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Thermal dehydroxylation of kaolinite under

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Applied Clay Science

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Research paper

Thermal dehydroxylation of kaolinite under isothermal conditions

Elisa Gasparini a,, Serena C. Tarantino a, Paolo Ghigna b, M. Pia Riccardi a, Erika I. Cedillo-Gonzlez c,
Cristina Siligardi c, Michele Zema a
a
Dipartimento di Scienze della Terra e dell'Ambiente, Universit di Pavia, via Ferrata 1, I-27100 Pavia, Italy
b
Dipartimento di Chimica, Universit di Pavia, viale Taramelli 16, I-27100 Pavia, Italy
c
Dipartimento di Ingegneria dei Materiali e dell'Ambiente, Universit degli Studi di Modena e Reggio Emilia, via Vigolese 905, I-41100 Modena, Italy

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

Article history: The dehydroxylation reaction of kaolinite from the industrial kaolin Sl-K (Germany) has been studied by thermal
Received 3 February 2012 analyses (TG, DTA) and ex situ annealing experiments. Heating experiments were performed at 450, 500, 550
Received in revised form 17 July 2013 and 600 C. At each working temperature, different heating times were used in order to follow the evolution
Accepted 19 July 2013
of the dehydroxylation process with time until completion of the reaction. Every heating run was performed
Available online 19 August 2013
on a new batch of sample, which was weighted before and after the heat-treatment. At the end of the heating
Keywords:
run, each sample was characterised by X-ray powder diffraction (XRPD) and FT-infrared attenuated total
Kaolinite reectance spectroscopy (FTIR-ATR). The dehydroxylation process was followed by monitoring the gradual
Dehydroxylation mass loss and the corresponding decrease in intensity of the most signicant peaks both in the diffraction
Kinetics patterns (disappearing of kaolinite peaks) and in the FTIR-ATR spectra (disappearing and changes in OH
X-ray diffraction and Si\O\Al bands), as determined by peak-prole and autocorrelation analyses. A kinetic analysis was
FT-IR performed using the Avrami method on the basis of sample mass loss and changes in the intensities of
Autocorrelation analysis XRPD and FTIR-ATR peaks under isothermal conditions. Two temperature regimes are found, with only
the data in range 500600 C being isokinetic. The activation energy values obtained in this temperature
range on the basis of the three measured parameters are comparable and are between 127 and
139 kJ mol1.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Kaolinite (hereafter, Kaol) is the main mineral phase of kaolin which
contains other phyllosilicates and feldspars, and other minerals such as
quartz, rutile, hematite, ilmenite, zircon, carbonates, sulphides, and
various ferrous and aluminium (hydr)oxides. Kaol, Al2Si2O5(OH)4,
is a dioctahedral phyllosilicate with a 1:1 type layered structure
and its space group is triclinic P1 (Bailey, 1980; Bish, 1993; Giese,
1991). A detailed and accurate description of Kaol structure is
provided by Brigatti et al. (2006).
Kaol is an important primary material in a variety of industrial
processes e.g., food-processing industry, oil shale processing, ceramic
industry, as a pozzolanic material, as a feedstock for geopolymer
cement, as a lling agent, to cite some (see, for example Bundy,
1993; Duxson et al., 2007; Prasad et al., 1991) and it is typically
used after transformation, via calcination, into its dehydroxylated
phase metakaolinite (hereafter, MKaol), Al2Si2O7, which is much
more reactive. MKaol is the rst phase to occur on heating Kaol in
the temperature range from 450 to 700 C, after the water desorption
step at T up to 100 C. The thermal transformation of Kaol to MKaol
has been studied for a very long time and by different techniques such
Corresponding author. Tel.: +39 0382985839; fax: +39 0382985890.
E-mail address: elisa.gasparini@unipv.it (E. Gasparini).
as thermal analysis (Balek and Murat, 1996; Castelein et al., 2001;
Dion et al., 1998; Nahdi et al., 2002; Ptek et al., 2010a, 2011;
Redfern, 1987), infrared spectroscopy (Prost et al., 1989; Temuujin
et al., 1998), X-ray diffraction (Artioli, 1997; Bellotto et al., 1995;
Temuujin et al., 1998), MAS-NMR (He et al., 2003; Massiot et al.,
1995; Temuujin et al., 1998), electron microscopy (Bergaya et al.,
1996; de Souza Santos et al., 2005), thermodilatometry (Chakraborty,
1992; Liu et al., 2002), efuent gas analysis (Ptek et al., 2010b) and
electron paramagnetic resonance (Djemai et al., 2001). Exact information
about the mechanism and the kinetics of the dehydroxylation process
remains contentious. This is because the dehydroxylation reaction
depends on many different factors such as Kaol structure (e.g., particle
size, shape and morphology, density of defects), associated minerals,
heating rate, sample treatment, pressure and partial water vapour
pressure (Artioli, 1997; Castelein et al., 2001; Dion et al., 1998; Ptek
et al., 2010a, 2011). However, it is known that the dehydroxylation
process in Kaol is accompanied by a change in the aluminium coordina-
tion from six- to a mixture of six-, ve- and four-fold (Gualtieri and
Bellotto, 1998; Leonard, 1977; MacKenzie et al., 1985; Massiot et al.,
1995; Rocha and Klinowski, 1990; Sperinck et al., 2010). Some authors
also found the presence in MKaol of three-fold coordinated Al cations
(Sperinck et al., 2010; White et al., 2011). Due to the loss of hydroxyl
groups, the initial crystalline layered structure of kaolinite is subjected
to local buckling and strain (White et al., 2010). The structure loses its

