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Journal of Food Engineering 110 (2012) 262268

Contents lists available at ScienceDirect

Journal of Food Engineering


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

Modication of cellulose acetate lms using nanollers based on organoclays


Francisco J. Rodrguez , Mara J. Galotto, Abel Guarda, Julio E. Bruna
Center for the Development of Nanoscience and Nanotechnology (CEDENNA), Food Packaging Laboratory (Laben-Chile), Department of Food Science and
Technology, Faculty of Technology, University of Santiago de Chile (USACH), Santiago, Chile

a r t i c l e

i n f o

Article history:
Available online 11 May 2011
Keywords:
Cellulose acetate
Montmorillonite
Organoclay
Nanocomposites

a b s t r a c t
The present work has been oriented on the development of cellulose acetate lms with nanollers of
montmorillonite/alkylammonium (hexa- and tetra-decyltrimethylammonium) and montmorillonite/
chitosan which have been synthesized using a cationic exchange process. All synthesized organoclays
have been characterized using X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Fourier
transform infrared spectroscopy (FTIR). These analyses conrmed the modication of clay structures
which proved to be dependent on the chemical structure of chosen organic precursor. On the other hand,
the different organoclays have been used to produce cellulose acetate nanocomposites by solvent-casting
technique. The nanocomposite lms have been characterized by XRD, TGA, Differential scanning calorimetry (DSC), oxygen and water vapor permeability and scanning electronic microscopy (SEM). All nanocomposites obtained showed the intercalation of polymer inside the clay structure and an important
reduction of oxygen transmission rate (OTR) compared to cellulose acetate lms without nanollers.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Plastic materials derived from petroleum become indispensable
materials to our society. Excellent mechanical performance, versatility, lightness, durability, low cost, and easy processing, are some
important properties of these materials. Because of this, consumption of these materials has grown considerably in recent decades.
One of the industries in which the impact of plastic materials has become decisive is the food packaging industry. Thus, thermoplastic
like polyolens (polyethylene, PE, polypropylene, and PP), polyethylen terephthalate (PET), polivinyl chloride (PVC), and poliamides are
the most used by this industry (Marsh and Bugusu, 2007).
Despite of advantages offered by traditional plastic materials a
serious problem has risen in recent years. Due to excessive consumption of these materials a massive accumulation of plastic waste has
been disposed in the environment. Considering the poor degradation
of traditional plastics in the environment, they have been classied as
highly polluting agents. To avoid this negative impact, the European
Union is promoting different strategies to confront this problem.
According to the European Directive on Packaging and Packaging
Waste the management of packaging and packaging waste should include as a rst priority the prevention of packaging waste and, as
additional fundamental principles, reuse of packaging, recycling
and other forms of recovering packaging waste which allow reducing
of the nal disposal of such wastes. However, so far these measures
Corresponding author. Address: Obispo Manuel Umaa 050 (9170201), Edicio
de Alimentos, Estacin Central, Santiago, Chile. Tel.: +56 2 7184520.
E-mail address: francisco.rodriguez.m@usach.cl (F.J. Rodrguez).
0260-8774/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2011.05.004

have failed to reduce signicantly the amount of wastes (Rudnik,


2008). Thus, the use of natural polymers has emerged as an alternative to face up to this problem. Nevertheless, properties such as high
permeability to gases, poor mechanical properties, and low melt viscosity, have restricted their use in a wide range of applications.
Regarding to this, technologies oriented to modify properties of natural polymers has been of great interest in the materials eld. In view
of the success of nanotechnology application on the use of nanollers
to modify the properties of traditional polymeric materials (Ray and
Okamoto, 2003), nanocomposites based on natural polymers have
been considered as the next generation of eco-friendly materials
(Darder et al., 2003). Therefore, it has been suggested that a major
application of this bio-nanocomposites will be in the development
of new food packaging systems (Sozer and Kokini, 2009).
According to nanocomposites preparation, nanoparticles used
as llers or additives in polymers for various desired effects are
receiving an increased interest for research and development. So,
nanoparticles like carbon nanotubes (CNTs), clays and metal oxides
have been used to modify the polymer performance (Esawi et al.,
2010; Vladuta et al., 2009; Wang and Guo, 2010). Concerning clays,
montmorillonite (MMT) has been the most commonly employed
clay mineral in the preparation of polymer composites (Hasegawa
et al., 2003; Morawiec et al., 2005). To ensure good compatibility
between the polymer and montmorillonite in composites, this layered silicate has been modied with quaternary ammonium or
phosphorous salts with long alkyl chains to produce organoclays
(Patel et al., 2005; Yang et al., 2007). It has been recognized that
the intercalation of an organic surfactant between the clay layers
is required in order to change the intergallery structure and to

