Materials Science and Engineering A 527 (2010) 574583

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Materials Science and Engineering A

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

Poly (trimethylene) terephthalate/m-LLDPE blend nanocomposites:

Evaluation of mechanical, thermal and morphological behavior
Sanjay K. Nayak , Smita Mohanty
Laboratory for Advanced Research in Polymeric Materials (LARPM), Central Institute of Plastic Engineering and Technology (CIPET),
B-25, CNI Complex, Patia, Bhubaneswar 751024, Orissa, India

a r t i c l e

i n f o

Article history:
Received 27 May 2009
Received in revised form 7 August 2009
Accepted 13 August 2009

Keywords:
Nanocomposites
Blends
Strength
XRD
TEM

a b s t r a c t
PTT/m-LLDPE blends and its nanocomposites were prepared using melt blending technique in a batch
mixer. Organically modied nanoclays have been used as nanoscale reinforcement to prepare blend
nanocomposites. Mechanical tests revealed optimum performance characteristics at PTT/m-LLDPE ratio
of 70:30. Further, incorporation of nanoclays showed higher tensile strength and modulus in the blend
nanocomposites as compared to optimized blend. The nanocomposites formation has been established
through X-ray diffraction and transmission electron microscopy. The thermal measurements have been
carried out using DSC and TGA. DSC thermograms revealed a maximum increase in the crystallization
temperature in the presence of clays in the blend system containing Cloisite 30B. TGA thermograms
indicated that the thermal stability of the blend increases with the incorporation of nanoclays. DMA
measurements reveal that the Cloisite 30B nanocomposite has maximum modulus as compared to other
nanocomposites.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Blending of two or more polymers has emerged as an established
route to design and tailor-made polymeric materials with desired
attributes for various high performance applications [14]. The
advantages of polymer blending include versatility, simplicity, and
inexpensiveness. However, most of the polymer pairs are inherently immiscible that results in incompatibility, with subsequent
phase separation in the blend matrix. Different approaches such
as use of compatibilizing agents, copolymers, grafting agents, reactive extrusion, etc., have been the commonly used techniques to
modify the interfacial region between the blends and increase the
compatibility [5,6]. Blending of ductile thermoplastics with impact
modiers leading to formation of super-tough blends wherein
there is 1020-fold increase in the impact strength of the base
matrix has gained substantial importance in the recent years.
Various notch-sensitive polymers of amorphous and crystalline
matrix, viz., polyamides [79], polyesters [1013] and polyolens
[14,15] have been reported. The studies collect the interest of
overtaking the notch sensitivity of these polymers and of understanding the parameters that inuence the toughening mechanism
[15].

Corresponding author. Fax: +91 67 2743863.

E-mail address: drsknayak@yahoo.com (S.K. Nayak).
0921-5093/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2009.08.026

More recently, layered silicates/organically modied nanoclays

have also been incorporated into the blend matrix, wherein the
organoclays itself aids in reducing the particle size of the matrix
polymer dispersed in the base matrix of the blend [16,17]. Layered silicates, with its inherent high aspect ratio ranging from 100
to 2000 offers more surface contact per unit ller within the polymer matrix resulting in enhanced performance characteristics [18].
With a minimum organoclay loading of 1%, nearly 10% increase in
mechanical properties have been reported. Blend nanocomposites
of a variety of polymers such as PP/EOC, PP/PA, PS/PMMA, PPO/PA6
have already been reported by several researchers, synthesized
through different techniques; in situ intercalative polymerization,
melt intercalation and solution intercalation [1924]. However,
studies on nanocomposites of polymer blend systems are few
[2025].
PTT, an aromatic polyester prepared by polycondensation reaction between propane-1,3-diol and terephthalic acid or dimethyl
terephthalate, has gained commercialization over the last years
[26]. PTT combines the mechanical properties of PET and processing characteristics of PBT, thus possessing the desired attributes
of thermoplastic polyester, wherein the properties such as dimensional stability, solvent and abrasion resistance are pre-requisite.
However, certain impediments such as low toughness, heat distortion temperature and viscosity, poor optical properties and
pronounced low temperature brittleness have restricted the optimum use of PTT, as engineering plastic in many applications.
Several attempts have already been made by various researchers

