J Therm Anal Calorim (2014) 115:3136
DOI 10.1007/s10973-013-3267-0
Kinetic study of template removal of Al-MCM-41 synthesized
at room temperature
Cristiane P. de Macedo Charles A. B. Negrao
Luiz G. M. de Macedo Jose R. Zamian
Geraldo N. da Rocha Filho Carlos E. F. da Costa
Received: 21 January 2013 / Accepted: 21 May 2013 / Published online: 29 June 2013
Akademiai Kiado, Budapest, Hungary 2013
Abstract The Al-MCM-41 molecular sieve with Si/
Al = 20 molar ratio was synthesized at room temperature
and characterized by X-ray diffractometry, surface area,
thermogravimetry, and infrared spectroscopy. The kinetic
study was conducted by Vyazovkin and Ozawa method, in
order to verify the activation energy during the Hofmann
degradation between 130 and 370 C, in which most of
surfactant removal occurs. The results suggest that the
activation energy for template removal is close to
80 kJ mol-1 lower in Al-MCM-41 synthesized at room
temperature, when compared to results obtained for mes-
opores Al-MCM-41 and MCM-41 synthesized by hydro-
thermal method. This lower activation energy may be
understood as consequence of textural properties, such as
higher pore size.
Keywords Al-MCM-41  Activation energy  Model free
kinetics  Room temperature synthesis
Introduction
Researchers seek to enhance the performance of the mes-
oporous MCM-41 since pure siliceous materials have
electrically neutral frameworks, which limit the use of
C. P. de Macedo  C. A. B. Negrao  J. R. Zamian 
G. N. da Rocha Filho  C. E. F. da Costa
Laboratorio de Catalise e Oleoqumica, Faculdade de Qumica,
Instituto de Ciencias Naturais, Universidade Federal do Para,
Belem, PA 66075-110, Brazil
L. G. M. de Macedo (&)
Faculdade de Biotecnologia, Instituto de Ciencias Biologicas,
Universidade Federal do Para, Belem, PA 66075-110, Brazil
e-mail: lgm@ufpa.br; drlgmm@gmail.com
these materials as catalysts [1]. These mesoporous MCM-
41 can be synthesized by several routes through the mod-
ification of variables such as, pH, surfactant concentration,
temperature, silicon source, synthesis time and aging,
among others. The presence of silanols groups in MCM-41
allows surface modification of this material. The modifi-
cation can be achieved by different ways, such as by direct
synthesis or by post-synthesis, but they have the drawback
of reducing the pore structure quality when compared to
pure silicon.
Direct synthesis can be done by the hydrothermal
method or at room temperature [2]. The hydrothermal
method involves heating the reactant at elevated tempera-
tures, and needs more synthesis time and more energy
consumption. On the other hand, the advantages of using
the room temperature route range from speed and lower
cost to the excellent reproducibility [3].
A way to improve the performance of MCM-41 as a
catalyst is substituting the Si4? by Al3? in the mesopore
walls [4]. With this substitution, the structure begins to have
a negative charge that can be compensated by protons, thus
generating the acid Brnsted sites. The number of formed
acid sites depends on the quantity of aluminum inserted
through synthesis [5]. The resulting solid is commonly used
in acid reactions [4], and is known as Al-MCM-41.
Several aluminum sources have been used in room
temperature synthesis of Al-MCM-41, such as aluminum
isopropoxide, aluminum sulfate, aluminum nitrate, alumi-
nate sodium [2], and aluminum chlorite [5]. These
Al-MCM-41 molecular sieves are attractive due to the
adjustable pore size, elevated surface area, and because
they have moderate acidity. Besides these advantages, the
calcination procedure can dealuminate the Al-MCM-41,
hence resulting in mesoporous with small amount of
Brnsted and Lewis acid sites [6].
123
32
The calcination step has attracted the attention of
researchers because it is one of the crucial steps in order to
obtain a material of optimal quality. It is also in this step
that the surfactant removal occurs. In general, kinetic study
of the surfactant removal is important because the exces-
