Materials Research Bulletin 47 (2012) 23362343

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Materials Research Bulletin

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Polymer/organosilica nanocomposites based on polyimide with benzimidazole

linkages and reactive organoclay containing isoleucine amino acid: Synthesis,
characterization and morphology properties
Shadpour Mallakpour a,b,*, Mohammad Dinari a
a
b

Organic Polymer Chemistry Research Laboratory, Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Islamic Republic of Iran
Nanotechnology and Advanced Materials Institute, Isfahan University of Technology, Isfahan 84156-83111, Islamic Republic of Iran

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 1 September 2011
Received in revised form 1 May 2012
Accepted 21 May 2012
Available online 30 May 2012

Polyimidesilica nanocomposites are attractive hybrid architectures that possess excellent mechanical,
thermal and chemical properties. But, the dispersion of inorganic domains in the polymer matrix and the
compatibility between the organic and inorganic phases are critical factors in these hybrid systems. In
this investigation, a reactive organoclay was prepared via ion exchange reaction between protonated
form of difunctional L-isoleucine amino acid as a swelling agent and Cloisite Na+ montmorillonite. Amine
functional groups of this swelling agent formed an ionic bond with the negatively charged silicates,
whereas the remaining acid functional groups were available for further interaction with polymer
chains. Then organo-soluble polyimide (PI) have been successfully synthesized from the reaction of 2(3,5-diaminophenyl)-benzimidazole and pyromellitic dianhydride in N,N-dimethylacetamide. Finally,
PI/organoclay nanocomposite lms enclosing 1%, 3%, 5%, 7% and 10% of synthesized organoclay were
successfully prepared by an in situ polymerization reaction through thermal imidization. The
synthesized hybrid materials were subsequently characterized by Fourier transform infrared
spectroscopy, X-ray diffraction, electron microscopy, and thermogravimetric analysis techniques. The
PI/organoclay nanocomposite lms have good optical transparencies and the mechanical properties
were substantially improved by the incorporation of the reactive organoclay.
2012 Elsevier Ltd. All rights reserved.

Keywords:
A. Composites
A. Nanostructures
B. Chemical synthesis
C. Electron microscopy
C. Thermogravimetric analysis (TGA)

1. Introduction
Rising claim for higher performance devices with smaller size,
lighter weight, and better quality, make polyimide (PI)s as a unique
substance in response to technological applications in a variety of
elds such as aerospace, automobile and microelectronic [1,2].
Among a large number of PIs which have been so far studied from
both academic and industrial viewpoints, aromatic PIs are the most
reliable heat-resistant polymers, which have combined excellent
properties, i.e., high glass transition temperatures (Tg), high
resistance to chemicals and radiations, relatively low dielectric
constants, and good mechanical properties [35]. Beyond excepted
advantages of such materials, PIs have limitations in processability
and solubility that caused recently signicant synthetic efforts
through the synthesis of new diamine or dianhydride monomers.
Several approaches for the preparation of soluble PIs such as the

* Corresponding author at: Organic Polymer Chemistry Research Laboratory,

Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111,
Islamic Republic of Iran. Tel.: +98 311 391 3267; fax: +98 311 391 2350.
E-mail addresses: mallak@cc.iut.ac.ir, mallak777@yahoo.com,
mallakpour84@alumni.u.edu (S. Mallakpour).
0025-5408/$ see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.materresbull.2012.05.033

incorporating of exible bridging linkages, bulky substituents,

non-coplanar conformation units, as well as pendent groups into
polymer backbone directed to signicant achievement [6]. The
incorporation of bulky pendent groups produces a chain separation
effect lowering the chain packing, which increases water
accessibility and improves solubility. Some bulky groups, such
as imidazole or benzimidazole, can form strong hydrogen bonds
with water. Consequently, polymers modied with benzimidazole
groups have shown enhanced solubility, better hydrophilicity, and
higher Tgs than unmodied polymers [79].
On the other hand, further improvement of the PI properties
such as higher thermal stability and lower dielectric constant by
the introduction of different nanoparticles makes these materials a
good choice for preparation of hybrid materials to development of
next generation resources which act in response to the demand of
highly very tiny electronic devices, super conductive materials, and
modern spacecrafts [1012]. Various combinations of PIs with
inorganic llers including silica, a layered silicate such as
montmorillonite or mica, aluminum nitride, titania, barium
titanate and carbon nano-tubes have been reported. The prepared
hybrid materials show outstanding thermal stability, mechanical
strength and physical properties [13,14].

