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Applied Clay Science 8081 (2013) 417425
Research paper
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 as thermal analysis (Balek and Murat, 1996; Castelein et al., 2001;
Dion et al., 1998; Nahdi et al., 2002; Ptek et al., 2010a, 2011;
Kaolinite (hereafter, Kaol) is the main mineral phase of kaolin which Redfern, 1987), infrared spectroscopy (Prost et al., 1989; Temuujin
contains other phyllosilicates and feldspars, and other minerals such as et al., 1998), X-ray diffraction (Artioli, 1997; Bellotto et al., 1995;
quartz, rutile, hematite, ilmenite, zircon, carbonates, sulphides, and Temuujin et al., 1998), MAS-NMR (He et al., 2003; Massiot et al.,
various ferrous and aluminium (hydr)oxides. Kaol, Al2Si2O5(OH)4, 1995; Temuujin et al., 1998), electron microscopy (Bergaya et al.,
is a dioctahedral phyllosilicate with a 1:1 type layered structure 1996; de Souza Santos et al., 2005), thermodilatometry (Chakraborty,
and its space group is triclinic P1 (Bailey, 1980; Bish, 1993; Giese, 1992; Liu et al., 2002), efuent gas analysis (Ptek et al., 2010b) and
1991). A detailed and accurate description of Kaol structure is electron paramagnetic resonance (Djemai et al., 2001). Exact information
provided by Brigatti et al. (2006). about the mechanism and the kinetics of the dehydroxylation process
Kaol is an important primary material in a variety of industrial remains contentious. This is because the dehydroxylation reaction
processes e.g., food-processing industry, oil shale processing, ceramic depends on many different factors such as Kaol structure (e.g., particle
industry, as a pozzolanic material, as a feedstock for geopolymer size, shape and morphology, density of defects), associated minerals,
cement, as a lling agent, to cite some (see, for example Bundy, heating rate, sample treatment, pressure and partial water vapour
1993; Duxson et al., 2007; Prasad et al., 1991) and it is typically pressure (Artioli, 1997; Castelein et al., 2001; Dion et al., 1998; Ptek
used after transformation, via calcination, into its dehydroxylated et al., 2010a, 2011). However, it is known that the dehydroxylation
phase metakaolinite (hereafter, MKaol), Al2Si2O7, which is much process in Kaol is accompanied by a change in the aluminium coordina-
more reactive. MKaol is the rst phase to occur on heating Kaol in tion from six- to a mixture of six-, ve- and four-fold (Gualtieri and
the temperature range from 450 to 700 C, after the water desorption Bellotto, 1998; Leonard, 1977; MacKenzie et al., 1985; Massiot et al.,
step at T up to 100 C. The thermal transformation of Kaol to MKaol 1995; Rocha and Klinowski, 1990; Sperinck et al., 2010). Some authors
has been studied for a very long time and by different techniques such 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
Corresponding author. Tel.: +39 0382985839; fax: +39 0382985890. groups, the initial crystalline layered structure of kaolinite is subjected
E-mail address: elisa.gasparini@unipv.it (E. Gasparini). 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
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 2.5. IR spectroscopy
in Table 1. All the heat-treated samples were then characterised by
means of XRPD and FTIR-ATR 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
2.4. X-ray powder diffraction 4 cm1 using a Thermo Scientic Nicolet iN10 MX micro-spectrometer.
Every spectrum, recorded in attenuated total reectance (ATR) with a
XRPD measurements were carried out by means of a Philips PW liquid nitrogen cooled mercury cadmium telluride (MCT) array detector,
1808 diffractometer with BraggBrentano geometry using Ni ltered was calculated by Fourier transformation of 256 interferometer scans
CuK radiation ( = 1.5418 ). Data were collected in the range 2 and total scanning time of 90 s. A germanium hemispherical internal
65 2 with a step width of 0.01 2 and time per step of 0.5 s for samples reection element (IRE) crystal with a diameter of 300 m was used.
heated at 450, 500 and 550 C and of 1.0 s for samples heated at 600 C. The ATR accessory is mounted on the XY stage of the FTIR microscope,
Peak prole analysis was performed using Voigt proles with the and the IRE crystal makes contact with the sample via a force lever
MultiPeakFitting routine from IGOR Pro software (Wavemetrics Inc., with pressure of 2 Pa. A 37.7 37.7 m aperture size was used.