sive exposure of the material to elevated temperatures can
destroy its mesoporous characteristics [7].
On the other hand, when kinetics of complex reactions is
studied, such as the decomposition of the surfactant or the
thermal decomposition of fuel oils, the traditional kinetic
methods cannot be normally applied. For this reason,
methods have been developed in order to investigate the
kinetics of these reactions [8]. For example, some studies
report the kinetic data of the surfactant removal from
molecular sieves MCM-41 and Al-MCM-41 synthesized
by the hydrothermal method with different silica sources
[7, 9, 10], using the methods developed by Ozawa [11] and
Vyazovkin [12, 13].
This study focuses the kinetic study of the removal of
the organic template cetyltrimethylammonium bromide
(CTAB) by Ozawa and Vyazovkin methods from Al-
MCM-41 synthesized at room temperature, as well its
characterization. The literature data on such template
removal for Al-MCM-41 and MCM-41 obtained under
hydrothermic synthesis conditions are also compared with
the present results.
Experimental
Materials
The reactants used were: cetyltrimethylammonium bro-
mide (CTAB, Aldrich), absolute ethylic alcohol (Nuclear),
ammonium hydroxide (Cromoline), hydrated aluminum
nitrate (Vetec), and Tetraethoxysilane (TEOS, Aldrich).
The reactants were used without previous treatment.
Al-MCM-41 synthesis
The material was synthesized according to the procedure
described in the literature [14] with hydrated aluminum
nitrate as source of aluminum. 2.5 g of CTAB was dis-
solved in deionized water under vigorous stirring. 60 g of
absolute ethanol was added to this mixture, with later
addition of 16.9 g of a solution of ammonium hydroxide
(29 % m/m) under agitation for 15 min. 0.42 g of the
aluminum source was added to the solution, which seemed
transparent, and afterwards 4.7 g of TEOS was added
drop by drop. The resulting gel obtained after the addition
of TEOS, with molar composition of 1TEOS:0.3CTAB:
123
C. P. de Macedo et al.
11NH3:58EtOH:114H2O:0.00112Al, was stirred for 2 h
Then the material was aged at room temperature for 20 h,
filtered by vacuum, washed several times with distilled
water, and dried at 60 C for 12 h. The obtained solid was
named Al-MCM-41(S).
Removal of organic surfactant from Al-MCM-41 sample
was performed by calcination: the sample was heated from
room temperature to 540 C at a heating rate of 5 C min-1,
and under nitrogen atmosphere (100 mL min-1). After
reaching the 540 C temperature, nitrogen flow was replaced
by synthetic air, at a rate flow of 100 mL min-1. The iso-
thermal treatment was kept at the same temperature for 2 h.
This sample was labeled as Al-MCM-41(C).
Sample characterization
X-ray diffraction (XRD)
X-ray diffractions were obtained on a PANalytical,
XPERT PRO MPD (PW 3040/60) diffractometer, using
powder method, at a 1.5 \ 2h \ 6 interval. Co Ka
(40 kV and 40 mA) radiation was used. The 2h scanning
speed was 0.02 min-1.
N2 adsorptiondesorption
Nitrogen adsorptiondesorption isotherms were obtained at
liquid nitrogen temperature using a Micromeritics TriStar
II model 3020 V1.03 apparatus. Before each measurement,
the sample was outgassed at 300 C for 2 h. The specific
surface area was determined according to the standard
BrunauerEmmettTeller (BET) [15]. Pore diameter and
pore volume obtained by the BarrettJoynerHalenda
(BJH) method [16] .
Thermal analysis (TG/DTA)
The thermal decomposition of Al-MCM-41(S) sample was
carried out on a simultaneous TG/DTA (Shimadzu DTG-
60H) thermogravimetric analyser. About 5 mg of the
samples were placed in platinum pans and heated from
room temperature to 700 C, at heating rates of 5, 10, 15,
20, and 25 C min-1 in a nitrogen flux of 50 mL min-1. To
obtain activation energy, the Ozawa [11] and Vyazovkin
[12, 13] methods were used.
Fourier transformed infrared spectroscopy (FTIR)
Infrared spectra were recorded in the 4000400 cm-1
spectral region by means of Thermo IR 100 spectrometer.
Kinetic study of template removal of Al-MCM-41 33