S. Mallakpour, M. Dinari / Materials Research Bulletin 47 (2012) 23362343

Recently PIssilica hybrid materials have received considerable

attention, because they often exhibit superior physical, mechanical
and thermal properties to conventional mineral-lled composites
or unlled polymers. These performance improvements such as
thermal stability, mechanical strength, molecular barrier, and
ame resistance depend greatly on the distribution, arrangement
of organoclay layered silicate and synergism between the layered
silicate and the polymer [1520]. In order to avoid the phase
separation in the resulting hybrid materials and achieve a highly
homogenous in the matrix, one approach is to control the chain
length of polymer segments, and the second one is the selection of
suitable coupling agents and/or the use of an effective compatibilizer [21,22]. The interaction of organoclay layered silicates with
polymers leads to intercalated or exfoliated nanocomposites (NCs).
In intercalated NCs, polymer chains are introducing between the
silicate layers, generating ordered lamella with an interlayer
distance of a few nanometers. In the second class silicate layers of
about 1 nm thick are exfoliated and dispersed in the polymer
matrix [23,24].
Naturally occurring montmorillonite (MMT) exists as anionically charged layers of magnesium/aluminum silicates and small
cations such as sodium or potassium located on the surface of each
platelet which balances the negative charge of layers. In addition,
MMT is hydrophilic because of the presence of strong electrostatic
forces between the layers and the ability to form hydrogen bonds
with water, so unmodied clays generally disperse poorly in
organic matrices. Thus, before preparation of polymer/MMT NCs,
modication is generally required through ion exchange reaction
between organic cations and inorganic cations to render hydrophilic MMT more organophilic to be compatible with polymer
molecules [16,2527]. The ease of dispersion depends on a number
of factors, including the nature of the organic cation and the
density of cationic sites on the platelets surfaces. This modication
also increase interlayer spacing of MMT, which expanded
interlayer spacing allow polymer molecules to enter and subsequently to intercalate the silicate layers [2830].
In this study, a series of organosoluble PIorganoclay NC
materials are successfully prepared by an in situ polymerization
reaction through thermal imidization. For this purpose, incorporation of hetroaromatic benzimidazol units into the polymer
backbone was designed to improve solubility while maintain
thermal stability of polymer. For preparation of the NCs based on
synthesized PI, naturally L-isoleucine amino acid was used as a
swelling agent that contains two amine and acid functional groups.
After converting amine functional group of the swelling agent into
a cation (NH3+), this cation formed an ionic bond with the
negatively charged silicate layers of MMT. The other functional
group (COOH) of the swelling agent can react with polymers
chains. The physical and mechanical properties of the resulting
NCs were done by various equipments.
2. Experimental
2.1. Materials
Solvents and chemicals were obtained from the Aldrich
Chemical Co. (Milwaukee, WI, USA), Riedel-deHaen AG (Seelze,
Germany), and Merck Chemical Co. (Germany). Pyromellitic
dianhydride (PMDA), L-isoleucine and hydrochloric acid (HCl)
were purchased from Merck Co. and was used without further
purication. N,N0 -Dimethyformamide (DMF) and N,N-dimethylacetamide (DMAc) were dried over barium oxide and then were
distilled under reduced pressure. 3,5-Dinitrobenzoyl chloride, 1,2phenylenediamine, hydrazine monohydrate, phosphorus pentoxide (P2O5), and methanesulfonic acid (MSA) were obtained from
commercial sources and used as-received. Cloisite Na+ was

2337

purchased from Southern Clay Products, Gonzales, Texas (USA).

