, 1981; Ondruška et al., 2015b; Podoba et al., 2014; Štubňa
and Kozík, 1996; Trnovcová et al., 2012) and illite (Kriaa et al., 2014;
Kubliha et al., 2016; Ondruška et al., 2015a, 2015b) have been experimentally studied using various experimental arrangements, making
any comparisons of these materials difficult. In this paper, we use
identical measurement arrangements for both materials to improve the
existing comparisons of their dehydration processes. Illitic clay and
kaolin were chosen because of their abundant use in ceramics due to
their favorable influence on firing process (Ferrari and Gualtieri, 2006;
Wattanasiriwech and Wattanasiriwech, 2011).
Thermal analyses (e.g. DTA, TGA, DSC, TDA) do not allow to observe motion of the electrical charge carriers. Therefore, the electrical
methods can be useful supplements to traditional thermal analyses. The
factors that influence the ionic DC conductivity in solids are the concentration of charge carriers, temperature, the availability of vacantaccessible sites which is controlled by the density of defects and/or
disordering of the structure, and the facility with which an ion can jump
into a neighboring site. This facility is controlled by the activation
energy which indicates the free energy barrier an ion must overcome
for a successful jump between the sites. When the charge of the ions is
large they find high conduction activation energy (CAE) barrier for
their jumps between sites. Therefore, monovalent ions of small or
medium diameters (e.g. Na+ or K+) when they are present in
Corresponding author.
E-mail address: jondruska@ukf.sk (J. Ondruška).
http://dx.doi.org/10.1016/j.clay.2017.08.012
Received 18 January 2017; Received in revised form 28 June 2017; Accepted 12 August 2017
Available online 07 September 2017
0169-1317/ © 2017 Published by Elsevier B.V.
Applied Clay Science 149 (2017) 8–12
M. Kubliha et al.
Fig. 1. Structure of a) kaolinite and b) illite.
Modified from Grim (1962).
with a diameter of 11 mm were obtained from this plastic mass using a
laboratory extruder. After a 5-day free drying, samples for thermal
analyses (DTG, EGA, DSC) and electrical measurements were cut.
The samples for measurements of the DC conductivity had dimensions of ∅11 × 2 mm. They were coated with conductive graphite
layers on both contact surfaces (so called “sandwich” arrangement). For
contact surfaces of electrodes, Pt foils were used. The electrical current
was measured with picoammeter Keithley 6517B at a constant voltage
of 10 V, in N2, using Novocontrol Concept 90, from 20 °C up to 400 °C
or 450 °C. The temperature was measured with sensitivity of ± 1 °C
using a Pt-PtRh10 thermocouple. The DC conductivity of green samples
was measured repeatedly in three runs. The 1st run was measured from
the room temperature up to 400 °C, the 2nd and 3rd runs were measured from the room temperature to 450 °C. All runs were done at an
increasing temperature with a heating rate of 5 °C/min.
Thermogravimetry (DTG) and DSC were measured using MettlerToledo TGA/SDTA 851 and Mettler-Toledo DSC 822, respectively, with
the heating rate of 5 °C/min. Specific surface areas of the samples
(330 mg) were measured using Sorptometer Kelvin 1042 with adsorptive gas N2 and carrier gas He. The samples for DTG and electrical
measurements were cut from the same blank; 48 mg compact samples
are used for DTG measurements.
The EGA was measured using Setaram LabSys 1600 thermal analyzer coupled with a Pfeiffer Omnistar Mass Spectrometer in an atmosphere of 79% of Ar + 21% of O2 with a flow rate of 60 ml/min.
Table 1
The chemical composition (in mass %) of illite and kaolin.
Illite
Kaolin
SiO2
Al2O3
Fe2O3
TiO2
CaO
MgO
K2 O
Na2O
L.O.I.