Results and discussion Table 1 Textural properties of the sample Al-MCM-41(C)

da100/ aa0/A SBET/ Pore Pore Network
The information of the Al-MCM-41(S) and Al-MCM- A m2 g-1 diameterb/ volumeb/ contraction/%
41(C) diffractograms were obtained by an X-ray diffraction A cm3 g-1
technique. Figure 1 shows three peaks with reflection of
36.70 42.37 1372 32.39 1.43 9.58
2h = 2.29, 3.92, and 4.54 for the Al-MCM-41(S) sample
a
and 2.39, 4.16, and 4.77 for the Al-MCM-41(C) sample. dhkl and a0were obtained from the XRD data using the formula
a0 = 2d100/31/2
The peak with highest intensity is due to the reflection line b
Pore diameter and pore volume were determined using BJH method
of plane (100), and another two of lower intensity, due to
the reflections of planes (110) and (200), and they are
characteristic of hexagonal mesopores [17]. asymmetric stretch of SiO; (c) in the region
An increase of the intensity of the three peaks was 10891069 cm-1 is related to the asymmetric internal
observed after the calcination process, as well a better stretch of TOT (T = Si, Al); (d) in the region
definition of the higher angle peaks, thus confirming the 974961 cm-1 is related to asymmetric stretch of CH3
hexagonal structure and orderly arrangement [18]. N?; (e) in the region 801795 cm-1 is related to the
The displacement of the peak with highest intensity symmetric stretch of TO (T = Si, Al) [7, 10].
from 2h = 2.29 to 2.39 was observed after calcination, After the calcination process, the vanishing of the bands
suggesting the contraction of the unit cell due to surfac- in 2914 and 2850 cm-1 shown in Fig. 2b indicates that the
tant removal and the condensation of the silanol groups process of surfactant removal was effective and as a result,
(SiOH) [19]. Table 1 shows the results of the textural pore cavities were generated.
properties as pore diameter, pore volume, surface area, net- The thermogravimetric curves for the Al-MCM-
work contraction as well unite cell parameters d100 and a0. 41(S) sample, represented in Fig. 3 indicate three mass
The infrared absorption spectra of the Al-MCM- losses were observed between 30 and 700 C. The first loss
41(S) and Al-MCM-41(C) are shown in Fig. 2. The wide (4.02 %) occurs between temperatures 30 and 130 C, and
band around 34313399 cm-1 is related to hydroxyl it is related to the elimination of physically adsorbed water
groups in the mesoporous structure; the absorption bands or to the evaporation of residual ammonium [20]. The
shown in Fig. 2a in 2914 and 2850 cm-1 are related to the second loss occurs between 130 and 370 C, and it is
stretching of the CH bonds from the CH2 and CH3 groups usually due to the elimination of trimethylamine (N(CH3)3)
of the surfactant species, while the band in through Hofmann degradation. Also, in this step a large
16421644 cm-1 can be assigned to physically adsorbed part of the surfactant (35.92 %) is removed by alkene
water molecules. evaporation (C16H32), and by the fragmentation of the short
Other vibration bands that can be observed are: (a) at carbonic chains, producing CO2, NO2, and H2O. The third
1478 cm-1 is related to the deformation of the CH2 bond; mass loss (5.16 %) was observed in the TG curve between
(b) in the region of 12351217 cm-1 is related to the temperatures 370 and 700 C, and it is usually assigned to

(100)

(110) (a)
Intensity/a.u.

(200)
Transmittance/a.u.

1478

(b)
Intensity/a.u.

1624-1644

(a)
801-795
2850

974-961
2914

3.5 4.0 4.5 5.0

2 /
3431-3399

(b)
1089-1069

(110) (200)
1235-1217

(a)
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 4000 3500 3000 2500 2000 1500 1000 500
2 / Wavenumber/cm1

Fig. 1 X-ray diffractogram patterns of a Al-MCM-41(S), b Al- Fig. 2 Infrared absorption spectroscopy for material: a Al-MCM-
MCM-41(C) 41(S) and b Al-MCM-41(C)

123
34 C. P. de Macedo et al.