The cation exchange capacity (CEC) of Cloisite Na+ is 92.6 mequiv./
100 g as reported by suppliers. This compound was used without
any further purication.
2.2. Characterization techniques
Fourier transform infrared spectroscopy (FT-IR) spectra of the
hybrid lms were recorded with a Jasco-680 (Japan) spectrometer
at a resolution of 4 cm1 and they were scanned at wavenumber
range of 4004000 cm1. Vibration bands were reported as
wavenumber (cm1). Thin lms of NCs were made by evaporating
solvent at 80 8C and used for FT-IR analysis. FT-IR spectra of Cloisite
Na+, organoclay and PI were also collected by making their pellets
in KBr as a medium. The band intensities are assigned as weak (w),
medium (m), shoulder (sh), strong (s), and broad (br).
The intercalation of polymers into the galleries of organoclay
was conrmed via X-ray diffraction (XRD) microscopy. The XRD
analyses were performed via X-ray diffractometer (Bruker, D8
Advance) with Cu Ka characteristic radiation (wavelength
k = 0.154 nm at 45 kV, 100 mA, and with a step size of 0.028 in
the range of 2u = 1.2108. XRD analysis was carried out to measure
the change in interlayer spacing of clay based on Braggs law.
Proton nuclear magnetic resonance (1H NMR) spectra were
recorded on Bruker Avance 400 MHz spectrometer operating
polymer solution in dimethylsulfoxide (DMSO-d6). The proton
resonances were designated as singlet (s) and multiplet (m).
Inherent viscosities were measured by a standard procedure
using a Cannon-Fenske routine viscometer (Germany) at the
concentration of 0.5 g/dl at 25 8C.
Thermogravimetry analysis (TGA) is performed with a STA503
win TA at a heating rate of 10 8C/min from 25 8C to 800 8C under
nitrogen atmosphere.
The dispersion morphology of the nanoparticles on PI matrix
was observed using eld emission scanning electron microscopy
(FE-SEM) [HITACHI; S-4160]. Transmission electron microscopy
(TEM) images were obtained using a Philips CM 120 microscope
with an accelerating voltage of 100 kV.
UVvis absorption of neat PI and PI/organoclay NCs was
measured by UV-Vis spectrometer, JASCO V-750 in the spectral
range between 200 and 800 nm.
Tensile properties of the NC lms were measured according to
DIN procedure 53455 having a crosshead speed of 5 mm min1
using Zwick 1446-60.
2.3. Organic modication of MMT
Accurately weighed 2 g of 325-mesh (<120 mm) screened ne
powdered Cloisite Na+ MMT with cation exchange capacity of
92.6 mequiv./100 g was slowly and carefully dissolved in the
protonated L-isoleucine amino acid solution, which was prepared
by dispersion of L-isoleucine amino acid with stoichiometric
amount of concentrated HCl in 100 ml of deionized water and
heating at 80 8C for 3 h. This reaction mixture was further heated
and maintained at 60 8C with vigorous agitation for 6 h. The mass
was cooled down to 40 8C and vacuum ltered. The solid wet cake
was washed with deionized water in a large beaker with rapid
stirring for 1 h and then it was dried in a vacuum oven at 80 8C for
24 h [31].
2.4. Synthesis of 2-(3,5-diaminophenyl)-benzimidazole
At rst 2-(3,5-dinitrophenyl)-benzimidazole 3 was prepared
from 3,5-dinitrobenzoyl chloride and 1,2-phenylenediamine using
MSA and P2O5 to yield 70% of this compound. Than 2-(3,5diaminophenyl)-benzimidazole (DABI) was prepared by reduction

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S. Mallakpour, M. Dinari / Materials Research Bulletin 47 (2012) 23362343

of dinitro precursor using palladium on activated carbon (Pd/C)