58.0
45.80
24.0
37.31
0.6
0.98
0.05
0.17
0.38
0.58
1.70
0.46
7.85
1.17
0.10
0.58
7.3
12.95
sufficiently high concentrations (Table 1) are the most probable
dominant charge carriers in silicates. The conduction activation energies can be determined using the Arrhenius relation
σ = σ0 exp(−Eσ kT )
(1)
where σ is the conductivity at absolute temperature T, k is Boltzmann
constant, Eσ is the conduction activation energy, and σ0 is the pre-exponential factor. The ionic conductivity relates to the heterodiffusion
coefficient D of dominant charge carrying ions by Nernst-Einstein
equation
σ D = nq2 kT
(2)
where n is the concentration of dominant charge carrying ions and q is
their charge.
Electrical methods allow only estimation of the product of concentration and mobility of dominant charge carriers. The used electrical
fields are low and do not influence the structure. The charge carriers,
i.e. alkali ions or H+, H3O+, and OH− ions from a decomposition of
water, are released by the heat and move in the electrical field; what
results in the electrical current. Thus, measurements of temperature
dependencies of the DC current can give a supplementary insight into
the dehydration processes in both materials.
The aim of this paper is to demonstrate the potential of DC conductivity measurements as supplementary methods for detection of
temperature regions of PBW and ChBW release (Kriaa et al., 2014;
Kubliha et al., 2016). This potential is demonstrated in this study of
dehydration mechanisms in illite and kaolin. It is also compared the
release of the physically bound water from illitic clay (86% of illite
+ 6% of montmorillonite) and kaolin (92% of kaolinite + 6% of illite/
muscovite) using the DC conductometry as to obtain a better understanding of differences of dehydration mechanisms in both materials.
3. Results and discussion
In raw kaolin samples, the measured specific surface area gives the
pore area equal to 10.33 m2. The initial mass of the physically bound
water in the sample 4.7 × 10− 3 g (according to TG) gives the area of
the monomolecular water layer of 9.64 m2, which is close to the pore
area in the sample. In illite samples, the measured specific surface area
gives the pore area equal to 13.62 m2. The initial mass of the physically
bound water is 12.54 × 10− 3 g, which can create a monomolecular
water layer of 25.71 m2. It is 1.9 times larger than the real pore area.
These results indicate that, in raw samples, water layers continuously
cover the crystallites of kaolin or illite at room temperature. In these
water coatings, self-ionization of water (2H2O → H3O+ + OH−,
H3O+ → H2O + H+) occurs. The created H+ ions, most likely, move
using the hopping Grotthuss mechanism (Agmon, 1995), in which very
mobile H+ ions jump between H2O molecules creating short living
H3O+ ions. The short increase of the conductivity between room temperature and 70 °C (Figs. 2 and 5) despite the evaporation of PBW demonstrates an intensive creation of H+ and OH– ions. After this, the
decrease of the conductivity is visible up to 150 °C because of the
evaporation of PBW which is the source of H+ and OH– ions.
Temperature dependencies of the DC conductivity of kaolin samples, measured 3 times successively, are presented in Fig. 2. The first
run shows 2 extremes, at 55 °C and 298 °C. The temperature of the first
2. Experimental
Füzérradvány illitic clay from Tokai region in Hungary is composed
of illite (86 mass %), montmorillonite (6 mass %), quartz (4 mass %)
and orthoclase (4 mass %). Sedlec kaolin from Czech Republic contains
kaolinite (92 mass %), illite/muscovite (6 mass %) and quartz (2 mass
%). Their chemical composition is summarized in Table 1.
Raw illite and raw kaolin were crushed and sieved with a mesh size
of 100 μm. The powder was mixed with distilled water to obtain a
plastic mass with a water content of ~20 mass %. Cylindrical blanks
9
Applied Clay Science 149 (2017) 8–12
M. Kubliha et al.
σdc [S.m-1]
500 400
300
200
of our investigations.
The mobility of H+ ions increases with an increasing temperature.