S.K. Nayak, S. Mohanty / Materials Science and Engineering A 527 (2010) 574583

to increase the toughness of PTT, by blending it with ABS [27],

EPDM [28] and EOC [29]. Compatibilization process in PTT/ABS
blend using epoxy or styrene butadiene maleic anhydride as compatibilizer has been studied by Xue et al. [27]. Existence of two
different compositions dependent Tg s, indicating partial miscibility of ABS phase within the PTT matrix has been reported.
Guerrica Echevarria et al. [29] have shown an increase in the
toughness of PTT with incorporation of EOC. Similar, several investigations on PTT/EPDM, PTT/PS, PTT/PBT, and PTT/PP have been
extensively studied and reported in literature [2831]. Metallocene
catalyzed polyethylene (m-LLDPE) has also been used as toughening agent because of presence of butene as a side chain in the
structure and arrangement of short chains in the macromolecule
with narrow molecular weight distribution [32]. Several studies
on aromatic polyester/LLDPE have been made and immiscibility
and phase-separated compositions due to structural considerations and different solubility parameter have been indicated
[3337].
In the present investigation, mechanical, thermal and morphological characterization of PTT/m-LLDPE blends and its
nanocomposites at variable weight percentages of organically
modied nanoclay have been investigated.

575

2.3. Morphological characterization

2.3.1. X-ray diffraction analysis
The interlayer gallery spacing of nanoclays in the nanocomposites was studied using wide angle X-ray diffraction at ambient
temperature using Philips XPert MPD (Japan), and Cu K radiation source operated at 40 kV and 18 mA.
2.3.2. Scanning electron microscopy (SEM)
The scanning electron microscopy (SEM) of impact fractured
blends and blend nanocomposites specimens was carried out using
JEOL-JSM T330A, Japan at 15 kV-accelerated voltage.
2.3.3. Transmission electron microscopy (TEM)
For TEM observation, the samples were stained with OsO4 vapor
and were subsequently microtomed at low temperature (55 C)
using Leica Ultracut Cryo-microtome (Japan) equipped with diamond knife. The ultra thin sections (ca. 40 nm, prepared from
3 mm thick plates) were examined using a Transmission Electron
Microscope (Philips CM12, The Netherlands) using an acceleration
voltage of 100 kV at 100 nm scale.
2.4. Mechanical properties

2. Experimental
2.1. Materials
PTT (Futura CPTT ) was purchased from M/s Futura Polymers
Ltd., India, having density of 1.3 g/cm3 and intrinsic viscosity of 0.915 dL/g (Phenol/Carbon Tetrachloride, 60/40). m-LLDPE
(Relene ) was obtained from M/s Reliance Industries Ltd., India,
having MFI of 1.0 g/10 min. The clay minerals used were commercially available Cloisite 30B (C30B, CEC of 90 meq/100 g clay),
organically treated montmorillonite (MMT) with, methyl tallow
bis-2-hydroxyethyl ammonium (MT2EtOH) and Cloisite 20A (C20A,
CEC of 95 meq/100 g clay) treated with organic modier dimethyldihydrogenated tallow ammonium (2M2HT), obtained from M/s
Southern Clay Products Inc., USA. Maleic anhydride and dicumyl
peroxide were purchased from E-Merck, India.
2.2. Preparation of PTT-m-LLDPE blend and blend
nanocomposites
Blends of PTT/m-LLDPE at various composition (90/10, 80/20,
70/30, 50/50 by weight) were prepared using a Torque Rheocord9000 (HAAKE , Germany), batch mixer, at a screw speed of 70 rpm
and 250 C for a duration of 6 min. Prior to blending, PTT was
predried at 120 C for 24 h. The m-LLDPE was added to the molten
PTT after 3 min of blending. Specimens were prepared using mini
Injection molding machine (HAAKE Minijet) at 245 C, barrel temperature, 840870 bar injection pressure and mold temperature of
110 C as per ASTM standard.
For a typical melt grafting m-LLDPE was pre-dried in vaccum
oven at a mild temperature of 60 C for 3 h. The grafting of m-LLDPE
was carried out in a twin screw extruder (Haake Germany) with
13 wt% of maleic anhydride (MA) and 0.05% of dicumyl peroxide. The percentage grafting of MA onto m-LLDPE was evaluated
using the titration method as reported by Guerrica Echevarria et al.
[16] and the most reacted MA-g-m-LLDPE (3 wt%) was selected for
preparation of blends and blend nanocomposites.
The blend composition was optimized at 70:30 ratio of PTT:mLLDPE and was maintained for preparation of polymer blend
nanocomposites using similar fabrication technique as reported
above. Prior to blending the organoclays were dried in vaccum oven
at 120 C for 16 h and the residence time in the mixer was optimized
to 8 min.

