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Applied Clay Science 146 (2017) 526534

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Applied Clay Science

journal homepage: www.elsevier.com/locate/clay

Research paper

Kaolinite-polymer compounds by grafting of 2-hydroxyethyl methacrylate MARK

and 3-(trimethoxysilyl)propyl methacrylate
Breno F. Ferreiraa, Katia J. Ciua, Eduardo J. Nassara, Miguel A. Vicenteb, Raquel Trujillanob,
Vicente Rivesb, Emerson H. de Fariaa,
Universidade de Franca, Av. Dr. Armando Salles Oliveira, Parque Universitrio, 201, 14404-600 Franca, SP, Brazil
GIR-QUESCAT, Departamento de Qumica Inorgnica, Universidad de Salamanca, 37008 Salamanca, Spain


Keywords: Novel kaolinite-polymer solids containing methacrylate groups were prepared by functionalization of the
Kaolinite Brazilian So Simo kaolinite with the monomers 2-hydroxyethyl methacrylate (HEMA) and 3-(trimethoxysilyl)
Polymer propyl methacrylate (TMSPM). Functionalization involved reux of the monomers in the presence of kaolinite
Functionalization previously intercalated with dimethylsulfoxide (DMSO). HEMA and TMSPM eectively displaced DMSO mole-
cules from the clay mineral interlayer, forming AleOeC bonds in organic-inorganic hybrid matrices. The re-
sulting materials were characterized by powder X-ray diraction, thermal analysis, infrared spectroscopy and
TEM analysis. Powder X-ray diraction evidenced the intercalation of DMSO, and its substitution by HEMA and
TMSPM. Thermal analyses indicated that HEMA- and TMSPM-functionalized kaolinite materials were thermally
stable up to 300 C. The shift of the infrared bands due to interlayer hydroxyl groups and the presence of bands
due to characteristic vibrations of the methacrylate groups (3349, 3331, 3290, and 1589 cm 1) also conrmed
the functionalization of the kaolinite with the monomers. The ability of both monomers to graft methacrylate
groups onto kaolinite interlayer space was also analyzed. The solids obtained were used as adsorbents of dye
methylene blue (MB), showing that the clay nanocomposites could remove the dye more eciently than the
isolated precursors (pure kaolinite and the polymers) separately. The kinetics of the process followed a pseudo-
second order model and equilibrium tted well to the Freundlich model.

1. Introduction nanocomposites based on clays to be among the most extensively in-

vestigated, also because the starting clay materials are easily available
Natural or synthetic inorganic compounds, such as clays (bento- and their intercalation chemistry has been studied for a long time
nite), clay minerals (kaolinite, montmorillonite, saponite, talc, mica, (Bergaya and Lagaly, 2013; Kotal and Bhowmick, 2015; Pavlidou and
and among others), quartz or calcium carbonate, have been widely used Papaspyrides, 2008). Insertion of monomers then leading to the poly-
in the preparation of hybrid materials with polymer matrices, in order meric organic matrix in the interlayer space of clay minerals leads to
to improve their properties, or simply to reduce costs. These raw ma- materials combining the functionalities of the organic component, such
terials are commonly classied as conventional llers and their mixing as reactivity and exibility, with the specic properties of the inorganic
with polymers produces conventional composites. However, although material, such as chemical and thermal stability, giving rise to new
conventionally lled or reinforced polymer materials have been widely materials with high functionalities and unique properties (Bergaya and
applied in various elds, these llers are often reported to impart Lagaly, 2013; Itagaki and Kuroda, 2003).
drawbacks to the resulting materials, such as weight earning, brittle- CPN with particular thermo-mechanical and electronic properties
ness, and opacity (Pavlidou and Papaspyrides, 2008). have been synthesized by using clays or clay minerals (bentonite or
Clay polymer nanocomposites (CPN) are a new class of composites montmorillonite) as inorganic llers and applying polymerization
in which at least one dimension of the dispersed particles is in the methods such as dispersion, emulsion, and in situ bulk polymerization
nanometer range, improving the interaction with the organic matrix. (Ianchis et al., 2009; Hassan et al., 2010; Liu et al., 2014). However, less
Layered clay minerals consist of layers of one to a few nanometers attention has been paid to kaolinite, which is the most abundant natural
thickness and hundreds to thousands nanometers length, which makes clay mineral and can give rise to interesting and useful CPN. Kaolinite

Corresponding author.
E-mail address: emerson.faria@unifran.edu.br (E.H. de Faria).

Received 27 May 2017; Received in revised form 28 June 2017; Accepted 5 July 2017
Available online 13 July 2017
0169-1317/ 2017 Elsevier B.V. All rights reserved.
B.F. Ferreira et al. Applied Clay Science 146 (2017) 526534

CH3 Table 1
H3C O Basal spacing (d001) of the hybrid materials, variation of basal spacing (d) in relation to
raw kaolinite, and size of the organic molecules.
CH3 Sample d001() d() Size of isolated molecules ()a

Kaol 7.14
Kaol-DMSO 11.20 4.06 4.0
O O Kaol-HEMA 11.40 4.26 4.4
O Kaol-TMSPM 11.55 4.41 4.5
H2C O a
Size of the molecules (calculated by ChemSketch 12.0).

Fig. 1. Molecular structures for HEMA (left) and TMSPM (right).


Transmittance (%)
200 cps Kaol-HEMA 30
Kaol-HEMA 30 WT
Kaol-HEMA 120
Intensity (cps)

Kaol-HEMA 120 WT

10% Kaol
4000 3800 3600 3400 3200 3000 2800 2600
Wavenumber (cm )

10 20 30 40 50 60
2 (Degree) 10 %
Transmittance (%)

200 cps Kaol-DMSO
Kaol-TMSPM 30
Kaol-TMSPM 30 WT
Kaol-TMSPM 120
Kaol-TMSPM 120 WT
Intensity (cps)

2000 1800 1600 1400 1200 1000 800 600
Wavenumber (cm-1)
Fig. 3. FT-IR spectra of both series of solids.