and hydrazine monohydrate in reuxed ethanol (yield: 77%; m.p.
242243 8C) [7,8,32].
2.5. Synthesis of reference PAAs and PI
Into a 100-ml three-neck round-bottom ask equipped with a
mechanical stirrer, nitrogen inlet, and drying tube containing
calcium chloride were placed DABI (2.00 g, 8.93 mmol) and DMAc
(10 ml). The solution was stirred until the diamine 4 completely
dissolved. Then PMDA with the same molar ratio of diamine was
added into the solution in four times within 1 h. The viscosity
increased quickly over 2 h. The mixture was stirred under nitrogen
at room temperature (R.T.) for another 8 h. The resulting yellowbrown poly(amic acid) (PAA) solution was clear and viscous. The
solution was subsequently used to prepare thin lms for
characterization. The inherent viscosity of the synthesized PAA
was 0.57 dl/g and the yield was 85%.
FT-IR (KBr, cm1): 25003500 (m, br), 1662 (m), 1554 (s), 1486
(w), 1422 (m), 1240 (m), 1072 (br), 1013 (w), 864 (m), 800 (w), 764
(m), 650 (w), 618 (m), and 560 (w).
The neat PI lm as reference was prepared by casting the PAA
solution onto a glass plate. After the lm was dried at R.T. for 2 h, it
was heated at 50, 80, 120, 200 and 250 8C for 1 h each, and at 300 8C
for 2 h, to obtain yellow colored transparent lms.
FT-IR (KBr, cm1): 3378 (m), 1776 (m), 1723 (s), 1600 (m), 1534
(w), 1457 (m), 1440 (m), 1376 (s), 1320 (s), 1276 (w), 1228 (w),
1097 (s), 1010 (m), 936 (w), 830 (s), 742 (m), 722 (s), 677 (m), 618
(m), and 565 (w).
2.6. In situ polymerization of PI/organoclay NCs by thermal
imidization
PAA/organoclay mixture and PI/organoclay NCs were prepared
by in situ polymerization, as shown by the ow charts in Fig. 1. An
appropriate amount of organophilic clay was introduced into 3 g of
DMAc under magnetically stirring for 24 h at R.T. (solution A),
1 mmol of diamine DABI was introduced into 1.5 g of DMAc under
magnetically stirring for 10 min at R.T. (solution B). And solution B
was introduced into solution A by stirring 24 h at R.T., 1 mmol of
PMDA was added into 1.5 g of DMAc under magnetically stirring at
R.T. (solution C). After that, solution C was added into solutions
A + B by stirring for 24 h at R.T. The resulting yellowish PAA/
organoclay solution was viscous and clear.
Imidization of PAA/organoclay for the synthesis of PI/organoclay hybrides was carried out by putting the samples in an aircirculation oven for 2 h at R.T. and then at 100, 150, 200, and 250 8C
for 1 h, respectively, and then at 300 8C for 2 h. Then the yellow
colored transparent samples were removed from the plate glass
and characterized with different techniques.

Fig. 1. Flow diagram for preparation of the PI/organoclay hybrid NC lms.

3.2. Preparation of benzimidazole diamine

3. Results and discussion

DABI 4 was prepared with a two-step procedure outlined in

Scheme 1. In the rst step, the dinitro 3 was obtained by the direct
condensation of 1,2-phenylenediamine and 3,5-dinitrobenzoyl
chloride with a mixture of P2O5/MSA as the convenient dehydrating agent and solvent [33]. In the second step, nitro groups were
reduced to the corresponding amino groups with hydrazine
hydrate as the reducing agent and palladium on activated carbon
as the catalyst. By this procedure, pure DABI was attained after
recrystallization [32].

3.1. Preparation of organoclay

3.3. Preparation of the PAI/organoclay NC lms

The organoclay chosen for dispersion in the PI needed enough

thermal stability to withstand the high temperature used to cure
the PI. This requirement led to the selection of thermally stable
molecules for surface modication of the clay. In this study,
positively charged of L-isoleucine amino acid swelling agent is
chosen to replace the chemically synthesized surfactant for
modication of Cloisite Na+. These phenomena causes enlarge in
the d-spacing which facilitates the entry of the host polymer
molecules into the organoclay gallery and they are more
hydrophobic than Cloisite Na+ for further applications.

The extent of improvement in the NC properties depended on

the state of dispersion of the silicate layers of the organoclay. Apart
from the chemical structure and the length of the organic moiety in
the organoclay, the processing conditions determined the state of
dispersion. Several approaches were examined by Delozier et al. for
PI-clay NCs [25]. According to their ndings, the best results were
obtained using an in situ polymerization technique, wherein PAA
was synthesized in the presence of organoclay, which was later
thermally imidized using a solution-casting technique. We used
this technique to prepare different NC lm samples (Scheme 1).

S. Mallakpour, M. Dinari / Materials Research Bulletin 47 (2012) 23362343

2339

Scheme 1. Preparation of benzimidazole containing aromatic diamine 4 and thermally stable PI/organoclay NCs.