Tensile properties were determined using Universal Testing

Machine (UTM), LR-100K (Lloyd Instruments Ltd., UK, as per ASTMD 638 respectively. Tensile test was performed using type V-tensile
dumbbells, at a cross-head speed of 5 mm/min and gauge length of
50 mm whereas exural test was determined, at cross-head speed
of 1.5 mm/min and span length 50 mm. Izod impact strength was
measured using Impactometer (CEAST, Italy) as per ASTM-D 256.
2.5. Dynamic mechanical analysis
The dynamic mechanical properties of samples, were investigated using DMA242 analyzer (NETZSCH, Germany) at xed
frequency of 1 Hz, heating rate of 10 K/min, under nitrogen atmosphere over a temperature range of 150 to 200 C in three point
bending mode.
2.6. Thermal analysis
Differential scanning calorimetry (DSC) measurements were
performed by scanning the (Diamond DSC Perkin Elmer Inc., USA)
samples from 0 to 270 C @ of 10, 20 and 30 C per min respectively
and holding for 5 min with subsequent cooling to 0 C at the same
rate under nitrogen atmosphere. The thermal stability was studied
from TGA/DTG curves using Pyris 7 TGA equipment (Perkin Elmer
Inc., USA). Samples of about 10 mg were heated from 50 to 700 C
at a heating rate of 20 C/min in nitrogen atmosphere.
3. Results and discussion
3.1. Property changes of PTT by blending with m-LLDPE
Youngs modulus and yield stress of PTT/m-LLDPE blend at
variable wt% of m-LLDPE are depicted in Figs. 1 and 2. It is evident that the Youngs modulus of PTT decreases linearly with the
increase in m-LLDPE content. This behavior is probably because
m-LLDPE is inherently weak and soft with elastomeric properties due to linearity in its structure with 510% branching.
Thus incorporation of soft elastomeric phase into rigid polymer results in reduction in crystallinity of the virgin polymer
with a consequent deterioration in tensile modulus. Further, as
referred by Zafari [32], the m-LLDPE phase is dispersed as spherical domains within the PTT matrix, which indicates immiscible

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S.K. Nayak, S. Mohanty / Materials Science and Engineering A 527 (2010) 574583

Figs. 1 and 2. Variation of Youngs modulus and yield stress of PTT/m-LLDPE as a function of m-LLDPE content.

characteristics. A similar decrease in tensile strength, was also

noticed with the incorporation of m-LLDPE. The yield stress
decreased drastically at low m-LLDPE contents and the values
were below the rule of mixtures considering the yield strength
of the elastomeric phase to be zero. This reduction in the tensile properties reveals inherently weak strength of m-LLDPE as
compared with PTT, which has been widely reported by various
authors for blends of polyesters with semi-crystalline polyolens
[1519].
Fig. 3 depicts the ductility of the blends as a function of mLLDPE content, the elongation of the blend matrix at 10 wt% of
m-LLDPE showed similar values as that of the virgin matrix polymer
which subsequently decreased at higher contents of the elastomeric phase. Similar behavior of reduction in the ductility of the
blends with the increase in the elastomer content has been reported
by various other thermoplastic rubber blend systems [29]. It has
been reported that the higher brittleness in PTT based blends; in
particular, is attributed to higher rubber particle size at same rubber
loadings.
Impact strength of PTT can be improved by blending with EPDM,
LLDPE, polyethylene octene elastomer (PEO) in the presence of a
compatibilizer [16]. PTT-maleated PEO (m-PEO) super toughness
blends at mPEO content of above 25 wt% has been reported, with
around 15-fold increase in the impact strength with an increase
shear rate during processing. Impact modication of PTT is possible
by interaction between the chain ends of PTT i.e. the hydroxyl and
carboxylic groups of PTT with a functionalized rubber component.
In the present discussion, maleic anhydride grafted m-LLDPE has
been used to compatibilize the blend system.
Izod impact strength of PTT/m-LLDPE blend is depicted in
Table 1. The impact strength of PTT was observed to be 26.80 J/m.
Incorporation of MA-m-LLDPE to the tune of 1030% results in an