10 20 30 40 50 60 molecules, that can later be substituted by other species (a host-guest

2 (Degree) displacement methodology), thus allowing to prepare functionalized
kaolinite hybrid materials containing compounds ranging from alk-
Fig. 2. Powder XRD patterns of Kaol-HEMA and Kaol-TMSPM composites after grinding
oxides to organic molecules and complexes (Bizaia et al., 2009; Arajo
in a ball milling for 30 and 120 min and washed with toluene (WT).
et al., 2014; Carvalho et al., 2014; da Silva et al., 2014; Barbosa et al.,
has attracted particular attention due to the structural features of its
(2-hydroxyethyl) methacrylate (HEMA) is a hydrosoluble monomer,
two types of interlayer surfaces, one formed by silicon-containing tet-
Fig. 1, that, under given conditions, can undergo polymerization at low
rahedral sheets and the other composed of aluminum-containing octa-
temperatures (from 20 C to + 10 C). This monomer can be used in
hedral sheets. The octahedral gibbsite-like aluminum surface contains a
the preparation of various hydrogels, for immobilization of proteins or
high density of hydroxyl groups that can be modied by intercalation
cells, and due to its biocompatibility it is widely used in Medicine, being
via reaction with organic molecules, thereby resulting in hybrid mate-
the basis for many hydrogel products such as soft contact lenses, and it
rials (Letaief et al., 2008; de Faria et al., 2010; Dedzo and Detellier,
is also applied as polymer binder for controlled drug release, adsorbent
2016). Kaolinite has been considered non-expansible for long time;
of body uids, and lubricious coatings (Hiraishi et al., 2015). The hy-
however, intercalation can be carried out using small and highly polar
droxyethyl pending species of the resulting HEMA polymer confer it

B.F. Ferreira et al. Applied Clay Science 146 (2017) 526534

Fig. 4. TEM micrographs of Kaol (top) and Kaol-HEMA and

Kaol-TMSPM derivatives (left) and after grinding by ball
milling for 30 min and washed with toluene (right).


Kaol-HEMA 30 1 m Kaol-HEMA 30 WT 1 m

1 m 1 m
Kaol-TMSPM 30 Kaol-TMSPM 30 WT

high hydrophilicity as well as good biocompatibility (Kodama et al., of glass bers in reinforced polyester composites and promotes a larger
2014; Gupta et al., 2016). Moreover, these groups can be used for number of crosslinks in acrylic type resins, thereby enhancing adhesion
complexation of various types of molecules or ions after chemical and durability of adhesives and coatings (Du and Chen, 2004).
modication or grafting. For these reasons, HEMA is perhaps the most Guo et al. have modied halloysite nanotubes with methacrylate
extensively investigated and used neutral hydrophilic monomer. groups and applied the resulting material to reinforce polyamide na-
Whereas the monomer is soluble, its homopolymer is water-insoluble nocomposites (Guo et al., 2009). This is the only paper we have found
and becomes plasticized and swollen in water. When it forms a como- related to functionalization of clay minerals similar to kaolinite. In this
nomer with other ester monomers, HEMA can be used to control hy- context, and considering that clay-polymer nanocomposites containing
drophobicity or to provide reactive sites (Di Nisio et al., 2016). On the methacrylate groups are potentially applicable in various scientic and
other hand, 3-(trimethoxysilyl)propyl methacrylate (TMSPM), Fig. 1, is technological areas, the functionalization of kaolinite with HEMA and
an organically modied alkoxide resembling rubber that is largely used TMSPM, by displacement of DMSO molecules from previously prepared
in the manufacturing and processing industry. It improves the strength kaolinite-DMSO samples, has been carried out. The materials resulting

B.F. Ferreira et al. Applied Clay Science 146 (2017) 526534

110 previously reported (De Faria et al., 2009) and its structural formula
100 100 1.0 was Si2.0Al1.96Fe0.03Mg0.01K0.02Ti0.03O7.06.
90 DTA The precursor DMSO-kaolinite was prepared according to the lit-
80 0.8
erature (Avila et al., 2010). Ka (20 g) was dispersed in a mixture of
DMSO (180 cm3) and H2O (20 cm3), and the dispersion was maintained
Mass (%)


at 60 C under agitation for 10 days. The solid was centrifuged at

0.4 2000 rpm, washed with ethanol, and oven-dried at 60 C. It was de-
noted as Kao-DMSO.
40 20
30 0.0
2.1.2. Synthesis of HEMA-kaolinite and TMSPM-kaolinite nanocomposites
0 The nanocomposite materials were obtained by mixing the pre-
-0.2 cursor (Kao-DMSO) with HEMA or TMSPM and keeping the mixture for
100 200 300 400 500 600 700 800 900
48 h at 150 C. The HEMA/Kao and TMSPM/Kao molar ratios were 5:1
Temperature (C)
(for calculating the molar mass of kaolinite, the half-cell theoretical
formula was considered, that is, its formula referred to 2 Si atoms,
100 TGA
100 1,0 Al2Si2O5(OH)4. The resulting material was washed with toluene ve
90 DTA times, oven-dried at 80 C, and designated as Kao-HEMA and Kao-
80 0,8
TMSPM, respectively. A portion of 5 g of each sample, Kao-HEMA or
Mass (%)