0.0005
ZT    
100 Ea R 2 Ea
0.0000 exp  dT  T exp  4
RT E RT
0.0005
0

DTG/% C1
80 0.0010 Substituting the temperature integral and making some
mathematical manipulation gives the following equation
Mass/%

0.0015
used in the Vyazovkin method,
0.0020  
60 b Rk0 Ea
ln 2 ln  5
0.0025 T Ea ga RT
0.0030
40
On the other hand, Eq. 3 could also be treated [27] as
0 100 200 300 400 500 600 700
AEa
Temperature/C g a qx 6
bR
Fig. 3 TG and DTG curves for Al-MCM-41(S) with ratio
10 C min-1 where x = (Ea/RT) and log q(x) % -2.315 - 0.4567x.
From Eq. 6 one can obtain the following expression used in
Ozawa method
the elimination of residual carbonic species and the con-
AEa Ea
densation of silanol groups [2123]. logga log  log b  2:315  0:457 7
The kinetic data of the surfactant removal from the R RT
pores were obtained through thermogravimetric analysis Thus, the activation energy can be obtained from Eq. 7 as
(TG). By applying an isoconversion method on the TG the slope of a plot of logb versus 1/T for fixed values of a
curves, one can obtain the activation energy as a function from experiments at different heating rates b. From Eq. 5,
of conversion a. They are based on the fact that constant similar results can be obtained from a plot of lnb/T versus
conversion of the reaction rate is only a function of tem- 1/T, but now the slope should have the value of -Ea/R.
perature. Furthermore, they are commonly used to obtain In a typical experiment, it is necessary to obtain at least
reliable kinetic information, and also of great advantage three different heating rates b. For the Al-MCM-41(S) TG
since avoid the use of explicit kinetic models [24]. In order curves in this study, five heating ratios were used (b = 5,
to compare directly the results from this study with the 10, 15, 20, and 25 C min-1), with temperature range from
results from literature, Vyazovkin and Ozawa (also known 130 to 370 C regarding to the thermal decomposition of
[25] as Flynn, Wall, and Ozawa or ASTM E698) methods the CTAB by Hofmann degradation [23]. Figure 4 shows
were applied to obtain the value for activation energy. the five conversion curves as a function of the temperature,
In both methods, the dependence of a as a function of time obtained by Eq. 8:
can be expressed as the following differential equation [26],  
mh  mt
a 8
d mh  mf
dT kT  f a 1
a where mh is the initial samples mass, mt is the samples
where k(T) is the temperature dependent rate constant and mass that varies in function of time or temperature, mf is
f(a) is a function that represents the reaction model. The the samples mass in the end of the step to be studied, and a
k(T) is usually represented by the Arrhenius equation, is the conversion.
  The levels of conversion of 10, 20, 30, 40, 50, 60, 70,
da A Ea 80, and 90 % were chosen in order to calculate the acti-
exp  f a 2
dT b kT vation energy by both isoconversion methods. In the
Vyazovkin method for each a conversion the values of lnb/
where A is the pre-exponential factor, b is a constant
T2a were plotted as a function of 1/Ta (represented in
heating rate, R is the gas constant (in J K-1 mol-1), and Ea
Fig. 5a), providing a series of lines with slope -Ea/R. In
is the activation energy. Integrating Eq. 2 gives
the Ozawa method, the logarithm of the heating rate (log b)
ZT   versus the inverse of the absolute temperature (1/Ta) was
A Ea plotted for the three heating rates. Thus, five straight lines
g a exp  dT 3
b RT were obtained (represented in Fig. 5b) with slope -Ea/R,
0
with R = 8,314 J mol-1 K-1.
Now Eq. 3 can be modified in order to be practical. Since The results obtained for the activation energies from the
E/2RT  1, the temperature integral can be approximated by Vyazovkin and Ozawa methods are presented in Table 2.