increase in the impact properties of PTT matrix in the blends. The

blend prepared at PTT: m-LLDPE ratio of 70:30 exhibits maximum
impact strength of 33.76 J/m, which subsequently reduces with the
increase in PTT content to 50 wt%. This indicates that m-LLDPE acts
as impact modier due to presence of metallocene and butene in
its structure, at lower concentrations. However, at larger concentration of m-LLDPE, weak interfacial adhesion between PTT and
m-LLDPE results in phase separation, which ultimately reduces the
impact strength in the blends. Furthermore, as widely reported by
various workers, at the blend ratio of 70:30, phase morphology
changes and beyond 30 wt% phase inversion occurs, wherein the
impact strength in the blend is primarily governed by m-LLDPE.
Additionally, incorporation of MA-g-m-LLDPE, increases the
impact strength to 44.23 J/m. This indicates enhanced compatibility of maleic anhydride modied m-LLDPE with PTT in comparison
with non-maleic anhydride modied m-LLDPE which is probably
because of the intermolecular dipoledipole interaction between
carbonyl oxygen ( ) in MA of MA-g-m-LLDPE and hydrogen in
the hydroxyl group (+ ) of PTT. However, these values are far from
the typical values of super tough blends which shows an impact
strength of 500600 J/m. As evidenced in PTT based m-PEO blends
[16], an attempt has been made to extrude PTT/MA-g-m-LLDPE
blends at 70/30 ratio at high shear rate to increase the toughness
characteristics. It was observed that the impact strength increased
drastically to 328 J/m. This phenomenon is attributed to reduction
in the interparticle distance (IDc). The detailed morphology of the
blends at high shear rate and the IDc is under further investigation
and shall be reported in the forthcoming articles.
The blending of functionalized polyolen also drastically affects
the thermal properties of PTT. The DSC melting scans of the matrix
polymer and the compatibilized blend matrix was carried out at
20 C and the corresponding Tm and Tc of both PTT and m-LLDPE
phase was noted in Table 2. Virgin PTT depicts a melting transition
around 247.59 C with m-LLDPE at 127 C. The DSC scan of the blend
reveals two distinct Tm , which reveals phase-separated morpholTable 1
Izod impact test of PTT virgin and PTT/m-LLDPE blends.

Fig. 3. Variation of ductility of PTT/m-LLDPE blend as a function of m-LLDPE content.

Compositions

Impact strength (J/m)

SD

PTT (V)
PTT/m-LLDPE (90/10)
PTT/m-LLDPE (80/20)
PTT/m-LLDPE (70/30)
PTT/m-LLDPE (50/50)
PTT/MA-g-m-LLDPE (70/30)
PTT/MA-g-m-LLDPE (70/30)
*High shear rate

26.80
31.22
31.22
33.76
31.11
44.23
328.0

1.63
1.27
1.37
1.35
2.27
1.82
1.13

NB: SD indicates standard deviation a minimum of ten test samples were used for
each test and data reported are average of ten samples.

S.K. Nayak, S. Mohanty / Materials Science and Engineering A 527 (2010) 574583

577

Table 2
Summary of DSC results of PTT/m-LLDPE blends.
Compositions (%)

Tm ( C)
m-LLDPE

PTT virgin
PTT/m-LLDPE (70/30)
PTT/MA-g-m-LLDPE (70/30)
m-LLDPE

128.50
128.12
129.00

Tc ( C)

Xc
PTT
247.59
232.23
233.12

ogy, in agreement with SEM image discussed in the later sections.

The lower melting transition was observed in m-LLDPE rich phase,
whereas the higher melting transition was found in PTT rich phase.
The degree of melt crystallization of the virgin PP, m-LLDPE
and the blends is also displayed in Table 2. It is observed that
incorporation of m-LLDPE or MA-g-m-LLDPE reduces the melting
temperature of PTT in the blend matrix. The melt crystallization of
the PTT/MA-g-m-LLDPE blend is lower than that of the neat component as well as PTT/m-LLDPE blend. Furthermore the crystallization
degree also reduces substantially in the grafted blend indicating
ne dispersion of m-LLDPE within the base matrix PTT. Additionally, the blend system does not show any appreciable increase or
decrease in the Tm and Xc of m-LLDPE.
3.2. PTT/MA-m-LLDPE blend nanocomposites

m-LLDPE

9.0
8.1
11.0

PTT
37.48
36.30
31.71

m-LLDPE

110.50
107.58
113.02

PTT
177.86
176.40
174.52

overall entropy lost during separation of the silicate galleries [35].

The morphology of the blend nanocomposites was further corroborated with TEM and SEM discussed in later sections.
3.2.2. Scanning electron microscopy (SEM)
The phase morphology of the 70PTT/30 m-LLDPE blend without and with 5 wt% organoclay is shown in Fig. 5. The comparison
is made with SEM images taken from the impact-fractured surfaces of the injection molded samples. The 70PTT/30m-LLDPE
blend [Fig. 5(a)] demonstrates a two-phase morphology indicating immiscibility in the blend system. The m-LLDPE particles are
randomly dispersed in polar PTT phase. The dispersed m-LLDPE
particles play a crucial role in improving impact strength. The
m-LLDPE particles are randomly dispersed because of non-polar
nature of m-LLDPE, within the polar PTT matrix, having a linear
and a semi-crystalline structure.