3.4. Characterization
3.4.1. FT-IR and 1H NMR spectra
The existence of the characteristic peaks for NH2 functions and
the absence of the original peaks arising from the NO2 groups in the
corresponding dinitro provided the successful formation of the
DABI. Absorption of amine NH2 and NH benzimidazole bonds
appeared around 3394 and 3323 cm1 and the peak at 1627 cm1
conrms the presence of NH deformation. Two absorption bands at
1577 and 1484 cm1, were characteristic peaks for aromatic rings.
The benzimidazole groups gave bands at 1484 cm1, 1590 cm1
and a shoulder at 1630 cm1 (Fig. 2).
Typical FT-IR spectra of PAA, PI, organoclay and PI/organoclay
NC5% were also shown in Fig. 2. In the spectrum of PAA, the

Fig. 2. FT-IR spectra of the diamine 4, PAA, PI, organoclay and PI/organoclay NC5%.

characteristic absorption bands of the amic acid appeared near

3466 (NH and OH stretching), 1722 (acid, C5
5O stretching), 1662
(amide, C5
5O stretching), and 1554 cm1 (NH bending). After
thermal imidization of PAA, the peaks observed for PAA
disappeared, and instead a series of new bands corresponding to
PI were observed. In the spectrum of PI, the characteristic
absorption bands of the imide ring appeared near 1776 (asymmetric C5
5O stretching), 1723 (symmetric C5
5O stretching), 1376
(CN stretching), and 722 cm1 (imide ring deformation). Furthermore, the representative FT-IR spectra of the organoclay and PI/
organoclay NC5% are shown in Fig. 2. Characteristic vibration
bands of organoclay were shown at 3630 cm1 (OH), 2963 cm1
(CH), 1700 cm1 (C5
5O), 1040 cm1 (SiO), 525 cm1 (AlO), and
1
468 cm (MgO). In the spectrum of the NC5%, the presence of a
peak at 1048 cm1 corresponding to the SiO and peaks at 400
600 cm1 for AlO and MgO indicated the incorporation of
organoclay in the PI matrix. From these gures, it can be concluded
that the NC lms not only have characteristic neat PI bands, but
also have characteristic peaks for organoclay.
In the 1H NMR spectra of DABI, appearances of the N-H protons
of benzimidazole group at 12.62 ppm as broad singlet peaks,
indicate presence of this group. The absorption of aromatic protons

Fig. 3. 1H NMR (500 MHz) spectrum of the diamine 4 in DMSO-d6 at R.T.

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S. Mallakpour, M. Dinari / Materials Research Bulletin 47 (2012) 23362343

3.4.3.2. TEM. TEM provides direct and unambiguous qualitative

evidence for the formation of a true nanoscale composite. Structures
of the organo-modied clay and PI/organoclay NCs were directly
investigated by means of TEM (Fig. 6). According to our previous
study, the layer-structure images of untreated Cloisite Na+ cannot be
observed with TEM [34]. Contrasting to unmodied Cloisite Na+,
organoclay modied with protonated isoleucine amino acid show
clear layer structures. Fig. 6ac shows the TEM micrographs of the PI/
organoclay NC5% with different magnication (100 nm, 70 nm and
50 nm) in which the brighter region represents the polymer matrix
while the dark narrow stripes represent the stacked and intercalated
stacked nanoparticles. Due to the potential interaction between the
carboxylic acid groups of the modier with imide and benzimidazole
groups of PI, the TEM micrographs of NC5% reveal well-exfoliated
structures. This suggests that a greater interaction force between PI
and organic modiers are required for formation of exfoliated
structures. Both exfoliated silicate lamellae and intercalated stacks
are visible, consistent with the XRD and FE-SEM results. The majority
of the particles observed were exfoliated silicate-lamella stacks.
Fig. 4. XRD of the Cloisite Na+, organoclay and different PI/organoclay NCs.

appeared in the range of 5.967.50 ppm. The proton of the amine

groups appeared as broad singlet peaks at 4.91 ppm (Fig. 3).
3.4.2. X-ray diffraction
Fig. 4 shows the XRD patterns of clay and NC samples. For
Cloisite Na+ clay, the diffraction pattern shows a distinct peak at
2u = 7.568 corresponding to 11.70 A, which is assigned to the 001
lattice spacing of MMT. After modication with protonated Lisoleucine amino acid, 2u decreased to 6.108, i.e., the d spacing
increased to 14.50 A for organoclay. The greater spacing in the
organoclay, when compared to Cloisite Na+ clay, would help the
silicate layers to disperse easily. In NC samples, no distinct peak
was observed at lower organoclay concentrations (up to 5%),
whereas for 7 and 10% organoclay concentrations, a distinct peak at
about 2u = 3.228 (d = 27.4 A) was observed. The peak observed in
2u = 7.568 corresponding to the basal spacing of organoclay has
disappeared in the NCs 1%, 3% and 5%, suggesting the disorder and
loss of structure regularity of the clay layers. Thus, the clay tactoids
are considered to be exfoliated and the 0.96-nm thick clay layers
are dispersed at the molecular level into PI. However, with the
increase of the organoclay loading more than 5%, the hybrids show
a slight peak at 2u = 3.228 that was corresponds to a d spacing of
2.74 nm suggesting that a small part of organoclay is not dispersed
in the molecular level. It also suggested a degree of intercalation of
PI into the organoclay galleries.