OR). Intensities of (001) peak of Kaol, hereafter labelled as (001)K, The evolution of the linewidth of IR bands with annealing time was
normalised with respect to (101) peak of quartz, labelled (101)Q, are analysed using an autocorrelation approach, which was introduced to
reported for all the heat-treated samples in Table 1. 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
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 heating time was about one week and, after this treatment, the reaction
to investigate phase transitions in minerals, has allowed, in particular, was not yet complete.
detailed studies of variations in linewidths of IR spectra due to the
effects of composition and cation order across mineral solid solu- 3.3. Ex situ annealing experiments: FTIR-ATR
tions (Balan et al., 2011; Blanch et al., 2008; Boffa Ballaran and
Woodland, 2006; Etzel and Benisek, 2008; Meyer et al., 2002; Pring The IR spectra of untreated and heat-treated Sl-K samples are shown
et al., 2008; Salje et al., 2010; Tarantino et al., 2005). The method in Fig. 4. The spectrum of the pristine Sl-K sample displays intense and
uses an autocorrelation function, dened as: well-resolved absorption bands and shows the four OH-stretching
bands between 3600 and 3700 cm 1. In particular, the stretching
Z
band of the intra-layer OH group is at 3620 cm 1; the other three
Corr; d 1 bands are at 3651, 3670 and 3689 cm 1 and correspond to the
stretching modes of the inner-surface OH groups (Balan et al.,
2001; Farmer, 1998). The three peaks observed between 1000 and
where () is the spectrum itself and ( + ) is the same spectrum 1200 cm 1 correspond to Si\O stretching modes whereas the
offset in frequency by , to extract and analyse spectral changes (Salje bands observed around 900 cm 1 correspond to bending modes
et al., 2000). An effective linewidth parameter corr, the main informa- involving OH groups (Balan et al., 2001). The double peak at around
tion on the linewidth of the IR spectrum is then obtained from the 750 cm 1 is indicative of the presence of quartz in the sample.
shape of the autocorrelation function in the limit of 0. It is propor- Signicant changes in width and intensity of OH-stretching bands
tional to the average width and mode splitting in the chosen segment of are monitored with increasing the heating time at each temperature.
the primary spectrum and proves to be rather more robust with respect Moreover, the bands at 3620 and 3689 cm 1 shift toward higher
to changes of baselines and instrumental noise than the usual line frequencies with increasing heating time. It is important to note
tting procedure. that all of these OH-stretching bands disappear after 120, 40 and
The spectral range chosen here for the calculation of corr is the 670 10 min of heating at 500, 550 and 600 C, respectively, long before
to 2000 cm1, i.e. the domain including the Si\O stretching modes and the Kaol diffraction peaks disappear from the diffraction patterns.
O\H bending modes. The variation of effective linewidth, expressed as At 450 C, after about one week of heating, the two external OH-
the parameter corr is reported for all the datasets of this study in stretching bands are still present to indicate the slow accomplish-
Table 1. ment of the dehydroxylation reaction.