0,6 Kao-TMSPM, was also ground in a Pulverisette 4 planetary ball milling,

dm/dT using a 250 cm3 ZrO2 bowl, and 5 balls of 20 mm, for 30 min at


0,4 250 rpm. Also, a blank experiment was carried out for both monomers
following the procedure above described, at 150 C for 48 h, but
exo 0,2
50 20 without the presence of the precursor (Kao-DMSO); these unlled
polymers were designated as poly-HEMA and poly-TMSPM.
30 -0,2 2.1.3. In situ polymerization
200 400 600 800
The polymerization degree was measured by means of a typical in
Temperature (C)
situ polymerization experiment (Hassan et al., 2010). The free
Fig. 5. Thermal curves of KaolHEMA (top) and KaolTMSPM (bottom) solids after monomer was placed into a reaction tube together with the Kao-DMSO
grafting test, performed in O2 atmosphere. complex. The polymer formed was washed with toluene and dried at a
temperature of 80 C until constant mass was reached. The polymer
Table 2 yield or percent of HEMA or TMSPM monomer conversion (Y, %) was
Yield of polymer obtained using the monomers HEMA and TMSPM, isolated and in the
calculated by the following equation:
presence of kaolinite, at dierent temperatures.
mass of polymer
Polymerization temperature (C) Yield of polymer (%) (Y) = x100
initial mass of monomer (1)
HEMA TMSPM Kaol-HEMA Kaol-TMSPM Blank materials HEMA and TMSPM were also washed with toluene
and dried at 80 C. The yield of the polymerization process was also
25 0 0 0 0
60 0 0 8.5 5.2 calculated by means of Eq. 1.
250 84,9 71,4 88.3 88.5
2.2. Dye adsorption studies

from the reaction between molten HEMA and TMSPM and the kaolinite- The adsorption of methylene blue (MB) by both clay-polymer ma-
DMSO solids were characterized by powder X-ray diraction, thermal terials Kao-HEMA and Kao-TMSPM was studied using 50 mg of each
analysis, infrared spectroscopy, and scanning electronic microscopy. solid and 5 cm3 of dye solutions, under magnetic stirring at room
Considering the promising nature of these solids and to verify the eect temperature. The kinetics was determined using a solution of average
of the intercalation of the polymers within the kaolinite interlayer and concentration (50 mgL 1), followed by UVVis spectroscopy; equili-
adsorbed on its surface on the adsorption capacity, their application to brium times of 10 min for Kao-HEMA and 4 h for Kao-TMSPM, re-
adsorb contaminants existing in aqueous media was studied, selecting spectively, were determined. The equilibrium study was investigated
the dye methylene blue (MB) as a model molecule (Moreira et al., using the range of concentrations between 0.1 and 700 mgL 1. In
2017). Thus, the solids in powder form (after ball milling process) were order to compare the inuence of the matrix on the hybrid materials,
tested as adsorbents for methylene blue from aqueous solution by batch parent kaolinite was used in the adsorption of methylene blue, as well
method. as the polymers HEMA and TMSPM, under the same conditions.

2. Experimental 2.3. Characterization techniques

2.1. Preparation of the samples The powder X-ray diraction diagrams of the solids were recorded
in a Siemens D-500 diractometer operating at 40 kV and 30 mA
2.1.1. Synthesis of the DMSO-kaolinite precursor (1200 W), using ltered Cu K radiation in the 2 angle 2 to 65. All
The kaolin used in this study came from the municipality of So the analyses were processed at a scan speed of 2min 1.
Simo in the State of So Paulo, Brazil, and was kindly supplied by the The thermal analyses (TG/DSC) were carried out in a TA
mining company Darcy R.O. Silva & Cia. It was puried according to the Instruments SDT Q600 Simultaneous DTA-TGA thermal analyzer, from
dispersion-decantation method (Avila et al., 2010), which yielded very 25 to 900 C, at a heating rate of 10 C/min and air ow of 100 cm3/
pure kaolinite, used for further intercalation experiments. In the for- min. The instrument also provides the dierential thermogravimetric
mulation of the intercalated and grafted compounds, puried kaolinite analysis (DTG) curve of the solid analyzed.
is abbreviated as Ka. The chemical composition of this kaolinite was The FT-IR spectra were recorded in a Perkin-Elmer 1739

B.F. Ferreira et al. Applied Clay Science 146 (2017) 526534

Scheme 1. Proposed reaction pathway for the grafting and in situ polymerization of HEMA and TMSPM on kaolinite and photography of the obtained materials without grinding on ball

spectrometer using the KBr pellet technique. eective, and only ca. 3% of the layers remained non-intercalated.
Transmission electron microscopy (TEM) was performed using a Thus, the expansion of the interlayer space produced by DMSO in-
Zeiss-902 microscope over samples ground and dispersed in ethanol by corporation was 4.06 , in agreement with literature data (Castrillo
using an ultrasonic apparatus; then, a drop of the dispersion was placed et al., 2015). Further treatment with the organic molecules did not
in a Cu grid and air dried before the study. result in any signicant increase of the basal spacings, which were
The absorption spectra in the ultraviolet visible (UVVis) region of 11.45 and 11.55 after treatment with HEMA and TMSPM, respec-
the solid material and for the adsorption studies were conducted on an tively. The remaining diraction eects, namely, those not depending
Agilent HP 8453 Value UVVis Spectrophotometer. on the stacking of layers along the c-direction, were not detected be-
cause of the formation of the polymers. The basal spacing of Kao-HEMA
and Kao-TMSPM were not far from the value of 11.20 observed for
3. Results and discussion
Kao-DMSO, but enough to be distinct of it. The incorporation of these
monomers into Kao-DMSO was carried out at 150 C, which guaranteed
Kao had a basal spacing of 7.14 , which increased up to 11.20 in
the complete displacement of DMSO molecules after 48 h of reaction.
the sample treated with DMSO (Fig. 2, Table 1); intercalation was very