263

F.J. Rodrguez et al. / Journal of Food Engineering 110 (2012) 262268

increase the distance between the layers (Paul et al., 2005). In this
way, the organoclays favor the nanoparticlepolymer interaction.
Considering cellulose as the most abundant natural polymer, its
application in the plastic area is attracting interest as a substitute
for traditional plastics. Studies applied to cellulose are centered
on cellulose derivates because these present better processability
than pure cellulose. Within cellulosic derivates, cellulose acetate
(CA) is of particular interest because it is a biodegradable polymer
and has excellent optical clarity and high toughness, therefore this
cellulose derivate can produce lms either by solvent-casting
(Meier et al., 2004) or melting techniques (Mohanty et al., 2003).
Studies oriented to develop nanocomposites from cellulose acetate are limited. Park et al. reported the effect of a compatibilizer
(Park et al., 2004a) and plasticizer (Park et al., 2004b) on the nanocomposite formation using a commercial organoclay by a melt process. In these studies, it has been observed an important reduction
of water vapor permeability (WVP) according to clay and plasticizer content; therefore, the addition of compatibilizer based on
maleic anhydride grafted cellulose acetate butyrate (CAB-g-MA) allowed to produce the clay exfoliation which was attributed to better interaction between CA and organoclay. Wibowo et al. (2006)
used cellulose acetate, triethyl citrate and organically modied
clay nanollers to produce a intercalated nanocomposite which
showed important changes on the mechanical properties. Recently,
Varsha et al. (2010) also reported the decrease of WVP of cellulose
acetate lms using ller based on nanosilver.
The aim of the present study is the development of organoclays
from different cationic organic components using an ionic interchange process and the assessment of the effect of these organoclays on the nanocomposites properties based on cellulose acetate.
2. Experimental
2.1. Materials
Montmorillonite (CloisiteNa+) with a cationic exchange capacity (CEC) of 92.7 meq/100 g and Cloisite30B were obtained from

Southern Clay Products Inc. Hexadecyltrimethylammonium bromide (P97%) and tetradecyltrimethylammonium bromide (99%)
were supplied by Merck and Sigma, respectively. Chitosan, low
molecular weight (7585% deacetylated) and Cellulose Acetate
(39.8 wt.% acetyl content. Mn ca. 30,000) were supplied by Aldrich.
2.2. Modication of montmorillonite: preparation of organoclays
(OMMT)
MMT (5.0 g) was dispersed in 150 mL of distilled water and
stirred with a magnetic stirrer for 1 h at 60 C. The suspension
was then underwent an ultrasonic treatment (Elmasonic bath
S60H, 50 Hz) for 30 min at 60 C. Alkyltrimethylammonium bromide (1.5 CEC) was dissolved in 50 mL of distilled water and added
to clay suspension. The suspension obtained was stirred for 1 h at
60 C and placed inside of ultrasonic bath for 30 min at 60 C. The
solid phase was ltered, washed with distilled water and ethanol
and dried at 70 C for 12 h. The organoclay was puried by means
of Soxhlet extraction using ethanol as solvent during 3 h. Afterward the puried solid was dried at 70 C for 12 h. Finally, the
organoclay was ground in an analytical mill (Cole Parmer 430102, 20,000 rpm) and the fraction under #200 Tyler screen
(75 lm) selected.
Preparation of organoclays from chitosan was similar to the
alkyltrimethylammonium. However, in this case it was necessary
rst to determine the charge capacity of chitosan (meq NH2/g
chitosan) to determine the appropriate quantity of this biopolymer
to modify the structure of montmorillonite according to the CEC
value of this. Thus, the charge capacity of chitosan was determined
by means of a potentiometric titration (Jiang et al., 2003). Basically
this method is oriented to the determination of the deacetylation
degree of chitosan through acidbase titration of protonated amino
group from polymer using a standardized NaOH solution; however,
it also allows to determine the equivalents of amino group per
gram of chitosan. Unlike the alkyltrimethylammonium/MMT, the
chitosan quantity corresponding to 1.0 CEC of clay (0.89 g) was dissolved in an acetic acid solution (2 v/v%).