0169-1317/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.clay.2013.07.017
418 E. Gasparini et al. / Applied Clay Science 8081 (2013) 417425

crystallographic order, as observed experimentally in conventional

diffraction studies via the lack of Bragg scattering from heated materials.
However, a transmission electron microscopy study showed that it has a
quasihexagonal periodic structure in the ab plane (Bergaya et al., 1996).
Moreover, the structure does not completely collapse along the c-axis
and maintains a two-dimensional regularity (Gualtieri and Bellotto,
1998), and it has been found to consist of planar entities which result
from the combination of two successive dehydroxylated sheets
(Bergaya et al., 1996).
The reduction of Kaol mass during the dehydroxylation process is of
ca. 11.214.2 wt.%, the theoretical value being 13.96 wt.% (Piga, 1995;
Ptek et al., 2010a). Some studies show that up to ca. 12 wt.% of the
total hydroxyl groups may be retained in the MKaol structure up to
thermal treatment at 900 C (Bellotto et al., 1995; Brown et al., 1985;
Gualtieri and Bellotto, 1998; MacKenzie et al., 1985; Redfern, 1987;
Watanabe et al., 1987), when a completely anhydrous phase is formed.
The kinetics of dehydroxylation of Kaol has been studied extensively
both by isothermal and non-isothermal methods, and the results
interpreted in terms of rst-order kinetics as well as on the basis of a
diffusion model (see Bellotto et al., 1995; Dion et al., 1998; Ptek
et al., 2011; Redfern, 1987, and references therein). Also a two-stage Fig. 1. Particle size distribution of raw Sl-K kaolin.
mechanism has been proposed for the hydroxyl release (Ortega et al.,
2010 and references therein). There is no general agreement even on
the value of the activation energy (Ea) associated to the process and
empirical values obtained by several authors are spread in a wide interval, 2.2. Thermal analysis
ranging between 140 and 250 kJ mol1. Moreover, higher discrepancies
are found in the presence of water vapour (Brindley et al., 1967; L'vov and Thermogravimetric analysis (TG) was carried out using a TA Instru-
Ugolcov, 2005 and references therein). Such discrepancies are due to the ments AutoTGA 2950HR with V6.1A data acquisition software. A Pt
fact that many parameters affect the kinetics of dehydroxylation of Kaol, crucible was lled with ca. 11 mg of Sl-K powdered sample and heated
from structure defectivity to grain shape, size and size homogeneity, at a rate of 20 C/min under nitrogen ow, from room temperature (RT)
and from heating rate and heating conditions (i.e., ambient vapour up to 1000 C. Differential thermal analysis (DTA) was performed with
pressure) to the presence of impurities. a TA Instruments 2910 Modulated DSC V4.4E, equipped with a 1600 C
The aim of this study is to analyse the thermal dehydroxylation/ DTA cell, on ca. 14 mg of sample. The sample was loaded into a Pt crucible
amorphization process of Kaol from kaolin of industrial importance and heated from 100 C up to 1200 C at a rate of 20 C/min. Measure-
containing 27% of quartz. In this study, the kinetic parameters of the ment was carried out in air with no gas ow, and Al2O3 was used as a
dehydroxylation process of Kaol are determined by ex situ thermal reference material. TG and DTA curves are reported in Fig. 2.
treatments associated to a multi-technique approach including sample
mass loss, X-ray power diffraction (XRPD), and Fourier transform- 2.3. Thermal treatments
infrared attenuated total reectance (FTIR-ATR) spectroscopy. FTIR-
ATR spectroscopy is commonly used for quality control in industry The annealing experiments were performed ex situ at four different
and has the advantage to require no or little sample preparation. temperatures: 450, 500, 550 and 600 C using a vertical furnace
Bands in IR spectra are highly sensitive to structural variations and, in Carbolite STF 15/450. At each working temperature, different heating
particular, linewidth can be a good probe for crystal heterogeneity. In times were used in order to time the evolution of the dehydroxylation
particular, the autocorrelation analysis is used for analysing the region process until the accomplishment of the reaction. Every heating run
of IR spectra of Si\O and Al\O stretching modes, which reect distor- was performed on a new batch of powdered sample (ca. 1 g) which
tions of the structural framework. was weighted before and after the heat-treatment. The samples were
loaded into a Pt crucible, heated in the vertical furnace and quenched
2. Experimental procedure at the end of the experiment. The sequence of thermal treatments, the