B.F. Ferreira et al. Applied Clay Science 146 (2017) 526534

However, signicant changes were found on comparing the dif-

fractograms from Kao-HEMA and Kao-TMSPM with those recorded for
Kao or Kao-DMSO. One of these dierences was the decrease of the
crystallinity of Kao-HEMA and Kao-TMSPM, as concluded from the
lower intensity of the maximum corresponding to the basal diraction
of the hybrid compounds as compared to Ka. The lower intensity of the
signal in the diraction diagrams of the hybrid compounds than in
those of Kao and Kao-DMSO suggested that the structure of kaolinite
somewhat decreased its crystallinity, as previously observed for ground
kaolinite (Gonzlez Jess et al., 2000; Liu et al., 2015). The loss of
crystallinity can be assigned to the disorder induced in the arrangement
of the layers by introduction of HEMA and TMSPM molecules in the
10 interlayer region, and their consequent polymerization. In fact, the
distance between the kaolinite layers was virtually the same as the
8 height of a monolayer of HEMA or TMSPM molecules, considering the
size of the monomers calculated with the aid of the free software
Kaol ChemSketch 12.0, Table 1 (http://www.acdlabs.com/download/).
6 Kaol-HEMA
qt (mg/g)

The d020 reections also underwent considerable changes, as com-

Kaol-TMSPM pared to those for the precursors Kao and Kao-DMSO. This may be at-
poly-TMSPM tributed to the exfoliation process, caused by the insertion of HEMA or
TMSPM, followed by the grinding process. During exfoliation, a la-
mella-lamella separation occurred, leading to the interaction of the
polymer with the exfoliated lamella. However, the presence in the
diractograms of the 060 reections, related to the natural structure of
0 the clay, indicated that the kaolinite structure was not modied in a,b
directions. This can be attributed to the formation of aggregates during
0 10 20 30 40 50 60
the polymerization processes, where part of the kaolinite may be ex-
Time (min) foliated, and other part may be just delaminated (Letaief et al., 2011).
Fig. 6. Kinetic study of the adsorption of MB on the dierent solids. The typical infrared absorption bands (Fig. 3 and Table S1) of in-
terlamellar hydroxyls located on octahedral layers were recorded at
45 3696, 3668, and 3653 cm 1 in the FTIR spectrum of Kao, while the
band at 3618 cm 1 corresponded to intralamellar hydroxyls. Inter-
40 calation with DMSO strongly aected these bands; two of them (3668,
and 3653 cm 1) shifted to 3538 and 3500 cm 1. Several authors have
attributed this shift to formation of hydrogen bonds between the in-
30 terlamellar hydroxyls of the clay mineral (S]OeHO) and the inter-
calated DMSO molecules. This interaction was conrmed by the shift of
the band characteristic of interlamellar AlOH groups from 938 cm 1

20 in parent kaolinite to 953 cm 1 in the Kao-DMSO solid. Bands at 2937

and 3022 cm 1 were ascribed to the CeH vibrations in DMSO (de Faria
et al., 2009).
10 Kaol The FT-IR spectra of samples Ka-HEMA and Ka-TMSPM displayed
Kaol-HEMA bands at 3699 and 3618 cm 1, characteristic of the OeH stretching
Kaol-TMSPM mode of inter- and intralamellar hydroxyls, respectively. The other two
0 poly-HEMA bands typical of intralamellar hydroxyls (3668 and 3653 cm 1) were
poly-TMSPM not detected. A broad band at 3600 cm 1 was also present in this re-
gion, being assigned to hydrogen bonding between hydroxyl groups or
0 100 200 300 400 500 600 700
adsorbed water in the hydrophilic polymers and conrming the ex-
Ce(mg.L ) foliation in the composites. Bands characteristic of methacrylate groups
Fig. 7. Equilibrium adsorption isotherms of MB on the dierent solids.
were also observed at 2993, 1728 and 1192 cm 1, attributed to CeH,
C]O, and CH3 isotactic poly(2-hydroxyethyl methacrylate), HEMA,
while the bands at 1454, 1388, and 1242 cm 1 corresponded to CH2,

Table 3
Adsorption kinetic parameters for MB onto kaolinite, the monomers, and the hybrid materials.

Samples Kinetic models

First order Pseudo second order Intraparticle diusion

q1(mgg 1) k1(min 1) R2 q2(g/(mgmin) k2(mgg 1) R2 kp (mg/(gmin1/2) C (mg/(gmin1/2) R2

Kaol 46.992 114.34 0.957 2.424 13.102 0.999 0.178 1.542 0.526
poly-HEMA 2.0580 0.4921 0.553 8.4670 2.5038 0.987 0.237 1.327 0.667
poly-TMSPM 0.3332 32.569 0.987 0.09037 0.4553 0.491 0.0379 0.0347 0.904
Kaol-HEMA 8.203 0.0525 0.769 1075.269 8.112 0.999 0,599 5.199 0.273
Kaol-TMSPM 9.199 0.0459 0.769 1351.351 9.115 0.999 0,669 5.850 0.669