(e)
(d)

16371536
3635 3435

Transmittance, %

1034

(c)

3434
3631

1637
1475

2850
2927

1036
3434
3633

(b)

1637
1477

2852
2927

1036
3410
3635

1637
1469

2852
2927

(a)
1036
1641

3434
3635

1051

4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber, cm

Fig. 1. Fourier transform infrared spectra of (a) montmorillonite (MMT), (b) Cloisite30B, (c) C14OMMT, (d) C16OMMT, and (e) ChOMMT.

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F.J. Rodrguez et al. / Journal of Food Engineering 110 (2012) 262268

Table 1
Results of the TGA of organoclays.

Step 1
Mass loss (%)
Temperature (C)a
Step 2
Mass loss (%)
Temperature (C)a
Step 3
Mass loss (%)
Temperature (C)a
a

MMT

Cloisite30B

C14OMMT

C16OMMT

ChOMMT

7.2
88

2.1
55

2.0
107

1.8
96

7.0
106

14.2
282 and 354

15.6
289 and 436

18.6
300 and 441

8.9
267

3.4
682

9.6
622

7.8
674

6.4
682

9.6
655

Process
Dehydration

Decomposition of organic component

Dehydroxilation

Obtained from the rst derivative of the TGA curve.

2.3. Preparation of cellulose acetate/OMMT nanocomposites


Nanocomposites were prepared by means of casting technique
using acetone as solvent. All nanocomposites consisted of 5 wt.%
of OMMT. 10 g of cellulose acetate were dissolved in 150 mL of
acetone under vigorous stirring for 1 h at ambient temperature.
0.53 g of OMMT was dispersed in 50 mL of acetone and sonicated
for 30 min at room temperature. Then, the cellulose acetate solution was added on organoclay suspension under vigorous stirring.
This mixture was stirred during 60 min and then sonicated during
30 min at room temperature. After that the mixture was added on
Petri disk and dried at 40 C in oven for 4 h. Finally, the lms were
removed from the glass disk and stored in polyethylene bags to
avoid contamination.
2.4. Characterization of organoclays and nanocomposites
2.4.1. Fourier transform infrared (FTIR)
This spectroscopic analysis was carried out in a Bruker IFS 66 V
spectrometer. MMT and OMMT were crushed and blended with
KBr. Spectra were taken with 4 cm1 resolution in a wave-number
range from 4000 to 400 cm1 with 32 scans.
2.4.2. Thermogravimetric analysis (TGA)
This thermal analysis was performed on a SDT 2960 DSC-TGA
instrument (TA Instruments) at a heating rate of 20 C/min from

room temperature to 850 C. All analyses were performed under


a ow of air.

2.4.3. Differential scanning calorimetry (DSC)


Differential scanning calorimetry analyses were conducted with
a Mettler DSC-822e calorimeter. Samples were heated from 25 C
to 300 C at a rate of 10 C/min. The sample weight was about
8 mg. All experiments were carried out under the purge of dry
nitrogen.

2.4.4. X-ray diffraction (XRD)


XRD analysis was carried out in a Siemens Diffractometer
D5000 (30 mA and 40 kv) using CuKa (k = 1.54 ) radiation at room
temperature. All scans were performed in a 2h range 210 at
0.02/seg.

2.4.5. Oxygen transmission rate (OTR)


The OTR of lms was determined with an Oxygen Permeation
Analyzer (MOCON OX-TRAN MS2/20), equipped with a Coulox
oxygen sensor with a sensitivity of 0.1 [cc/(m2 day atm)]. Measurements were carried out at 23 C and 0% RH until a steady-state oxygen transmission rate was achieved. Output values were expressed
as the oxygen transmission rate in [cc/(m2 day)].