2.1. Characterization of raw material

The raw material used for the present study is a German industrial
kaolin, labelled Sl-K, which was provided by Sibelco Italia S.p.A. The
mineralogical composition of this kaolin, obtained by combining XRPD
and thermal analyses, assuming complete dehydroxylation, is 73 wt.%
Kaol and 27 wt.% quartz. Its chemical composition, determined by X-
ray uorescence methods, is: SiO2 67.0%, Al2O3 31.5%, Fe2O3 0.32%,
TiO2 0.24%, CaO 0.12%, MgO 0.23%, and K2O 0.35%, and its measured
ignition loss is 10.02% (the theoretical value for pure Kaol is 13.96%, as
stated above). The particle size distribution, measured by a Sympatec
Helos particle size analyser equipped with a laser diffraction sensor, is
reported in Fig. 1. It shows two maxima, indicating an average particle
size of ca. 3 m for Kaol and an average particle size of ca. 10 m for
quartz, as also conrmed by microscopic observations. The Sl-K kaolin
sample was used for all the analyses described below without further
grinding or manipulation. Fig. 2. TG (left axis) and DTA (right axis) curves of Sl-K kaolin measured at 20 C/min.
 E. Gasparini et al. / Applied Clay Science 8081 (2013) 417425 419

initial and nal masses and the corresponding water losses are reported
in Table 1. All the heat-treated samples were then characterised by
means of XRPD and FTIR-ATR spectroscopy.
2.4. X-ray powder diffraction
XRPD measurements were carried out by means of a Philips PW
1808 diffractometer with BraggBrentano geometry using Ni ltered
CuK radiation ( = 1.5418 ). Data were collected in the range 2
65 2 with a step width of 0.01 2 and time per step of 0.5 s for samples
heated at 450, 500 and 550 C and of 1.0 s for samples heated at 600 C.
Peak prole analysis was performed using Voigt proles with the
MultiPeakFitting routine from IGOR Pro software (Wavemetrics Inc.,
OR). Intensities of (001) peak of Kaol, hereafter labelled as (001)K,
normalised with respect to (101) peak of quartz, labelled (101)Q, are
reported for all the heat-treated samples in Table 1.
2.5. IR spectroscopy
For IR spectroscopy, approximately 0.4 g of powder of each sample
was pressed under vacuum to produce a pellet. Spectra were recorded
at room temperature from 400 to 4000 cm1 with a resolution of
4 cm1 using a Thermo Scientic Nicolet iN10 MX micro-spectrometer.
Every spectrum, recorded in attenuated total reectance (ATR) with a
liquid nitrogen cooled mercury cadmium telluride (MCT) array detector,
was calculated by Fourier transformation of 256 interferometer scans
and total scanning time of 90 s. A germanium hemispherical internal
reection element (IRE) crystal with a diameter of 300 m was used.
The ATR accessory is mounted on the XY stage of the FTIR microscope,
and the IRE crystal makes contact with the sample via a force lever
with pressure of 2 Pa. A 37.7 37.7 m aperture size was used.
The evolution of the linewidth of IR bands with annealing time was
analysed using an autocorrelation approach, which was introduced to
determine subtle energy shifts and changes in linewidth for complicated

Table 1
Sequence of thermal treatments and relevant parameters.