B.F. Ferreira et al. Applied Clay Science 146 (2017) 526534

CH3 and CeO stretching of syndiotactic HEMA (Hassan et al., 2010), amount of silica that increased the mass of the nal residue.
strongly suggesting the polymerization of the monomer. However, the Based on the thermal analysis results, the amount of HEMA and
band typical of the interlamellar aluminol group at 938 cm 1 was TMSPM molecules per unit cell of kaolinite was quantied, the resulting
absent in the spectra of the two samples, thus conrming the con- formulae being Kao(HEMA)1.319 and Kao(TMSPM)0.524 (Kao denotes
densation of kaolinite hydroxyl groups with hydroxyl or silanol groups the half-cell of kaolinite). As observed, the total amount of HEMA units
from HEMA or TMSPM, respectively. The shift of the bands due to in- existing in the composite was higher than that of Kao-TMSPM, probably
terlamellar hydroxyls and the development of new bands corresponding because HEMA is much smaller. However, the eective degree of
to methacrylate groups evidenced the formation of methacrylate units functionalization was higher in the Kao-TMPSM sample, that is, a lower
based on HEMA and TMSPM within the interlamellar region of kaoli- amount of HEMA remains intercalated between kaolinite layers, as
nite. At The absence of bands due to S]O vibrations in the spectra of previously discussed by FTIR.
the nal solids demonstrated the total substitution of DMSO by both The yield of polymer obtained for both monomers at dierent
monomers. temperatures was evaluated for the hybrid and the blank materials
The changes caused by grafting and ball milling of kaolinite deri- (Table 2). In both cases, the yield of polymer was directly related to the
vatives were concluded from the morphological analysis of the solids reaction temperature: it was null at 25 C, low at 60 C for the hybrid
prepared by TEM (see Fig. 4). Raw kaolinite was composed of platy, materials, and null for the blank at this temperature, and very sig-
euhedral particles with typical pseudo-hexagonal morphology nicant at 150 C, mainly for the hybrid materials, reaching values
(Gardolinski and Lagaly, 2005). The samples resulting after grafting close to 90%. Comparing both monomers, although they reached si-
with HEMA or TMSPM displayed thicker particles. Kao-HEMA and Kao- milar yield of polymers at high temperatures, it seemed that HEMA
TMSPM derivatives contained disordered particles with separated clay polymerized faster at the intermediate temperature, suggesting that the
layers, thereby furnishing composites whose layers were dispersed into clay played an important role on the polymerization process, empha-
the polymer matrix. Consequently, solids with spherical and tubular sized by the fact that the yield of polymerization of TMSPM increased in
morphology were formed, shapes totally dierent from the dispersed the presence of the matrix, although this was only a preliminary result.
pseudo-hexagonal particles of pure Ka. It was not possible to determine On the basis of data previously reported for pillared bentonite clays
the platelet thickness based on these images, while the average length (Hassan et al., 2010), the various polymerization reactions that take
was about 100200 nm. The thickness seemed somewhat higher than place on the surface acidic sites of kaolinite are summarized in Scheme
for a single kaolinite platelet, which could be a consequence of the 1. Brnsted acid sites were mainly responsible for the initiation step,
tilted platelets that were obliquely inclined to the sectioned plane, as which occurred upon attack of the cloud of the monomer, whereas a
previously shown by Zsirka et al. (2015). complementary role may be played by amphoteric sites in terms of
The presence of elongated particles with a length of ~500 nm and HEMA and TMSPM organization during the propagation step. Thus,
external diameter of ~30 nm was veried, which was consistent with some cationic sites of the clay can interact with the growing monomer
the calculated minimum internal diameter for a tube comprised of a chains, forming the exfoliated polymer-clay composite. Briey, the in-
single kaolinite layer. The solids obtained after ball milling contained a itiation step generated active species from monomers. Then, the active
fraction with sizes and morphologies similar to those of ground Ka, as species interacted with non-polymerized monomers during the propa-
well as numerous spherical particles with sizes ranging from 30 to gation step, giving rise to growing chains. Next, a disproportionation
100 nm. The spherical morphology may be a consequence of the pre- process took place, with subsequent rearrangement, followed by a re-
sence of curved kaolinite layers and of the breaking of the larger initiating step and additional growth of polymeric chains. During in situ
crystals during the ball milling treatment. These spherical packets polymerization, the polymer chains penetrated into the kaolinite in-
consisted of aggregates of kaolinite with straight layers. The presence of terlayer space. Depending on the horizontal or vertical orientation and
methacrylate groups in the interlayer space of the clay essentially dispersion of the polymers, formation of intercalated, grafted, or par-
contributed to a higher degree of formation of spheroidal and nano- tially exfoliated (partially functionalized) nanocomposites was induced.
tubular particles. According to the XRD data, exfoliation of the clay in the hybrid mate-
Thermal analysis of the solids after the polymerization tests (Fig. 5) rials was not complete. However, formation of a mixture was possible,
gave evidence of four and ve consecutive mass loss steps for samples with a fraction of material still delaminated, and other fraction ex-
Kao-HEMA and Kao-TMSPM, respectively, according to the DTG curves foliated (Letaief et al., 2011).
recorded. The mass losses below 100 C (4%) in the TG curves were
assigned to the loss of weakly held surface water loss. For Kao-HEMA, 3.1. Methylene blue (MB) adsorption tests
the next mass loss showing a maximum mass loss at ca. 240 C (36%) is
attributed to removal by combustion of the polymer from the surface of The adsorption ability of Kao-TMSPM and Kao-HEMA was tested
the clay, while the mass loss between 350 and 375 C can be attributed against methylene blue (MB) solutions. In both cases, the dye con-
to removal (combustion) of the polymer located between the kaolinite centration decreases with contact time until a certain constant point
layers and functionalized onto the matrix. Kaolinite dehydroxylation was reached, and no further removal of dye from the solution occurred.
occurred at 448 C (11%), a temperature slightly lower than that re- Kinetic studies carried out using a dye concentration of 50 mgL 1
corded for pure kaolinite, suggesting that the grafting process induced a showed that the time required for reaching the equilibrium were 5 min
higher exposition of the interlayer hydroxyls. For the Kao-TMSPM solid, for both solids (Fig. 6). In order to study the inuence of the matrix on
the mass loss in the 355455 C region was attributed to removal of the the adsorption capacity, the adsorption on kaolinite and on the blank
polymer moieties on the surface of the clay and the polymer linked in compounds (poly-HEMA and poly-TMSPM) was carried under the same
the matrix. The spherical morphology acquired by the hybrid after the conditions as on the hybrid materials.
milling process (see TEM images) and the intensity of the thermal ef- The adsorption isotherms for both solids (Fig. 7) can be classied as
fects suggested that most of the polymer was dispersed onto the surface L group in Giles classication, belonging to subgroups 2 and 3 for Kao-
of the clay and the protection oered by the matrix to the polymer was HEMA and Kao-TMSPM solids, respectively (Giles and Smith, 1974).
more eective in this sample than in the Kao-HEMA solid. This agreed The inexion point in the isotherm of Kao-TMSPM suggested the
with the fact that dehydroxylation of kaolinite occurred in Kao-TMSPM complete recovery of the rst monolayer and the beginning of a second
at very high temperature, 534 C. Removal of residual carbon (coke) recovering layer of the adsorbate on the surface of this adsorbent. The
was also observed, as previously reported (de Faria et al., 2012). The adsorption capacities were 30.5 and 39.8 mg/g for Kao-HEMA and Kao-
dierences in the mass loss eects may also be due to the fact that while TMSPM, respectively, and evidenced the higher anity of Kao-TMSPM
HEMA decomposed completely, TMSPM decomposition generated an matrix for MB, and the presence in this solid of a higher number of