(f) 3,11 nm

1,65 nm
1,32 nm

(e)

2,16 nm

1,80 nm

(e)
Intensity (a.u)

Intensity (a.u)

(d)

1,76 nm

(c)
(b)

2,15 nm

(d)
2,20 nm

(c)

1,85 nm
1,26 nm

(b)
1,18 nm

(a)
2

(a)
10

2theta (degree)
Fig. 2. X-ray diffraction pattern of (a) MMT, (b) Cloisite30B, (c) C14OMMT, (d)
C16OMMT, and (e) ChOMMT.

10

2 theta (degree)
Fig. 3. X-ray diffraction pattern of (a) cellulose acetate (CA), (b) CA + MMT, (c)
CA + Cloisite30B, (d) CA + C14OMMT, (e) CA + C16OMMT, and (f) CA + ChOMMT.

265

F.J. Rodrguez et al. / Journal of Food Engineering 110 (2012) 262268

2.4.7. Scanning electronic microscopy (SEM)


The SEM micrographs of nanocomposites lms were obtained
from an JSM-5410 Jeol Scanning Microscope with accelerating voltage at 10 kV. Samples were coated with gold palladium using a
Sputtering System Hummer 6.2. To the cross-section analysis, the
samples were previously fractured under liquid nitrogen.
3. Results and discussion
3.1. Organoclay characterization
Fig. 1 shows the FTIR spectra of different organoclays synthesized, a commercial organoclay (Cloisite30B) and montmorillonite
(CloisiteNa+). The organoclays synthesized from alkyltrimethylammonium bromides showed similar bands to those of commercial
organoclay, a clay modied with methyl, tallow (65% C18, 30%
C16 and C14), bis-2-hidroxyethyl, quaternary ammonium chloride. The exclusive bands observed between 30002800 cm1
(CH2 stretching band) and 14801450 cm1 (CH2 bending
Table 2
Results of DSC and TGA of nanocomposite lms.
Sample

CA
CA + Cloisite30B
CA + C14OMMT
CA + C16OMMT
CA + ChOMMT

TGA
Tm
(C)a

D Hf
(Jg1)a

TStep1b

TStep2b

TStep3b

182
173
180
178
184

216
206
215
214
216

1.90
1.29
1.91
1.88
1.67

55
86
98
86
9

371
381
377
377
376

550
610
612
598
568

Obtained from second scan of the DSC thermogram.


Obtained from the rst derivative of the TGA curve.

OTR
WVTR

1200

1200

1000

1000

800

800

600

600

400

400

200

200

OTR (cm /m day)

a
b

DSC
Tg
(C)a

band) to Cloisite30B, hexadecyltrimethylammonium/MMT (C16


OMMT) and tetradecyltrimethylammonium/MMT (C14OMMT)
conrmed the presence of the long alkyl chain of ammonium surfactant (Vazquez et al., 2008; Zhao et al., 2003). On the other hand, the
spectrum of organoclay from chitosan/MMT (ChOMMT) showed a
signal at 1536 cm1 which has been assigned to the deformation
of the protonated amine group from polysaccharide (NH
3 ) (Darder
et al., 2003). The rest of signals from different organoclays are
according with vibrational band characteristic of the silicate minerals, such as, 3630 cm1 (AlOH stretching), 3430 cm1 (OH
stretching from interlayer water), 1640 cm1 (OH bending from
absorbed water), 1050 cm1 (SiO stretching) (Patel et al., 2005;
Yang et al., 2007).
The presence of organic component in clay was also determined
by means of a thermogravimetric analysis (TGA). Results of TGA
analysis are resumed at Table 1. MMT, C14OMMT, C16OMMT and
ChOMMT showed a dehydration process under 200 C (Xie et al.,
2001a) and dehydroxylation of the aluminosilicate from 620
680 C (Xie et al., 2002). Water elimination was more important
for MMT and ChOMMT because the most hydrophilic character
compared with other organoclays where the organic ammonium
component is characterized by a high hydrophobic character.
Regarding commercial organoclay (Cloisite30B) a mass loss of
2.1% was observed at 55 C. This process is observed in the dehydration zone; however, it could also be attributed not only to the dehydration process, but also to other solvent which could be used to
synthesize the commercial organoclay. Therefore, all organoclays
presented an organic material decomposition zone between 200
500 C which evidenced the presence of organic component in the
clay structure (Xie et al., 2001b). In DTG, multiple peaks were observed in Cloisite30B, C14OMMT and C16OMMT. These peaks
have been assigned to decomposition process of different types of
bonding of surfactant molecules in the organoclay (Xi et al.,
2005). On the other hand, the ChOMMT organoclay showed a
decomposition process at 267 C which has been assigned to degradation and deacetylation of chitosan (Wang et al., 2005). Therefore,
the ChOMMT presented the lowest incorporation of organic component (8.9 wt.%). This result could be explained due to steric hindrance of chitosan which difcults its incorporation inside the
clay structure.