Time (min) Initial weight (g) Final weight (g) Lost H2O (mol)1 (001)K area2 corr (cm1) WL XRD IR

Untreated 0.351 (2) 23.0 0.000 0.000 0.000

T = 450 C
60 1.0003 0.9798 0.00087 0.325 (6) 37.2 0.161 0.076 0.241
120 1.0000 0.9770 0.00101 0.315 (6) 41.6 0.187 0.103 0.317
240 1.0002 0.9752 0.00112 0.304 (6) 42.1 0.207 0.134 0.326
1380 1.0000 0.9484 0.00260 0.202 (4) 57.6 0.483 0.426 0.581
4650 1.0000 0.9394 0.00310 0.162 (3) 62.7 0.577 0.539 0.678
9743 1.0007 0.9290 0.00372 0.078 (2) 81.6 0.691 0.777 1.000

T = 500 C
30 1.0004 0.9496 0.00256 0.187 (4) 58.0 0.475 0.466 0.520
60 1.0006 0.9288 0.00373 0.108 (3) 75.8 0.693 0.693 0.786
90 1.0001 0.9214 0.00411 0.075 (2) 81.0 0.765 0.787 0.877
120 1.0004 0.9122 0.00464 0.036 (2) 90.8 0.863 0.897 1.009
150 1.0002 0.9113 0.00468 0.036 (2) 87.8 0.870 0.899 0.965
180 1.0005 0.9102 0.00476 0.025 (1) 91.4 0.885 0.929 1.018
210 1.0009 0.9080 0.00490 0.018 (1) 93.3 0.911 0.948 1.105
240 1.0004 0.9071 0.00493 0.023 (2) 90.2 0.916 0.935 1.000
420 1.0002 0.9039 0.00510 0.007 (1) 0.947 0.980
840 1.0001 0.9025 0.00517 0.005 (1) 0.961 0.985
3900 1.0000 0.8986 0.00538 0.000 1.000 1.000

T = 550 C
5 1.0000 0.9723 0.00127 0.292 (2) 0.232 0.169
10 1.0000 0.9356 0.00332 0.127 (3) 69.6 0.609 0.628 0.698
20 1.0001 0.9189 0.00425 0.065 (2) 89.3 0.782 0.815 0.993
30 1.0003 0.9083 0.00486 0.027 (2) 89.0 0.892 0.925 0.990
40 1.0001 0.9064 0.00495 0.020 (2) 91.5 0.910 0.946 1.026
50 1.0001 0.9022 0.00519 0.012 (1) 0.951 0.967
60 1.0000 0.9025 0.00516 0.008 (1) 89.1 0.949 0.978 0.991
120 1.0000 0.8997 0.00532 0.000 90.3 0.978 1.000 1.009
180 1.0001 0.9013 0.00524 0.000 86.3 0.962 1.000 0.949
240 1.0001 0.8987 0.00538 0.000 89.7 0.989 1.000 1.000
420 1.0001 0.8954 0.00557 0.000 1.023 1.000
780 1.0001 0.8976 0.00544 0.000 1.000 1.000

T = 600 C
5 1.0002 0.9313 0.00357 0.113 (2) 69.7 0.637 0.679 0.654
7 1.0001 0.9200 0.00419 0.076 (2) 79.5 0.749 0.784 0.792
10 1.0003 0.9110 0.00471 0.038 (2) 92.8 0.840 0.893 0.978
12 1.0000 0.9060 0.00497 0.018 (1) 89.0 0.887 0.949 0.924
14 1.0002 0.9039 0.00510 0.013 (1) 93.2 0.910 0.964 0.983
16 1.0001 0.9034 0.00512 0.012 (1) 90.1 0.914 0.967 0.94
18 1.0003 0.9033 0.00514 0.007 (1) 90.3 0.917 0.979 0.943
20 1.0000 0.9004 0.00528 0.007 (1) 92.5 0.943 0.979 0.973
30 1.0002 0.8968 0.00549 0.000 92.9 0.981 1.000 0.979
40 1.0004 0.8945 0.00563 0.000 94.4 1.006 1.000 1.000
240 1.0000 0.8947 0.00560 0.000 1.000 1.000