3.4.4. Thermal properties

The TGA curves for Cloisite Na+ and organoclay of L-isoleucine
amino acid were reported in our previous study [31]. The results
show that the decomposition of Cloisite Na+ occurs in two steps:
one before 100 8C was attributed to the desorption of water from
the interlayer space, another around 660 8C due to dehydroxylation of the layers and proceeds till around 700 8C. The presence of
organic cations in organoclay increases the number of decomposition steps and it was shown that the decomposition of an
organoclay takes place in four steps. At 800 8C, the residue for
organoclay is up to 87%.
The results of the TGA for pure PI and PI hybrid lms with 3%,
5%, 7% and 10% of organoclay are shown in Fig. 7 and Table 1 in
nitrogen atmospheres. All the NCs were found to have single step
decomposition and be stable up to 440 8C. The 10% weight loss
temperatures of the NCs were higher than those of the pristine PI.
The higher thermal stability of NCs when compared to the pure PI
was attributed to the formation of char-like material as a result of
the decomposition of organoclay and this material acted both as a
barrier to mass transport of the decomposed products to the
surface of the decomposing polymer and as a thermal barrier to
prevent additional exposure of the polymer to the ame. The
percent char yield at 800 8C increased with an increase of
organoclay content in the NCs, which indicated that the dispersion
of organoclay in the PI matrix was uniform. Char yield can be
applied as decisive factor for estimated limiting oxygen index (LOI)
of the polymers based on Van Krevelen and Hoftyzer equation [35].

3.4.3. Morphology studies

LOI 17:5 0:4CR;

3.4.3.1. FE-SEM. The morphological images of the Cloisite Na+ and

organoclay were studied by SEM technique in our previous study
[31]. Before modication, Cloisite Na+ shows massive, aggregated
morphology and in some instances, there are some bulky akes.
After modication, organoclay has more fragments of smaller size
and they are formed with irregular shapes. The morphological
images of the pure PI, NC3% and NC10% were studied by FE-SEM
(Fig. 5). Pure PI exhibited rigid fracture deformation morphology
(Fig. 5a and b). The FE-SEM micrographs of the NC5% show that the
organoclay platelets were uniformly distributed without agglomeration at low organoclay content (Fig. 5c and d). When the
organoclay was increased to 10%, agglomeration of clay particles
was observed as indicated by the white circle in the FE-SEM
micrograph (Fig. 5e and f). Silica domains can be clearly observed
with good dispersion to the organic polymer matrix.

The NC3%, NC5%, NC7% and NC10% have LOI values in rang of
4246% which were calculated from their char yield at 800 8C. On
the basis of LOI values, all NCs can be classied as selfextinguishing materials (Table 1). From these data it is unambiguous that neat PI and it is NCs are thermally stable owing to
existence of various linkages such as imide and benzimidazoles
groups in polymer backbones.

where CR char yield

3.4.5. Optical transparency

When single layers of layered silicates are dispersed in a
polymer matrix, the resulting NC is optically clear in visible light.
The lms prepared with the solvent casting process are almost
colorless, and their levels of transparency are increases with the
organoclay content. Moreover, since the hybrid lms have phase
domains smaller than the wavelengths of visible light, the

S. Mallakpour, M. Dinari / Materials Research Bulletin 47 (2012) 23362343

2341

Fig. 5. FE-SEM images of the (a and b) pure PI, (c and d) PI/organoclay NC5%, and (e and f) PI/organoclay NC10%.

materials are transparent even for clay loadings up to 5 wt.%. Fig. 8

shows the UVvisible transmission spectra of pure PAI and NC
materials with 3, 5, 7 and 10 wt.% of organoclay. The spectra of
NC3% and NC5% were slightly affected by the presence of the
organoclay and retained the high transparency, indicating that
intercalated NC materials might exist at low clay contents.
Furthermore, NC7% and NC10% had a lower transparency resulting
from agglomeration of the organoclay particles. The translucencies
of the NC lms come from the nanoscale dispersion of the
organoclay particles in the matrix polymer.