Therefore, an increase of the electrical current with an increasing
temperature is observed at the beginning of heating (Fig. 2). At the
same time, released water molecules evaporate from the sample, and
the number of H+ and OH– charge-carriers decreases. Therefore, at the
first run, a sharp decrease of the DC conductivity takes place from 60 °C
up to 150 °C. In the low-temperature region, 20 °C–200 °C, the main
charge carriers are H+ and OH−. After the evaporation of the PBW,
monovalent Na+, and K+ ions gradually become dominant charge
carriers. In the temperature range of 210 °C–300 °C, the slope of the
relationship σ(1/T) is almost constant which gives a conduction activation energy of 0.76 eV. It indicates a cooperative movement of mobile
ionic species (Na+, K+, and H+). At 298 °C, an anomaly in the temperature dependence of the DC conductivity indicates that the last
fraction of PBW is hydrolyzed to H+ and OH– ions. The OH– ions associate with mobile alkali ions into neutral complexes that do not
contribute to the DC conductivity. Thus, the slope of the temperature
dependence decreases (Trnovcová et al., 2007). This association process
does not influence the DTG plots. It is not observed in EGA as water
molecules are not emitted. Above 350 °C, the effect of the PBW on the
DC conductivity disappears. The conductivities during the first, second,
and third runs of measurements are identical. Their conduction activation energies are the same, equal to 1.19 ± 0.02 eV. This value is
common for the motion of alkali metal ions in oxide ceramics and
glasses (Majková et al., 1977; Trnovcová et al., 2007).
In the 2nd run, the temperature dependence of the DC conductivity
of kaolin samples is approximately composed of 2 parts: 1) the lowtemperature part, where only tightly bound H+ and OH– ions of an
almost constant concentration are the dominant charge carriers, with
conduction activation energy of approximately 0.32 eV, and 2) the
high-temperature part with Na+ and K+ charge carriers, with conduction activation energy of 1.19 ± 0.02 eV. In the 3rd run, contribution of H+ and OH– ions to the DC conductivity is almost totally
suppressed, and the low-temperature part has a conduction activation
energy of 1.02 ± 0.02 eV. The conduction activation energy of
~0.3 eV is characteristic for proton conduction in solids, the conduction activation energy of ~ 1 eV is common for a movement of K+ and
Na+ ions in oxide glasses and ceramics (Majková et al., 1977;
Trnovcová et al., 2007). It is evident that, in kaolin, there is no phase
transformation up to 450 °C because the temperature dependencies of
the DC conductivity above 350 °C for all three runs are identical. Thus,
our results imply that in kaolin, dehydroxylation starts at a temperature
higher than 450 °C.
Temperature dependencies of the DC conductivity of raw illite
samples, measured 3 times successively, are presented in Fig. 5. The
first run shows 3 maxima, at 72 °C, 186 °C, and 298 °C, resulting from
the PBW release. These temperatures coincide with DTG plots (Fig. 6),
which show 3 minimums at 59 °C, 166 °C, and 266 °C. The EGA indicates only two peaks of emission of H2O with maximums at 56 and
263 °C (Fig. 7) which are almost the same temperatures as those in
DTG. The discrepancy of the temperatures between different experimental methods results from the increasing mobility of H+ ions with an
increasing temperature. This increase partly compensates for the decrease of the proton concentration and shifts the DC conductivity
maxima to higher temperatures.
Up to 220 °C, the dominant charge carriers in illite are H+ and OH–
ions moving in the water cover of the illite crystals. An increase in the
conduction activation energy at higher temperatures indicates that alkali metal ions, especially K+ ions present in substantial amounts in
illite, contribute to the DC conductivity due to their rapidly increasing
mobility with an increasing temperature. At 298 °C, in a narrow temperature range, an association reaction between alkali metal ions and
released OH– ions into neutral complexes slows down the increase of
the DC conductivity with an increasing temperature.
In the 2nd run, after heating at 400 °C, the temperature dependence
T [°C]
100
1x10-6
1x10-8
1x10-10
10-12
10-14
1.5
2.0
2.5
3.0
3.5
1000/T [K-1]
0.0
-0.1
-0.2
-0.3
-0.4
-0.5
-0.6
-0.7
-0.8
-0.9
-1.0
0.0
-2.0x10-5
-4.0x10-5
DTG [s-1]
DSC [W.g-1]
Fig. 2. Temperature dependencies of the DC conductivity of kaolin samples: 1st run (□),
2nd run (○), and 3rd run (∆).
-6.0x10-5
-8.0x10-5
-1.0x10-4
DSC
DTG
0
100
-1.2x10-4
200
300
400
500
600
T [°C]
H2O ionic current [10-12 A]
CO2 ionic current [10-14 A]
Fig. 3. DSC and DTG curves of kaolin.