WVTR (g/m day)

2.4.6. Water vapor transmission rate (WVTR)


The WVTR of each tested lm was determined using a MOCON
Permatran W 3/31 Tester. Measurements were carried out at
37.8 C and 100% RH until a steady-state water vapor transmission
rate. An infrared detector was used for quantication of the WVTR
in the lm. Output values were expressed as water vapor transmission rate in [g/(m2 day)].

0
CA

B
30
te
si
oi
l
+C
CA

T
M
M
O
14
+
CA

T
M
M
O
16
+
CA

T
M
M
O
Ch
+
CA

Sample
Fig. 4. Effect of nanollers on oxygen and water vapor transmission rate of different lms.

266

F.J. Rodrguez et al. / Journal of Food Engineering 110 (2012) 262268

At difference of TGA and FTIR analysis, the X-ray diffraction


(XRD) is the most important analysis to determine the incorporation of organic component inside of interlayer zone in the clay.
According to XRD results (Fig. 2), all synthesized organoclays
showed an important shifted of d001 (d-spacing) characteristic peak
of montmorillonite (2h = 7.50) to lowest 2h values. This effect is
produced by the larger size of cationic organic component than sodium cation present in unmodied clay. Therefore, the interlayer
distance in organoclays modied with quaternary ammonium ions
increased according to the length of alkylic chain of surfactant.
Thus the interlayer distance to these organoclays increased in order: C14OMMT (1.76 nm) < C16OMMT (1.80 nm) < Cloisite30B
(1.85 nm). These results are in good agreement with molecular
dynamics simulations performed by Zeng and Yu (2008). About
ChOMMT an increase of interlayer distance was also observed,
however, the XRD pattern showed an irregular distribution with
at least two maximums. Similar behavior was reported in the preparation of chitosan nanocomposites by Darder et al. (2003). This effect could be explained due to polymeric nature of chitosan which
would produce different dispositions of polymer chain inside of
interlayer zone with a broad interlayer distance distribution in
contrast with small molecules such as surfactants.

the thermal stability of cellulose acetate is slightly increased by


the presence of organoclay in the system which is according with
a nanocomposites properties (Pavlidoua and Papaspyrides, 2008).

3.2. Nanocomposites characterization


Films of cellulose acetate nanocomposites were obtained by
means of solvent-casting technique using a 5 wt.% of each organoclay. Cellulose acetate lms are characterized by a high transparency; however, the incorporation of a low content of nanoller
signicantly affected this property.
To evaluate the type of nanocomposites obtained, the lms
were analyzed by XRD (Fig. 3). All nanocomposites showed a d001
diffraction plane which was shifted to lower 2h value respect to
the corresponding organoclay. These results conrmed that cellulose acetate has been intercalated inside the clay structure; however, this intercalation was more important to ChOMMT. This
effect could be due to a greater afnity between cellulose acetate
and chitosan (Liu and Bai, 2005). In contrast, lms fabricated with
cellulose acetate and pure montmorillonite presented a slight
shifted of the d001 signal. Thus, these results conrmed the importance of using modied clays to produce nanocomposites.
The nanocomposite lms from cellulose acetate were also analyzed by differential scanning calorimetry and thermogravimetric
analysis (Table 2).
Regarding DSC analysis, the cellulose acetate without nanoller
shows a Tg value of 182 C and Tm value of 216 C which is consistent with other studies (Lui et al., 1999). Nanocomposites based on
Cloisite30B showed the greatest decrease in Tg, Tm and fusion enthalpy respect to other nanocomposites. This effect could be explained by the presence of organic component with alcoholic
groups (2-hidroxyethyl) inside of polymer structure which could
be acting as a plastizicer agent decreasing the Tg value and hindering the polymer cristalization. This alcoholic component would be
released by the introduction of cellulose acetate chains in the
organoclay structure. In addition, no changes in the shape of the
melting points of cellulose acetate in presence of the different
organoclays were observed, changes that could evidence a nucleating effect on the crystallization process. On the other hand, thermogravimetric analysis showed three processes where mass
losses were observed which are in concordance with other reported studies (Arthanareeswaran et al., 2004). The rst process
ocurrs at a temperatures lower than 100 C and it represents the
loss of water. The second process corresponding to the main thermal degradation of cellulose acetate chains (370 C) and the last
one is identied as the carbonization of the degradaded products
to ash at 550 C. This thermal analysis allowed to observe that