Very few papers have been published on the preparation of polymer blend nanocomposites from organically modied nanoclays. In
this section toughened PTT based blend nanocomposites have been
discussed and especially the dispersion states of organoclays have
been highlighted in detail.
PTT/MA-m-LLDPE/organoclay ternary nanocomposites were
prepared using melt intercalation technique to obtain toughened
PTT with higher mechanical properties. Since the toughened blends
displayed optimum performance, the nanocomposites were fabricated using PTT/MA-m-LLDPE blend at an optimized blend ratio of
70:30. It is expected that for the polymer layered silicate hybrid
based on the blend system that the dispersion and migration of the
silicate in two phases would provide important guidelines regarding formation mechanism of the blend nanocomposites.
3.2.1. X-ray diffraction analysis (XRD)
The XRD patterns of different organically modied clays are
depicted in and Fig. 4(a). It is evident that the d001 spacing of the
silicate layers increases in the following order: C30B < C20A. C20A
nanoclay shows a diffraction pattern corresponding to 2 = 3.65
while C30B shows around 4.70 . Such an increase in the order of
d001 spacing correlates with the order of particle size reduction.
The state of dispersion of the silicate layers in the blend matrix
has also been investigated using X-ray diffraction patterns represented in Fig. 4(b). The mean interlayer spacing of plane (d001 ) of
C30B was 1.85 nm. In case of the 70PTT/30m-LLDPE/5C30B hybrid,
the characteristic peak shifted to a smaller angle corresponding
to d001 spacing of 3.7 nm, because of intercalation of polymer
chains into silicate galleries [28]. A similar shifting of angles to
3.5 nm was also observed in PTT/m-LLDPE/C20A nanocomposites
system revealing the formation of intercalated structure. Furthermore, it was also noticed that the X-ray diffractograms in the blend
nanocomposites system reveals a broad and a shallow diffraction
peak which is probably due to decrease in coherent layer scattering
[36,38].
Furthermore, in all the cases another small diffraction peak was
observed around 5.75.8 , which reveals the presence of tactoids.
Intercalation of the polymer chains leads to decreased entropy of
the system with a simultaneous increase in the conformational
freedom of the surfactant molecules, thereby compensating the

Fig. 4. (a) WAXD of nanoclays: (a) C20A (b) C30B. (b) WAXD of (a) PTT/mLLDPE/C20A (b) PTT/m-LLDPE/C30B blend nanocomposites.

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S.K. Nayak, S. Mohanty / Materials Science and Engineering A 527 (2010) 574583

Fig. 5. SEM micrographs of (a) PTT/m-LLDPE (70/30), (b) PTT/MA-g-m-LLDPE (70/30), (c) PTT/MA-m-LLDPE (70/30)/C20A 5%, (d) PTT/MA-g-m-LLDPE (70/30)/C30B 5%.

Addition of organoclay reduces the particle size of m-LLDPE and

increases the interfacial adhesion between the phases of two polymers. It is supposed that organoclay particles dispersed in a polar
PTT can prevent the coalescence of the randomly dispersed nonpolar elastomeric phase. This is also because of very slight extent of
enthalpic interaction between polar matrix and hydrophilic organoclay surface. The blend nanocomposites prepared using C30B
represents optimum reduction of particle size and enhancement
in interfacial adhesion between polymer phases. This is due to high
concentration of surfactants in C30B and approximately similar
solubility parameters with PTT. Similar type of investigations has
also been reported by Ray et al. [18]. C20A blend nanocomposites
also exhibited comparatively less reduction in particle size vis-a-vis
C30B system which is probably due to its high hydrophobicity compared with the later nanoclay, but less concentration of surfactants
and dissimilar solubility parameter.
Further the rubber particle size was measured in representative zones of the cryogenically fractured impact specimens and
the weight average particle size (dw ) was calculated from approximately 200 particles as follows [29]:
dw =

nd2
nd

where n is the number of particles with size d. The average interparticle distance () was calculated using the following equation:

=d

  1/3

k

6


1

where  is the volume fraction of the elastomer and k is the geometric constant equal to 1 for a cubic lattice [7].
Using the above equation the interparticle distance incase of
PTT/m-LLDPE blend matrix was found to be 0.6 m which reduced