WL, XRD, IR are the degrees of conversion calculated from weight loss, (001)K diffraction peak, and IR corr, respectively.
1
Calculated after subtraction of 0.5% from initial weight (corresponding to adsorbed water, as deduced from TG) and hence relative to dehydroxylation process only.
2
Area of (001) diffraction peak of kaolinite measured by peak prole analysis (see text) and normalised with respect to (101) of quartz.
420 E. Gasparini et al. / Applied Clay Science 8081 (2013) 417425
vibrational spectra (Salje et al., 2000). This method, initially developed
to investigate phase transitions in minerals, has allowed, in particular,
detailed studies of variations in linewidths of IR spectra due to the
effects of composition and cation order across mineral solid solu-
tions (Balan et al., 2011; Blanch et al., 2008; Boffa Ballaran and
Woodland, 2006; Etzel and Benisek, 2008; Meyer et al., 2002; Pring
et al., 2008; Salje et al., 2010; Tarantino et al., 2005). The method
uses an autocorrelation function, dened as:
Z
Corr; d 1 bands are at 3651, 3670 and 3689 cm 1 and correspond to the
where () is the spectrum itself and ( + ) is the same spectrum
offset in frequency by , to extract and analyse spectral changes (Salje
et al., 2000). An effective linewidth parameter corr, the main informa-
tion on the linewidth of the IR spectrum is then obtained from the
shape of the autocorrelation function in the limit of 0. It is propor-
tional to the average width and mode splitting in the chosen segment of
the primary spectrum and proves to be rather more robust with respect
to changes of baselines and instrumental noise than the usual line
tting procedure.
The spectral range chosen here for the calculation of corr is the 670
to 2000 cm1, i.e. the domain including the Si\O stretching modes and
O\H bending modes. The variation of effective linewidth, expressed as
the parameter corr is reported for all the datasets of this study in
Table 1.
3. Results and discussion
3.1. Thermal decomposition of kaolinite: Thermal analysis
The TGDTA plots of Sl-K sample are shown in Fig. 2. Different
thermal effects are evident from the curves. At T below 150 C, the
adsorbed water is removed. In the TG curve, this effect corresponds to
a mass loss of ca. 0.5%, while, in the DTA plot, this desorption process
is visible as a weak endothermic peak. The second event is recorded in
the TG curve by a signicant mass loss, of ca. 9.5%, and corresponds to
the dehydroxylation of Kaol and formation of MKaol. The mass loss, as
measured by the TG plot, permits to quantify the content of Kaol in
Sl-K sample to ca. 73%. In the DTA plot, the dehydroxylation reaction
is visible as a strong endothermic valley peaked at 528 C.
Dehydroxylation temperatures, recorded in literature, range
between 530 and 630 C and, in some cases, they reach 700 C.
Usually, dehydroxylation temperatures below 570 C are ascribed
to disordered kaolinites (Smykatz-Kloss, 1974). The last two
effects in the DTA curve are exothermic peaks. The rst, peaked at
1009 C, is sharp and is related to mullite formation according to
the following reaction: 3(2Al2O33SiO2) 2(3Al2O32SiO2) + 5SiO2
(Castelein et al., 2001; Ptek et al., 2010a). The second is a large
broad peak in the region from 1100 to 1300 C which may be also related
to mullitization from MKaol (Chakraborty, 2003; Wang et al., 2011).
3.2. Ex situ annealing experiments: XRPD
The XRPD patterns of the Sl-K sample before and after each thermal
treatment at 450, 500, 550 and 600 C are shown in Fig. 3. The XRPD
pattern of the untreated sample shows the presence of Kaol and
quartz. At each temperature, with increasing the heating time, the
diffraction peaks of Kaol become less intense, thus indicating the
progress of the dehydroxylation and, consequently, the transformation
of Kaol into the X-ray amorphous phase MKaol. Completion of the
dehydroxylation reaction, as deduced by the absence of diffraction
peaks of Kaol from the visual inspection of the diffractograms, was
attained in ca. 40 min at the highest working temperature, i.e. 600 C,
ca. 180 min at 550 C and ca. 240 min at 500 C. At 450 C, the longest