Fig. 5. Scanning electronic microscopy analysis of the cross-sections (left) and


surface (right) of the different nanocomposites from cellulose acetate. 9a) CA, (b)
CA + Cloisite30B, (c) CA + C14OMMT, (d) CA + C16OMMT, and (e) CA + ChOMMT.

F.J. Rodrguez et al. / Journal of Food Engineering 110 (2012) 262268

It has been well accepted that clays favors the char formation
which hinders the out-diffusion of the volatile decompositon products, as a direct result of the decrease in permeability of nanocomposite (Leszczynska et al., 2007).
The effect of clay on the nanocomposites permeability was
determined for both oxygen and water vapor by means of oxygen
and water vapor transmission rate determination, respectively
(Fig. 4). All nanocomposites showed an important reduction of
OTR value compared with cellulose acetate alone; however, this
reduction was not dependent on the intercalation degree of polymer inside of clay structure. The effect of layered silicates on gas
permeability has mainly been attributed to its high aspect ratio.
These properties facilities the generation of a tortuos path which
produces an increase of path length for permeating solute molecules enhancing the barrier properties of nanocomposites (Solovyov and Goldmen, 2008). On the other hand, the effect of clay
on WVTR was not signicant. Here, the high water anity of cellulose acetate by water would be more important than the barrier effect of layered silicate.
Finally, the different lms from nanocomposites were analyzed
by SEM (cross-section and lm surface). Fig. 5 (left) shows SEM
micrographs of the cross-section of different lms. All samples presented a homogenuos structure without an important presence of
pores on the lm structure as other studies based on cellulose acetate (Gemili et al., 2009). This fact would explain that the permeability process is controled by difusion rather a capillarity
mechanism in these lms. Fig. 5 (right) shows the SEM micrographs of surface of lms. Here it was possible to observe important differences between nanocomposites and cellulose acetate
alone; the presence of organoclay modied the surface texture
what was more important for organoclays with higher molecular
weight of organic component.
4. Conclusion
It was possible to obtain different organoclays by means of
an interchange process between montmorillonite and alkyl
ammonium salts or chitosan. The modication of layered silicate
was dependent on the molecular weight of different organic
additives.
On the other hand, the preparation of lms using solvent-casting techniques allowed the polymer intercalation inside of layered
structure of montmorillonite. Regarding to the intercalation process was conrmed the importance of organoclays to produce
nanocomposites. Therefore, the highest level of intercalation was
observed to organoclays modied with chitosan. Concerning the
properties of nanocomposites, all of them showed an important
decrease of oxygen transmission rate but not water vapor. Microscopic analysis evidenced a non-porous structure of cellulose acetate nanocomposites which explain that the permeability process
is controlled by a diffusion process rather a capillary mechanism.
Finally, the hybrid structures present a slight effect on the thermal
decomposition of cellulose acetate.
Acknowledgements
The authors thank to Comisin Nacional de Investigacin
Cientca y Tecnolgica, CONICYT, for the nancial support from
Programa Bicentenario de Ciencia y Tecnologa (Project PDA-22)
and Programa de Financiamiento Basal para Centros Cientcos y
Tecnolgicos de Excelencia (Project FB0807). To Departamento de
Investigaciones Cientcas y Tecnolgicas, Universidad de Santiago
de Chile, DICYT-USACH (Project 080971RM). Finally, the authors
thanks to Southern Clay Products by donation of CloisiteNa+ and
Cloisite30B.

267

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