to 0.02 m with compatibilization with maleic anhydride. Further,

the particle size in the blend matrix also reduced from 0.46 to
0.38 m upon reactive compatibilization which further conrmed
decreased interfacial tension with chemical reactions between the
maleic group and terminal hydroxyl groups of PTT.
Additionally, incorporation of organically modied nanoclays
reduced the particle size further to 0.18 m in case of PTTMA-m-LLDPE/C20A and 0.03 m in PTT-MA-m-LLDPE/C30B blend
nanocomposites respectively. As reported by Guerrica et al. [29]
lower, interparticle distance promotes increased toughness in the
blends. In our investigation, the blend nanocomposites exhibited
substantially lower  = 0.02 m in case of PTT-MA-m-LLDPE/C20A
and 0.003 m in PTT-MA-m-LLDPE/C30B which further corroborates with our ndings.
3.2.3. Transmission electron microscopy (TEM)
To elucidate the dispersion of clay in the blend nanocomposites
in detail, Fig. 6 illustrates the TEM micrographs of PTT/mLLDPE/C20A, and PTT/m-LLDPE/C30B. The dark lines represent the
thickness of individual clay layers or agglomerates. Thick darker
lines represent stacked silicate layers due to clustering or agglomeration. It was observed from the micrographs that clay particles
preferentially resided in the PTT phase rather than m-LLDPE phase
as also discussed in SEM analysis. In case C30B blend nanocomposites, it was found that stacked and intercalated silicate layers
are well dispersed within the blend matrix especially in polar
phase. Due to similar solubility parameter, C30B attributes high
level of enthalpic interaction resulting semi-exfoliation as well
as well dispersion in the blend matrix. This observation again
conrms the compatibilization efciency of C30B, as previously
assessed by SEM and by the reduction of particle size. It was interesting to note that the organoclay has a strong tendency to be
located in the PTT phase and the domain size of dispersed parti-

S.K. Nayak, S. Mohanty / Materials Science and Engineering A 527 (2010) 574583

Fig. 6. TEM micrographs of (a) PTT/m-LLDPE/C30B 5% and (b) PTT/m-LLDPE/C20A

5%.

cle effectively reduced, due to obstacle created by exfoliated clay,

as shown in Fig. 6(b) and (c). However, a mixed nanomorphology was obtained in PTT/m-LLDPE/C20A nanocomposites; there
were regions of ordered/disordered intercalation. Few stacks of
intercalated clay layers were also observed in PTT/m-LLDPE/C20A
nanocomposites.
3.2.4. Mechanical properties of toughened PTT/m-LLDPE blend
nanocomposites
3.2.4.1. Effect of clay loading on tensile properties. The mechanical properties of PTT/m-LLDPE blend nanocomposites at various
wt% of organically modied clays are also depicted in Table 3. It
is evident that tensile properties of blend increase with addition of
35 wt% C20A, and C30B nanoclay. Tensile strength of blend matrix
increases from 37.92 to 50.86 MPa in PTT/m-LLDPE/C20A and
53.24 MPa in PTT/m-LLDPE/C30B blend nanocomposites respectively at 5 wt% of nanoclay loading, which indicates stiffening effect
of nanoclay layers. A similar linear increase in tensile modulus to

579

the tune of 63.3% in C20A and 76.5% in C30B respectively was also
obtained as compared with the blend matrix. The tensile properties in a polymer blend are largely dependent on composition,
chemical structure, and level of dispersion. As reported by Zafari
[32], in the case rubber toughened PTT nanocomposites, the clay
particles show diminution effect on the rubber particle size which
thereby inuences the level of dispersion of the rubber particles in
the blend matrix. In the present investigation, similar phenomenon
might have resulted in positive effect on the dispersion of m-LLDPE
within the blend matrix. In other words, presence of nanoclay aids
in controlling the blend morphology by reducing the particulate
size of m-LLDPE, thus increasing its dispersibility within PTT.
As observed from the table, the blend nanocomposites prepared
using C30B nanoclay shows optimum increase in tensile strength
to approximately 40% and tensile modulus of 76.5% as compared
with blend matrix at 5 wt% clay loading. The differences in the
chemical structure and concentration of the organic modier used
in the nanoclay plays a vital role in dispersion of layered silicates
within the blend matrix. According to Vaia and co-workers [23,24],
the interlayer structure of the organically modied layered silicate
should be optimized to attain maximum congurational freedom
of the functionalizing chains upon layer separation and increase
the potential reaction sites at the interlayer surface. In the present
context, the methyl tallow bis-2-hydroxy ethyl quaternary ammonium intercalant in C30B has two OH groups in its structure, which
might have interacted with the carboxylic group of PTT resulting
in enhanced polarpolar interactions of the silicate layer within
PTT phase. This phenomenon contributes to an increase in tensile
strength and tensile modulus. C20A, modied with a ditallow intercalant, results in hydrophobicity of the ammonium cations, thereby
lacking in strong polar interaction within the matrix polymer.
Furthermore, as observed by Hottaand and Paul [42], LLDPE
nanocomposites prepared using surfactant with more number of
alkyl tails exhibits better dispersion of clay as compared with one
alkyl tail surfactant. In addition, surfactant with long carbon atoms
in alkyl chain induces much degree of exfoliation of clay in polyolen nanocomposites. Hence it is assumed that blend matrix in
C30B nanoclay is distributed predominantly in PTT phase. The ditallow surfactants in C20A nanoclay offers on the other hand more
hydrophobic characteristics and thus is expected to migrate more
to the dispersed m-LLDPE phase.