heating time was about one week and, after this treatment, the reaction
was not yet complete.
3.3. Ex situ annealing experiments: FTIR-ATR
The IR spectra of untreated and heat-treated Sl-K samples are shown
in Fig. 4. The spectrum of the pristine Sl-K sample displays intense and
well-resolved absorption bands and shows the four OH-stretching
bands between 3600 and 3700 cm 1. In particular, the stretching
band of the intra-layer OH group is at 3620 cm 1; the other three
stretching modes of the inner-surface OH groups (Balan et al.,
2001; Farmer, 1998). The three peaks observed between 1000 and
1200 cm 1 correspond to Si\O stretching modes whereas the
bands observed around 900 cm 1 correspond to bending modes
involving OH groups (Balan et al., 2001). The double peak at around
750 cm 1 is indicative of the presence of quartz in the sample.
Signicant changes in width and intensity of OH-stretching bands
are monitored with increasing the heating time at each temperature.
Moreover, the bands at 3620 and 3689 cm 1 shift toward higher
frequencies with increasing heating time. It is important to note
that all of these OH-stretching bands disappear after 120, 40 and
10 min of heating at 500, 550 and 600 C, respectively, long before
the Kaol diffraction peaks disappear from the diffraction patterns.
At 450 C, after about one week of heating, the two external OH-
stretching bands are still present to indicate the slow accomplish-
ment of the dehydroxylation reaction.
Bands in the MIR range, related to Si and Al, also show large variations
as a consequence of annealing. During the heating treatments a change
in the relative intensities of the peaks at 1004 and 1028 cm1 is rst
evident, nally the Si\O peaks become a unique broad band centred at
higher frequency. Moreover, an increase in linewidth is immediately
evident from visual inspection of this region. The 910 and 935 cm1
bands related to Al\O\H disappear after different heating times at dif-
ferent heating temperatures: 210 min at 500 C, 40 min at 550 C and
10 min at 600 C; at 450 C these bands do not yet disappear after
about one week.
Previous IR studies of the dehydroxylation and transformation
processes in Kaol mainly dealt with the analysis of OH-stretching
regions (Johnston et al., 1990; Prost et al., 1989) and the analysis is
limited to temperatures up to 600 K. At higher temperatures, the
loss of the OH signal prevents to carry out a quantitative analysis at
high degrees of dehydroxylation (e.g. see Rahier et al., 2000). There-
fore, here we propose to follow the process by analysing the large
changes observed in the MIR region to bands related to fundamental
structural features of Kaol and MKaol. This allows to indirectly
increase the sensitivity of the measurements and to circumvent
uncertainties related to the tting of very weak OH-stretching
bands, especially at high degrees of transformation, and to the
subtraction of baseline due to nonstructural water. In the MIR region,
an overall increase in linewidth is observed as a function of increas-
ing annealing time. Beside instrumental prole, the shape of infrared
absorption bands is mainly given by the convolution of an intrinsic
line prole (due to the lifetime of the relative phonons) and a distri-
bution function of phonon frequencies due to local structural hetero-
geneities of the samples (Salje et al., 2000). An increase in system
heterogeneity and strain accompanies the transformation from
Kaol into MKaol (Gualtieri and Bellotto, 1998; White et al., 2010),
hence analysis of linewidth can give insights into the evolution of
the reaction. The strong overlapping of bands and difculties in
determining precisely the baseline in the spectra make a quantita-
tive determination of linewidth difcult using traditional peak tting
methods. In order to circumvent these problems, the evolution of the
linewidth with annealing time was analysed using an autocorrela-
tion approach. This method is particularly suited to investigate the
transformations of low-symmetry minerals such as kaolinite, whose
 E. Gasparini et al. / Applied Clay Science 8081 (2013) 417425 421