123
Kinetic study of template removal of Al-MCM-41 35

Table 2 Activation energy for the conversion of 1090 % of Al-

100 5 C min1
MCM-41(S) obtained by Vyazovkin and Ozawa models
10 C min1
15 C min1 Conversion/% Vyazovkin Ea/kJ mol-1 Ozawa Ea/kJ mol-1
80
20 C min1
25 C min1 10 85.16 85.08
Conversion/%

60 20 82.97 79.60
30 83.45 79.97
40 40 87.28 83.62
50 85.08 81.34
20 60 86.55 82.64
70 91.83 87.84
0 80 93.54 89.47
150 200 250 300 350 400 90 100.94 96.80
Temperature/C Ea average 88.53 5.87 85.15 5.50

Fig. 4 Conversion curve as a function of the temperature of Al-

MCM-41(S)
At 10 % conversion, Vyazovkin and Ozawa methods
suggests an activation energy of 85.16 and 85.08 kJ mol-1,
respectively. As the conversion goes on, the activation
energy slightly increases and at 90 % conversion, the
activation energies obtained by Vyazovkin and Ozawa
methods are 100.94 and 96.80 kJ mol-1, respectively.
Since Ea varies with a, this point should be interpreted in
terms of multi-step mechanisms [25].
The mean activation energy values for surfactant removal
obtained in the range of 1090 % of conversion suggested by
the Vyazovkin and Ozawa methods were, respectively,
88.53 5.87 and 85.15 5.50 kJ mol-1. These results are
close to 80 kJ mol-1, lower than the ones reported in the
literature for mesoporous obtained through hydrothermal
synthesis: Souza et al. [9] reports the value of 166
8.2 kJ mol-1, and Braga et al. [7] reports the value of
177.26 26 kJ mol-1, both being results for mesopores
MCM-41 without the addition of aluminum, and using the
Vyazovkin method. Braga et al. [7] also studied the surfactant
removal from MCM-41 through the Ozawa method, obtaining
a value of 173.7 23 kJ mol-1. With the insertion of alu-
minum in the structure (Al-MCM-41), Araujo et al. [10]
reports values obtained by the Vyazovkin method, of 165.8
and 270.1 kJ mol-1 for the temperature ranges of 100310 C
and 310600 C. One possible explanation for the difference
of the activation energy values obtained in this study, and the
values obtained by Souza [9], Araujo [10] and Braga [7] can
be understood as a function of the pore size: For example,
textural properties regarding pore size obtained by room
temperature synthesis in this study like SBET and pore vol-
ume (1372 m2 g-1 and 1.43 cm3 g-1) are larger than ones
obtained by Braga (757 m2 g-1 and 0.63 cm3 g-1). Higher
pore size would give less diffusional resistance and would be
more effective toward template removal. Although Souza [9]
and Araujo [10] didnt publish the textural parameters, it is
sensible to expect that Souzas values should be similar to the
ones from Braga, based on the fact that ticker pore wall
samples are formed in higher temperatures [28], resulting in
lower surface areas and pore volume values.

Fig. 5 Linear fits of the a 1.2 b 1.7

logarithms of heating rate
1.1 1.6
versus the reciprocal absolute 90 %
temperature for different 1.0 1.5 10 %
60 % 90 % 60 % 30 %
extends of conversion: a using 0.9 30 % 10 % 1.4
Vyazovkin model and b using 0.8
Log /C cm1
Ln /T 2/T 2

the Ozawa model 1.3

0.7
1.2
0.6
0.5 1.1
0.4 1.0
0.3 0.9
0.2 0.8
0.1
0.7
0.0
0.6
1.7 1.8 1.9 2.0 2.1 2.2 1.7 1.8 1.9 2.0 2.1 2.2
1000/T/K1 1000/T/K1

123
36
Conclusions
A mesoporous molecular sieve Al-MCM-41 was synthe-
sized at room temperature and initially characterized by
X-rays diffraction confirming the hexagonal ordering of the
structure. The kinetic studies done in this study through the
Ozawa and Vyazovkin methods suggest that the Al-MCM-
41 synthesized at room temperature is close to 80 kJ mol-1
lower activation energy for template removal than the
Al-MCM-41 obtained by hydrothermal synthesis. In other
words, the activation energy for template removal value for
room temperature synthesized Al-MCM-41 is practically
half of the correspondent activation energy value obtained
from hydrothermal synthesis, and this probably occurs due
to textural and pore characteristics.
Acknowledgements C. P. de Macedo thanks CAPES (Coordenacao
de Aperfeicoamento de Pessoal de Nvel Superior) for the doctoral
scholarship, and also CNPq (Conselho Nacional de Desenvolvimento
Cientfico e Tecnologico) and FAPESPA (Fundacao de Amparo a
Pesquisa do estado do Para) for financial support.
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