3.4.6. Mechanical properties

The amount of organoclay added to PI signicantly affects the
observed mechanical properties. The stressstrain curves of pure
PI and NC materials with 3, 5 and 10 wt.% of organoclay are shown
in Fig. 9. The strength and modulus values were found to be
enhanced with respect to those of PI for ller contents up to a
critical content, with inferior values above that content. It appears
that there is a critical amount of ller beyond which the llers
reinforcing capacity diminishes. The tensile strength of the neat PI
matrix is 75 MPa. The tensile strength of the NCs with 3, 5 and

Fig. 6. TEM images of PI/organoclay NC10% with different magnications.

S. Mallakpour, M. Dinari / Materials Research Bulletin 47 (2012) 23362343

2342

Fig. 7. TGA thermograms pure PI and different PI/organoclay NCs.

Fig. 9. Representative stressstrain curves for the neat PI, NC3%, NC5% and NC10%.

4. Conclusions

Fig. 8. UVvis of the pure PI and different NCs.

10 wt.% of organoclay are 87, 102 and 96 MPa, respectively. The

maximum stress at break was found to increase initially with
increase in organoclay content, and at 5 wt.% organoclay showed a
maximum value of 102 MPa relative to the 75 of the neat PI. This
decrease in the ultimate tensile strength is mainly owing to the
agglomeration of ller particles over critical organoclay content.
The general tendency for improvement in the stress level is
increased by the addition of organoclay which play the role of
reinforcement. Another reason for the enhancements in the tensile
modulus of NCs is the strong interaction between the PI matrix and
organoclay via formation of hydrogen and chemical bonding [21].
From these results, it is deduced that the reinforcing effect of the
organoclay is very marked. As the organoclay content in the
polymer increases, the stress level gradually increases but at the
same time the strain of the NCs decreased.

Table 1
Thermal properties of the neat PI and different NC lms.

Organoclay content (wt.%)

T10 a

Char yield (%)b

LOIc

0
3
5
7
10

421
440
449
461
467

58
61
64
67
71

40.7
41.9
43.1
43.3
45.9

Temperature at which 10% weight loss was recorded by TGA at heating rate of
10 8C min1 in a N2 atmosphere.
b
Weight percent of the material left undecomposed after TGA at maximum
temperature 800 8C in a N2 atmosphere.
c
Limiting oxygen index (LOI) evaluating at char yield at 800 8C.

In this study at rst a processable PI was prepared based on

aromatic imide and pendant heterocycles benzimidazole moieties
in the side chain. From the chemical point of view, the
incorporation of benzimidazoles group into the backbone of
polymer systems results in versatile polymers with interesting
properties such as thermal stability and good solubility. Difunctionalized L-isoleucine swelling agent was used for organomodication of Cloisite Na+. The amine function of modier formed an
ionic bond with negatively charged silicates and free acidic group
is available for further reaction with imide and benzimidazole
groups of the PI. PIorganoclay NC hybrids with different
organoclay contents ranging from 1 to 10 wt.% with good dispersed
silicate layers in the PI matrix have been successfully synthesized
by an in situ polymerization. XRD, TEM and FE-SEM results
demonstrated that NCs containing low organoclay content were
found to have an exfoliated structure whereas at higher clay
concentration, agglomeration was observed leading to intercalated
structures. Dispersed organoclay platelets into PI matrix were
found to increase the thermal stability such as the enhancement of
thermal decomposition temperature and char yield of PI/organoclay NCs based on the TGA studies. Moreover, the original reactive
swelling agent becomes a part of the polymer molecules, and it
makes these NCs more stable thermally and stronger mechanically.
According to mechanical properties, as the organoclay content in
the polymer increases, the stress level gradually increases but at
the same time the strain of the NCs decreased.
Acknowledgments
We wish to express our gratitude to the Research Affairs
Division, Isfahan University of Technology (IUT), Isfahan, for partial
nancial support. Further nancial support from National Elite
Foundation (NEF), Iran Nanotechnology Initiative Council (INIC)
and Center of Excellency in Sensors and Green Chemistry Research
(IUT) is gratefully acknowledged.
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