Fig. 3. X-ray powder diffraction patterns of Sl-K untreated sample and after each thermal treatment. Working temperatures are shown in the graphs as labels. Q = quartz; K = kaolinite.
422 E. Gasparini et al. / Applied Clay Science 8081 (2013) 417425
Fig. 4. Selected regions of FTIR-ATR spectra collected for Sl-K untreated sample and after
each thermal treatment. Working temperatures are shown in the graphs as labels.
spectrum displays several overlapping bands, and has been already
applied to this phase (Balan et al., 2010; Fourdrin et al., 2009). With
respect to tting procedures, it does not require any assumption on
the number of peaks, a point that has been previously debated for the
kaolinite spectrum (Farmer, 1998, 2000).
As evident in Table 1 and expected, the empirical broadening factor
obtained from the spectra autocorrelation increases with annealing
time. The increase of the empirical broadening factor results from
local structural changes induced by disruption of the Kaol structure
and can give insight into the transformation behaviour even in the
case in which the spectra can be interpreted as a mixture of Kaol and
MKaol.
3.4. Kinetics of dehydroxylation of kaolinite
Kinetics of a chemical process can be described by the general
equation d / dt = k f(), where is the degree of conversion of
the reaction, k the rate constant at a given temperature, and f()
the kinetic model function, usually an empirical function dependent
on the mechanism of reaction. The selection of the f() function is
one that best approximates the experimental data but the main
disadvantage is that several kinetic models may provide a similar
statistical goodness-of-data approximation. This is generally more
critical for ex situ methods since a lower number of experimental
points are typically measured, while in situ methods allow the
measurement of the evolution of the process almost continuously.
Furthermore, the degree of conversion is often not directly observed
by experimental measurements and hence must be derived from
known relationships.
The process object of this study can be expressed by the reaction:
Al2 Si2 O5 OH4 KaolAl2 Si2 O7 MKaol 2H2 Og :
The degree of conversion of this reaction can then be dened as
the quantity of Kaol transformed into MKaol, the latter being more
difcult to quantify given its amorphous state. In this study, different
parameters directly related to the degree of conversion of the reaction
have been monitored at RT on quenched samples (Table 2). In Fig. 5,
the variations with time under isothermal conditions at the four work-
ing temperatures of this study are reported for: (a) moles of water lost
during heating, as determined by the difference between initial and
nal mass after the thermal treatment; (b) intensity of (001)K
diffraction peak of Kaol, normalised to (101)Q diffraction peak of
quartz; and (c) average linewidth, expressed as corr, of IR bands in
the 670 to 2000 cm 1 region, as determined by the autocorrelation
analysis. The evolution of all these parameters with time follows an
exponential law of type y = k0 + k1exp( k2x) at T = 500, 550
and 600 C, while the same function does not give a good t to the
data for the 450 C datasets. The tted values of the exponential con-
stants k2 are reported in Table 2 for the curves relative to 500, 550
and 600 C datasets. To a rst approximation, such values can be
treated as model-independent kinetic constants of the dehydroxylation
process. When put in an Arrhenius plot, such exponential constants
yield the following activation energy values: 128 10 kJ mol1 (linear
regression R = 0.997) from water loss, 136 9 kJ mol1 (R = 0.998)
from diffraction, and 131 32 kJ mol1 (R = 0.976) from IR. The three
methods yield indeed very similar results, although errors result fairly
higher from IR data.
A kinetic analysis has been performed by testing different rate equa-
tions, indicative of different mechanisms. Actually, given the relatively
low number of points measurable by ex situ experiments, several kinetic
models provide quite similar results and discerning the rate controlling
process by judging the goodness of t between data and a given rate
equation is not an easy task. Nonetheless, it is possible to employ a
general empirical rate equation in which the function f() is expressed
in some general manner with a variable parameter that reects the
 E. Gasparini et al. / Applied Clay Science 8081 (2013) 417425 423