3.2.4.2. Effect of clay loading on impact properties. The impact

strength of PTT/MA-m-LLDPE blend as a function of clay loading is also depicted in Table 3. The test results reported in the
table reveals that the impact strength increases considerably to
the tune of 28.3% in PTT/MA-m-LLDPE/C30B and 18% in PTT/MAm-LLDPE/C20A blend nanocomposites systems at clay loading of
5 wt%. Based on thermodynamic arguments, it is concluded that
all the organic intercalant used in the surface modication of the
clays, imparts moderate to poor dispersion characteristics in PTT
and m-LLDPE phases. The PTT/nanoclay and m-LLDPE nanoclay
interactions per chain are smaller than PTT/m-LLDPE, which subsequently results in physicosorption of the nanoclay, the PTT and the
m-LLDPE on the nanoclay rather that forming interfaces [3942].
This contributes to improved miscibility of PTT/m-LLDPE blends

Table 3
Effect of nanoclay loading on the tensile and impact properties of PTT/m-LLDPE blend.
Compositions

Tensile strength (MPa)

SD

Tensile modulus (MPa)

SD

Impact strength (J/m)

SD

PTT/MA-g-m-LLDPE (70/30)
PTT/MA-m-LLDPE (70/30)/C20A 3%
PTT/MA-m-LLDPE (70/30)/C20A 5%
PTT/MA-m-LLDPE 70/30)/C30B 3%
PTT/MA-m-LLDPE 70/30)/C30B 5%

38.12
47.16
50.86
49.47
53.24

1.31
2.03
2.31
1.89
2.03

1420
2160
2322
2340
2507

2.32
2.45
3.54
3.23
2.89

44.23
50.76
52.23
53.88
56.76

1.82
1.92
1.03
1.32
2.09

580

S.K. Nayak, S. Mohanty / Materials Science and Engineering A 527 (2010) 574583

Fig. 7. Temperature dependence of storage modulus (E ) at 1 Hz for blend and

nanocomposites at 5% loading of nanoclay.

with incorporation of all the nanoclays. However, the mechanical

performance of the blend matrix varies in the following order:
PTT/MA m LLDPE/C30B > PTT/MA m LLDPE/C20E
> PTT/MA m LLDPE.
This further indicates improved interactions in C30B system as
compared with C20A and predominant role of PTT base matrix. In
all the characterization studies indicated in later sections compatibilized blend and its nanocomposites have been considered.
3.2.5. Dynamic mechanical analysis (DMA) of toughened
PTT/m-LLDPE blend nanocomposites
3.2.5.1. Storage modulus (E ). The reinforcing effect of nanoclay in
nanocomposites under variable temperature has been ascertained
using dynamic mechanical analysis. The dynamic storage modulus (E ) versus temperature traces of PTT, PTT/m-LLDPE blend and
blend nanocomposites are shown in Fig. 7. A gradual decrease in
E with increasing temperature from 150 to 200 C was observed.
It was noted that incorporation of m-LLDPE decreased the storage modulus of PTT matrix due to softening of diluting effect of
the soft elastomeric phase. Conversely, addition of organoclay into
the blend matrix results in a remarkable increase in the storage modulus over the entire investigated temperature range. This
improvement is in agreement with the moduli data obtained from
static mechanical tests as discussed earlier. This further indicates
that the presence of organoclay strongly dictates the plastic and
elastic deformation in the blend matrix. The intercalated/exfoliated
organoclay platelets dominate the reinforcing effect, while reducing the chain mobility of the polymer molecule. However, E of
the PTT matrix remain higher than the blend nanocomposite systems over the entire investigated temperature range. The blend
nanocomposites prepared using C30B organoclay displays optimum E .
3.2.5.2. Loss factor (tan ). The tan curves (Fig. 8) of virgin PTT
matrix displayed only a single peak corresponding to its glass transition. On the other hand, the blend displayed two different peaks
associated with the  relaxation of m-LLDPE phase and Tg of PTT
phase indicating typical characteristics of immiscible blends. However, the Tg of PTT phase in the blend reduced in the presence
of soft elastomeric m-LLDPE phase. The transition peak of mLLDPE phase in the blend matrix displayed a broad transition region
around 120 C, which is probably Tg of an elastomer. Incorporation
of organoclay however shifts the Tg of the blend matrix to higher
temperature regions indicating the reinforcing effect of the organoclays, which restricts the segmental motion of the matrix chains.