Bands in the MIR range, related to Si and Al, also show large variations
3. Results and discussion 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
3.1. Thermal decomposition of kaolinite: Thermal analysis evident, nally the Si\O peaks become a unique broad band centred at
higher frequency. Moreover, an increase in linewidth is immediately
The TGDTA plots of Sl-K sample are shown in Fig. 2. Different evident from visual inspection of this region. The 910 and 935 cm1
thermal effects are evident from the curves. At T below 150 C, the bands related to Al\O\H disappear after different heating times at dif-
adsorbed water is removed. In the TG curve, this effect corresponds to ferent heating temperatures: 210 min at 500 C, 40 min at 550 C and
a mass loss of ca. 0.5%, while, in the DTA plot, this desorption process 10 min at 600 C; at 450 C these bands do not yet disappear after
is visible as a weak endothermic peak. The second event is recorded in about one week.
the TG curve by a signicant mass loss, of ca. 9.5%, and corresponds to Previous IR studies of the dehydroxylation and transformation
the dehydroxylation of Kaol and formation of MKaol. The mass loss, as processes in Kaol mainly dealt with the analysis of OH-stretching
measured by the TG plot, permits to quantify the content of Kaol in regions (Johnston et al., 1990; Prost et al., 1989) and the analysis is
Sl-K sample to ca. 73%. In the DTA plot, the dehydroxylation reaction limited to temperatures up to 600 K. At higher temperatures, the
is visible as a strong endothermic valley peaked at 528 C. loss of the OH signal prevents to carry out a quantitative analysis at
Dehydroxylation temperatures, recorded in literature, range high degrees of dehydroxylation (e.g. see Rahier et al., 2000). There-
between 530 and 630 C and, in some cases, they reach 700 C. fore, here we propose to follow the process by analysing the large
Usually, dehydroxylation temperatures below 570 C are ascribed changes observed in the MIR region to bands related to fundamental
to disordered kaolinites (Smykatz-Kloss, 1974). The last two structural features of Kaol and MKaol. This allows to indirectly
effects in the DTA curve are exothermic peaks. The rst, peaked at increase the sensitivity of the measurements and to circumvent
1009 C, is sharp and is related to mullite formation according to uncertainties related to the tting of very weak OH-stretching
the following reaction: 3(2Al2O33SiO2) 2(3Al2O32SiO2) + 5SiO2 bands, especially at high degrees of transformation, and to the
(Castelein et al., 2001; Ptek et al., 2010a). The second is a large subtraction of baseline due to nonstructural water. In the MIR region,
broad peak in the region from 1100 to 1300 C which may be also related an overall increase in linewidth is observed as a function of increas-
to mullitization from MKaol (Chakraborty, 2003; Wang et al., 2011). ing annealing time. Beside instrumental prole, the shape of infrared
absorption bands is mainly given by the convolution of an intrinsic
3.2. Ex situ annealing experiments: XRPD line prole (due to the lifetime of the relative phonons) and a distri-
bution function of phonon frequencies due to local structural hetero-
The XRPD patterns of the Sl-K sample before and after each thermal geneities of the samples (Salje et al., 2000). An increase in system
treatment at 450, 500, 550 and 600 C are shown in Fig. 3. The XRPD heterogeneity and strain accompanies the transformation from
pattern of the untreated sample shows the presence of Kaol and Kaol into MKaol (Gualtieri and Bellotto, 1998; White et al., 2010),
quartz. At each temperature, with increasing the heating time, the hence analysis of linewidth can give insights into the evolution of
diffraction peaks of Kaol become less intense, thus indicating the the reaction. The strong overlapping of bands and difculties in
progress of the dehydroxylation and, consequently, the transformation determining precisely the baseline in the spectra make a quantita-
of Kaol into the X-ray amorphous phase MKaol. Completion of the tive determination of linewidth difcult using traditional peak tting
dehydroxylation reaction, as deduced by the absence of diffraction methods. In order to circumvent these problems, the evolution of the
peaks of Kaol from the visual inspection of the diffractograms, was linewidth with annealing time was analysed using an autocorrela-
attained in ca. 40 min at the highest working temperature, i.e. 600 C, tion approach. This method is particularly suited to investigate the
ca. 180 min at 550 C and ca. 240 min at 500 C. At 450 C, the longest 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
Table 2
Exponential constants k2 from unconstrained ts of selected parameters vs. time and relevant parameters (m, k) of Avrami analysis.
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)
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
4. Conclusions
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.
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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