Table 2
Exponential constants k2 from unconstrained ts of selected parameters vs. time and relevant parameters (m, k) of Avrami analysis.

T (C) Weight loss (001)K peak area IR corr

k2 m k k2 m k k2 m k

450 0.39 (3) 0.0002 (1) 0.58 (3) 0.0002 (1) 0.33 (3) 0.0004 (2)
500 0.021 (2) 0.64 (5) 0.019 (7) 0.020 (1) 0.75 (6) 0.020 (7) 0.024 (2) 0.94 (4) 0.025 (5)
550 0.081 (7) 0.68 (5) 0.095 (5) 0.08 (1) 0.74 (4) 0.10 (2) 0.13 (1) 0.8 (3) 0.1 (3)
600 0.20 (1) 0.73 (4) 0.220 (3) 0.226 (4) 0.94 (6) 0.24 (4) 0.24 (2) 0.81 (7) 0.24 (6)

Standard deviations are in parentheses.

rate controlling mechanism. A well established data analysis procedure is where k is the kinetic constant and m is indicative of the mechanism
the JohnsonMehl or Avrami method (Avrami, 1939; Hancock and controlling the reaction rate. By integrating and taking the logarithms,
Sharp, 1972), which assumes: it follows:
d m m1
k t 1
dt lnln1 m ln t m lnk

which corresponds to the linearized form of the Avrami equation. The

values of k and m can be calculated from the intercept and slope of
the graph ln(ln(1 )) versus ln t, the so-called lnln plot. In
Fig. 6a, the variations of , as calculated from mass loss, intensity of
(001)K diffraction peak and IR bands (WL, XRD, IR, respectively),
assuming complete dehydroxylation, are reported as a function of ln t.
The corresponding lnln plots are reported in Fig. 6b. The curves
relative to T = 500, 550, and 600 C show nearly the same slope
and indicate then isokinetic data, while a different temperature regime
for the dehydroxylation reaction of Kaol is found at lower temperatures,
given the different slopes shown by the datasets relative to 450 C.
Values of m and k are reported for all the temperatures in Table 2. Kinetic
constants k are reported in an Arrhenius plot in Fig. 7. Activation energy
associated to the process, in the temperature range 500600 C, has been
determined on the basis of the three measured parameters, which
yielded: 137 19 kJ mol 1 (R = 0.99) from mass loss, 139
22 kJ mol 1 (R = 0.987) from intensity of XRPD peaks, and
127 38 kJ mol 1 (R = 0.959) from intensity of IR bands.
Such values are indeed very similar, indicating that the three param-
eters give a direct response to the degree of transformation of Kaol into
MKaol. The activation energy determined for Kaol from a sample
containing 27% of free quartz results to be in the lower limit but
within the range of previously published data (Bellotto et al., 1995;
Dion et al., 1998; Ortega et al., 2010).

4. Conclusions

The dehydroxylation reaction of Kaol was studied, under isothermal

Fig. 5. Variations with time under isothermal conditions for: (a) moles of water lost, as
determined by the difference in mass before and after the thermal treatment; (b) intensity
of (001) diffraction peak of Kaol, normalised to (101) of quartz; (c) average linewidth of IR
bands in the 6701400 cm1 region, as determined by the autocorrelation analysis.
Diamonds: 450 C (time scale on upper axis); circles: 500 C; squares: 550 C; triangles:
600 C. Exponential ts are reported as dashed lines.
conditions, at different temperatures: 450, 500, 550 and 600 C by
monitoring the variations in water content, intensity of the (001)K
diffraction peak and average linewidth of IR spectra from 670 to
1400 cm 1 using the autocorrelation approach. The variations of
these three variables as a function of heating time at each working
temperature, analysed by the Avrami method, allowed to obtain kinetic
constants for the dehydroxylation process and, from these, the empirical
activation energy. Different mechanisms controlling the rate of the reac-
tion are found, as only datasets relative to T = 500, 550, and 600 C
resulted to be isokinetic. The activation energy values obtained in the
temperature range 500600 C on the basis of the three measured
parameters are comparable and range between 127 and 139 kJ mol1.
Finally, the excellent correlation between sample mass-loss and
changes in the intensities of XRPD and FTIR-ATR peaks allows the
consideration of FTIR-ATR spectroscopy as a quick promising tool for
evaluating the degree of dehydroxylation and of MKaol formation.
Such study allows determining the best conditions in terms of
temperature and time to activate Kaol by thermal methods, also at
an industrial level.
424 E. Gasparini et al. / Applied Clay Science 8081 (2013) 417425
Fig. 6. Left column: degree of conversion calculated from mass loss (WL), (001) diffraction peak of Kaol (XRD) and average linewidth of IR bands in the 6701400 cm1 region (IR)
plotted vs. ln t; right column: corresponding lnln plots. Symbols as in Fig. 5.
Fig. 7. Arrhenius plots relative to Kaol dehydroxylation kinetics. Open diamonds: data
relative to mass loss; solid squares: data relative to XRPD; crosses: data relative to FT-IR.
Linear ts through 500600 C points are reported as dashed lines.
Acknowledgements
The authors are grateful to L. Marinoni for the assistance with XRPD
measurements. The authors also thank F. Bergaya and an anonymous
reviewer for their comments which helped in improving the manu-
script. E. Gasparini has been supported by the Italian Ministry of Educa-
tion, University and Research scholarship (Fondo per il sostegno dei
giovani).
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