90
H2O ionic current
CO2 ionic current
80
70
60
50
40
30
20
10
0
0
200
400
600
800
1000
T [°C]
Fig. 4. EGA plots of kaolin; H2O release (○), CO2 release (□).
maximum coincides with the DTG plot (Fig. 3), which shows a
minimum at 65 °C. The DTG plots of kaolin give only one minimum for
the release of the PBW. The results of mass spectrometric measurements
indicate also only one peak of emission of H2O connected with the
release of the PBW with a maximum at 106 °C (Fig. 4). The released
mass of the PBW represents a ~1.5% loss of the initial mass of the
sample. Fig. 3 and Fig. 4 also show DTG, DSC and EGA results over
400 °C, i.e. show the influence of dehydroxylation which is not a topic
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Applied Clay Science 149 (2017) 8–12
M. Kubliha et al.
σdc [S.m-1]
500 400
300
200
activation energy of 1.22 eV, is observed. It results from the onset of
dehydroxylation during the preceding heating to 450 °C. Upon partial
dehydroxylation, the DC conductivity of illite increases due to the enhanced concentration of defects; a slightly higher conduction activation
energy indicates that alkali metal ions are moving in a more disordered
structure (Freund, 1967).
T [°C]
100
1x10-6
1x10-8
4. Conclusions
1x10-10
The comparison of results of the DC conductivity measurements of
kaolin and illite leads to the following conclusions:
The loss of physically bound water in “as received” kaolin samples
takes place in two steps, visible in the temperature dependencies of the
DC conductivity at 55 °C and 298 °C. Up to 220 °C, the dominant charge
carriers are H+ and OH– ions. At higher temperatures, K+ and Na+ ions
contribute to the DC conductivity.
The loss of physically bound water in “as received” illite samples
takes place in 3 steps, which are visible in the temperature dependencies of the DC conductivity at 72 °C, 186 °C, and 298 °C. Up to
220 °C, the dominant charge carriers are H+ and OH– ions. At higher
temperatures, K+ ions contribute to the DC conductivity.
After heating at 400 °C, in the low-temperature part of the temperature dependence of the DC conductivity H+ and OH– ions are the
dominant charge carriers, with conduction activation energy of 0.31 eV
in both materials. At higher temperatures, Na+ and K+ ions are
dominant charge carriers with a conduction activation energy of
1.19 ± 0.02 eV in kaolin; K+ ions are most important charge carriers
with a conduction activation energy of 1.12 ± 0.02 eV in illite.
Above 400 °C, the dehydroxylation starts in illite samples and the
DC conductivity of illite increases. The slightly higher conduction activation energy (1.22 eV) indicates that alkali metal ions are moving in
a more disordered structure.
In contrary to illite, kaolin has only 2 stages of PBW release and its
dehydroxylation starts above 450 °C. At the 2nd run, when dehydroxylation does not start, temperature dependencies of the DC conductivity
of both materials are very close.
10-12
10-14
1.5
2.0
2.5
3.0
3.5
1000/T [K-1]
0.0
0.05
0.00
-1.0x10-5
-0.05
-0.10
DTG [s-1]
DSC [W.g-1]
Fig. 5. Temperature dependencies of the DC conductivity of illite samples: 1st (▽), 2nd
(◇), and 3rd (◁) run.
-2.0x10-5
-0.15
-3.0x10-5
-0.20
DSC
DTG
-0.25
-4.0x10-5
-0.30
0
100
200
300
400
500
600
T [°C]
Fig. 6. DSC and DTG curves of illitic clay.
H2O ionic current [10-11 A]
CO2 ionic current [10-14 A]
Acknowledgement
45
H2O ionic current
CO2 ionic current
40
35
This work has been supported by the Ministry of Education, Science,
Research, and Sport of the Slovak Republic [grant number VEGA 1/
0162/15]. The authors thank ceramic plant PPC Čab for providing
Sedlec kaolin. The authors are also indebted to Mr. J. Biber (Inter-ILI
Engineering Office, Hungary) for providing illitic clay.
30
25
20
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