B.F. Ferreira et al. Applied Clay Science 146 (2017) 526534

adsorption sites. The presence of polymeric species formed upon the must work simultaneously in the control of the adsorption process in
polymerization reaction may tentatively play a positive synergistic ef- kaolinite-polymer nanocomposites.
fect on the adsorption process, although there was not enough evidence Due to the fast mass transfer eects, the shape of qt vs. t1/2 plot was
to support undoubtedly this conclusion. curved at a small time limit. All the plots had the same general feature,
an initial curved portion followed by a plateau. The initial portion was
3.2. Kinetic modeling attributed to the bulk diusion and the linear portion to the in-
traparticle diusion.
The knowledge of the adsorption kinetics is a fundamental point in
adsorption studies, constituting the rst step in the investigation and
3.3. Equilibrium modeling
providing valuable evidences of the possibility of technological appli-
cation of a given adsorbent for a particular separation. In this study, the
Both hybrid adsorbents (Kao-HEMA and Kao-TMSPM) tted well to
rst-order and the pseudo-second-order kinetic models were used to
the Freundlich model (Fig. S5), evidencing that multilayer adsorption
elucidate the adsorption mechanism. The formula for the rst-order
contributed to the interaction between MB and the kaolinite-polymer
kinetic model is given as (Lagergren, 1898):
compounds. However, Kao, HEMA and TMSPM showed typical
1 k 1 1 Langmuir ts (Fig. S5) and conrmed that a monolayer covering the
= 1 +
qt q1 t q1 (2) dye was formed onto the kaolinite surface, evidencing the similar en-
ergies between the adsorption sites. These results could explain the
where q1 and qt (mg/g) are the amounts of adsorbate adsorbed at increasing of the adsorption capacity of the hybrid materials Kao-HEMA
equilibrium and at dierent times t, respectively, and k1 (min 1) is the and Kao-TMSPM. The polymers grafted/intercalated in the interlayer
rate constant of the rst-order model for the adsorption process. Values space and on the surface promoted the increasing on adsorption sites
of k1 were calculated from the slope of the plots of 1/qt versus 1/t (Fig. with distinct energies from the raw kaolinite and induced the multilayer
S2). mechanism. The higher anity for both hybrids evidenced that similar
The pseudo-second-order kinetic model can be described by the mechanisms occurred for adsorption on Kao-HEMA and Kao-TMSPM
equation (Ho and Ofomaja, 2006): solids.
t 1 t
= +
qt (k2 q22 ) q2 (3) 4. Conclusions
where q2 (mg/g) is the maximum adsorption capacity for the pseudo-
second-order adsorption, qt (mg/g) is the amount of MB adsorbed at Two new nanocomposite materials based on 2-hydroxyethyl me-
equilibrium at time t (min) and k2 (g/(mgmin)) is the rate constant of thacrylate and 3-(trimethoxysilyl)propyl methacrylate (HEMA and
the pseudo-second-order adsorption. Values of k2 and q2 were calcu- TMSPM) monomers and layered kaolinite previously intercalated with
lated from the plot of t/qt against t (Fig. S3). DMSO were prepared by the displacement method followed by in situ
The kinetic parameters for the adsorption of MB on the hybrid polymerization. The dispersion of the inorganic nanolayers from kao-
materials and on the reference solids (Table 3) indicated that the data linite into the polymer matrix was successfully conrmed by several
tted much better to the pseudo second-order kinetic model than to the techniques. Homogeneous dispersions of completely exfoliated clay
rst-order one, evidencing that the adsorption process occurred by a nanolayers have been achieved based on HEMA-kaolinite and TMPSM-
physisorption mechanism. kaolinite materials. This was attributed to the compatibility of the clay
Moreover, the almost perfect t to the pseudo-second order model layers with polar hydroxyl groups in the polymers and also to the
enabled to propose that the interaction of each MB molecule with the breaking of layers of the clay mineral induced by the ball milling pro-
surface of Kao, TMSPM, Kao-HEMA and Kao-TMSPM involved si- cess. The use of an organosilane with a methacrylate terminated
multaneously more than one surface site. The increasing of k2 (rate polymer promoted the eective grafting of methacrylate units into the
constant) in comparison to the value determined for Ka evidenced that kaolinite interlayer space, the silanization reaction being an eective
the kaolinite-polymer nanocomposites exhibited a higher anity for route for the preparation of nanocomposites based on methacrylate
MB than the raw clay mineral. From the values calculated for the rate terminated alkoxide and kaolinite. HEMA based composites exhibited a
constant k2, it can be highlighted that the free polymers (without the higher degree of monomer incorporation into the kaolinite matrix, ca.
clay mineral), HEMA and TMSPM, had a extremely low anity for MB, 2.5 times, incorporated not only into the interlayer space, but also on
suggesting that the adsorption capacity was due to the changes induced the external surface of kaolinite layers. Preliminary adsorption studies
by the matrix on the polymerized materials. using methylene blue as test molecule revealed a higher anity of both
When the mentioned models cannot identify diusion eects, the polymer-clay nanocomposites for this dye.
intraparticle diusion model can be also used to elucidate the diusion
mechanism (Xue et al., 2011). The intraparticle diusion model is ex-
pressed as:

qt = k p t 1 2 +C (4) This work has been carried out in the frame of a SpainBrazil
Interuniversity Cooperation Grant, nanced by MEC (PHBP14/00003)
where qt (mg/g) is the amount of adsorbate adsorbed at equilibrium at and CAPES (317/15) and a Cooperation Grant jointly nanced from
time t (min), C is the zero intercept of the straight line adjusted to the Universidad de Salamanca and FAPESP (2016/50322-2). The Brazilian
experimental points when plotting qt vs t1/2, and kp (mg/(gmin1/2)) is group thanks support from Brazilian Research funding agencies FAPESP
the intraparticle diusion rate constant. Values of kp and C were cal- (2013/195233 and 2016/01501-1) and CNPq (311767/2015-0 and
culated from the plot of qt versus t1/2 (Fig. S4). In the particular case of 305398/2015-6).
both hybrid adsorbents the value of R2 was very low, evidencing that
the matrices did not adjust to this model and also that no intraparticle
diusion problems occur, except for TMSPM, which R2 was close to 0.9. Appendix A. Supplementary data
A C value dierent of zero was obtained for adsorbents Kao, Kao-
HEMA and Kao-TMSPM. Therefore, intraparticle diusion was not the Supplementary data to this article can be found online at http://dx.
determinant step of the process of mass transfer; another mechanism doi.org/10.1016/j.clay.2017.07.009.

B.F. Ferreira et al. Applied Clay Science 146 (2017) 526534

References of in-vitro release data of cisdichlorodiamminoplatinum (II) encapsulated into poly

(2-hydroxyethyl methacrylate) nanocarriers. Mater Sci Eng C Mater Biol Appl 58,
Arajo, F.R., Baptista, J.G., Maral, L., Ciu, K.J., Nassar, E.J., Cale, P.S., Vicente, Hassan, S.A., Yehia, F.Z., Hassan, H.A., Sadek, S.A., Darwish, A.S., 2010. Various char-
M.A., Trujillano, R., Rives, V., Gil, A., Korili, S.A., de Faria, E.H., 2014. Versatile acteristics and catalytic performance of iron (II) phthalocyanine immobilized onto
heterogeneous dipicolinate complexes grafted into kaolinite: catalytic oxidation of titania- and vanadia-pillared bentonite clay in in-situ polymerization of methyl me-
hydrocarbons and degradation of dyes. Catal. Today 227, 105115. thacrylate - an attempt to synthesize novel polymer/iron phthalocyanine/pillared
Avila, L.R., de Faria, E.H., Ciu, K.J., Nassar, E.J., Cale, P.S., Vicente, M.A., Trujillano, clay nanocomposites. J. Mol. Catal. A-Chem. 332, 93105.
R., 2010. New synthesis strategies for eective functionalization of kaolinite and Hiraishi, N., Tochio, N., Kigawa, T., Otsuki, M., Tagami, J., 2015. Molecular level eva-
saponite with silylating agents. J. Colloid Interface Sci. 341, 186193. luation on HEMA interaction with a collagen model. Dent. Mater. 31, 8892.
Barbosa, L.V., Maral, L., Nassar, E.J., Cale, P.S., Vicente, M.A., Trujillano, R., Rives, V., Ho, Y., Ofomaja, A.E., 2006. Pseudo-second-order model for lead ion sorption from
Gil, A., Korili, S.A., Ciu, K.J., Faria, E.H., 2015. Kaolinite-titanium oxide nano- aqueous solutions onto palm kernel ber. J. Hazard. Mater. 129, 137142.
composites prepared via sol-gel as heterogeneous photocatalysts for dyes degrada- Ianchis, R., Donescu, D., Petcu, C., Ghiurea, M., Anghel, D.F., Stanga, G., Marcu, A., 2009.
tion. Catal. Today 246, 133142. Surfactant-free emulsion polymerization of styrene in the presence of silylated
Bergaya, F., Lagaly, G., 2013. Handbook of Clay Science, second edition. Elsevier. montmorillonite. Appl. Clay Sci. 45, 164170.
Bizaia, N., Faria, E.H., Ricci, G.P., Cale, P.S., Nassar, E.J., Castro, K.A.D.F., Nakagaki, S., Itagaki, T., Kuroda, K., 2003. Organic modication of the interlayer surface of kaolinite
Ciu, K.J., Trujillano, R., Vicente, M.A., Gil, A., Korili, S.A., 2009. Porphyrin-kao- with propanediols by transesterication. J. Mater. Chem. 13, 10641068.
linite as ecient catalyst for oxidation reactions. ACS Appl. Mater. Interfaces 11, Kodama, Y., Barsbay, M., Gven, O., 2014. Poly(2-hydroxyethylmethacrylate) (PHEMA)
26672678. grafted polyethylene/polypropylene (PE/PP) nonwoven fabric by -initiation:
Carvalho, A.L., Ferreira, B.F., Martins, C.H.G., Nassar, E.J., Nakagaki, S., Machado, G.S., synthesis, characterization and benets of RAFT mediation. Radiat. Phys. Chem. 105,
Rives, V., Trujillano, R., Vicente, M.A., Gil, A., Korili, S.A., de Faria, E.H., Ciu, K.J., 3138.
2014. Tetracarboxyphenylporphyrin kaolinite hybrid materials as ecient cata- Kotal, M., Bhowmick, A.K., 2015. Polymer nanocomposites from modied clays: recent
lysts and antibacterial agents. J. Phys. Chem. C 118, 2456224574. advances and challenge. Prog. Polym. Sci. 51, 127187.
Castrillo, P.D., Olmos, D., Gonzlez-Benito, J., 2015. Kinetic study of the intercalation Lagergren, S., 1898. About the theory of so-called adsorption of soluble substances. K.
process of dimethylsulfoxide in kaolinite. Int. J. Miner. Process. 144, 7074. Kungl. Svenska Vetenskapsakademiens Handlingar. 24, 139.
Dedzo, G.K., Detellier, C., 2016. Functional nanohybrid materials derived from kaolinite. Letaief, S., Tonle, I.K., Diaco, T., Detellier, C., 2008. Nanohybrid materials from interlayer
Appl. Clay Sci. 130, 3339. functionalization of kaolinite. Application to the electrochemical preconcentration of
Di Nisio, C., D'Aurora, M., di Giacomo, V., Stuppia, L., Cataldi, A., Gatta, V., 2016. cyanide. Appl. Clay Sci. 42, 95101.
Transcriptome modications in human gingival broblasts exposed to 2-hydro- Letaief, S., Liu, Y., Detellier, C., 2011. Single kaolinite nanometer layers prepared by an in
xyethyl methacrylate. Gene 582, 3846. situ polymerization exfoliation process in the presence of ionic liquids. Langmuir
Du, J., Chen, Y., 2004. Atom-transfer radical polymerization of a reactive monomer: 3- 27, 1524815254.
(trimethoxysilyl)propyl methacrylate. Macromolecules 37, 63226328. Liu, P., Zhu, L., Guo, J., Wang, A., Zhao, Y., Wang, Z., 2014. Palygorskite/polystyrene
de Faria, E.H., Lima, O.J., Ciu, K.J., Nassar, E.J., Vicente, M.A., Trujillano, R., Cale, nanocomposites via facile in-situ bulk polymerization: gelation and thermal proper-
P.S., 2009. Hybrid materials prepared by interlayer functionalization of kaolinite ties. Appl. Clay Sci. 100, 95101.
with pyridine-carboxylic acids. J. Colloid Interface Sci. 335, 210215. Liu, Q., Li, X., Cheng, H., 2015. Insight into the self-adaptive deformation of kaolinite
de Faria, E.H., Ciu, K.J., Nassar, E.J., Vicente, M.A., Trujillano, R., Cale, P.S., 2010. layers into nanoscrolls. J. Colloid Interface Sci. 450, 361365.
Novel reactive amino-compound: tris(hydroxymethyl)aminomethane covalently Moreira, M.A., Ciu, K.J., Rives, V., Vicente, M.A., Trujillano, R., Gil, A., Korili, S.A., de
grafted on kaolinite. Appl. Clay Sci. 48, 516521. Faria, E.H., 2017. Eect of chemical modication of palygorskite and sepiolite by 3-
de Faria, E.H., Ricci, G.P., Maral, L., Nassar, E.J., Vicente, M.A., Trujillano, R., Gil, A., aminopropyltriethoxisilane on adsorption of cationic and anionic dyes. Appl. Clay
Korili, S.A., Ciu, K.J., Cale, P.S., 2012. Green and selective oxidation reactions Sci. 135, 394404.
catalyzed by kaolinite covalently grafted with Fe(III) pyridine-carboxylate com- Pavlidou, S., Papaspyrides, C.D., 2008. A review on polymerlayered silicate nano-
plexes. Catal. Today 187, 135149. composites. Prog. Polym. Sci. 33, 11191198.
Gardolinski, J.E.F.C., Lagaly, G., 2005. Grafted organic derivatives of kaolinite: I. da Silva, T.H., de Souza, T.F.M., Ribeiro, A.O., Ciu, K.J., Nassar, E.J., Silva, M.L.A., de
Synthesis, chemical and rheological characterization. Clay Miner. 40, 537546. Faria, E.H., Cale, P.S., 2014. Immobilization of metallophthalocyanines on hybrid
Giles, C.H., Smith, D., 1974. A general treatment and classication of the solute ad- materials and in-situ synthesis of pseudo-tubular structures from an aminofunctio-
sorption isotherm - I. Theoretical. J. Colloid Interface Sci. 47, 755765. nalized kaolinite. Dyes Pigments 100, 1723.
Gonzlez Jess, J., Huerta, F.J., Linares, J., Ruiz Cruz, M.D., 2000. Textural and structural Xue, A., Zhou, S., Zhao, Y., Lu, X., Han, P., 2011. Eective NH2-grafting on attapulgite
transformations of kaolinites in aqueous solutions at 200 C. Appl. Clay Sci. 17, surfaces for adsorption of reactive dyes. J. Hazard. Mater. 194, 714.
245263. Zsirka, B., Horvth, E., Mak, ., Kurdi, R., Kristf, J., 2015. Preparation and char-
Guo, B., Zou, Q., Lei, Y., Jia, D., 2009. Structure and performance of polyamide 6/hal- acterization of kaolinite nanostructures: reaction pathways, morphology and struc-
loysite nanotubes nanocomposites. Polym. J. 41, 835842. tural order. Clay Miner. 50, 329340.
Gupta, M.K., Bajpai, J., Bajpai, A.K., 2016. Optimizing the release process and modelling