Fig. 8. Temperature dependence of tan at 1 Hz for blend and nanocomposites at

5% loading of nanoclay.

Furthermore, the relaxation peak of m-LLDPE could not be noticed

in the blend nanocomposites, which are probably due to inhibition
of the relaxation mechanism of the elastomeric in the presence of
organoclays.
3.2.6. Thermal characterization
3.2.6.1. Differential scanning calorimetry (DSC). DSC thermogram of
virgin PTT, virgin m-LLDPE, 70PTT/30m-LLDPE blend and the blend
nanocomposites is depicted in Fig. 9. As already cited in the earlier
sections virgin PTT depicts a melting transition around 247.59 C
with m-LLDPE at 129 C. Similar to the blend, the DSC curves of the
blend nanocomposites also exhibited two distinct Tm s conrming
presence of a phase-separated morphology. However, incorporation of organically modied nanoclays increased the Tm of the PTT
phase in blend matrix (235.23 C in PTT/MA-g-LLDPE/C20A and
236.11 C in PTT/MA-g-LLDPE/C30B blend nanocomposites) while
reducing the Tm of the m-LLDPE phase. This indicates improved
compatibility of nanoclay in the PTT matrix. The same can also be
established through solubility parameter based on enthalpic interaction.
Nanoclays are assumed to be polar compound with very high
solubility parameter (Table 4). Hence, in case of polymers with
low solubility parameter, the polymer become in compatible with
nanoclay, which results in the restriction of the polymer chains
in entering gallery space. In the present context, m-LLDPE having a
low solubility parameter does not allow the chains to accommodate
within the gallery space of the clay. On the contrary, the solubility parameter of PTT ranges between 20.04 and 21.02 (J/cm3 )1/2
as per group contribution theory which matches with C30B 21.5

Fig. 9. (a) DSC melting thermogram @ 10 C/min (a) PTT virgin, (b) PTT/m-LLDPE
(70/30), (c) PTT/MA-m-LLDPE (70/30), (d) PTT/m-LLDPE (70/30)/C20A 5%, and (e)
PTT/m-LLDPE (70/30)/C30B 5%.

S.K. Nayak, S. Mohanty / Materials Science and Engineering A 527 (2010) 574583

581

Table 4
Solubility parameters of nanoclay.
Nanoclay type

Solubility parameter (J/cm3 )1/2

C30B
C20A
C15A

21.5
16.8
16.8

(J/cm3 )1/2 . This fact might have contributed to enhanced compatibility of C30B vis-a-vis C20A with solubility parameter 16.8
(J/cm3 )1/2 in the PTT phase, enhancing the Tm .
The crystallization exotherms of PTT/m-LLDPE blend and blend
nanocomposite system were obtained at three different cooling
rates. The exothermic trace shifted to lower temperature region
with the increase in the cooling rates. Table 5 summarizes the
crystallization temperatures of PTT, its blend and blend nanocomposites. It is evident that the Tc of PTT matrix decreases from 177.86
to 176.40 C with incorporation of m-LLDPE indicating elastomeric
effect due to amorphous nature and low spherulitic growth of mLLDPE. However incorporation of nanoclay increases the Tc of PTT
phase in the blend matrix considerably. Other researchers have
reasonably explained this phenomenon that the nanoclay acts as
an effective nucleating agent. Due to facile adsorption of polymer
chains onto the surface of nanoclay resulting in enhanced crystallization temperature. Similar increases in melt crystallization
temperature in PTT organoclay nanocomposites have also been
reported by various authors. On the contrary, the Tc of m-LLDPE
phase in the blend matrix reduces with the incorporation of nanoclays. This further conrms that the nanoclay has been widely
distributed in the PTT rich phase, which has inuenced the overall
performance characteristics in the blend matrix. The nanocomposite prepared using C30B nanoclay shows an optimum increase in
Tc up to 191.55 C, thus revealing efcient compatibility.
Briey summarizing, Tc of blend nanocomposites is higher as
compared with the blend matrix and follows the following increasing orderblend matrix < C20A blend nanocomposites < C30B
blend nanocomposites.
The differences in the crystallization behaviors primarily
depend on the functionality of nanoclays and its dispersion in each
case is different. Although it is evident that the nanoclays not only
promotes nucleation, but also provides large surface area for the
crystals to grow. Figs. 1012 indicate the effect of cooling rates on
crystallization temperature of blend and blend nanocomposites. As
cooling rate increases, crystallization peak temperature (Tp ) of PTT
phase in all compositions decreases. C30B nanocomposites show
a maximum crystallization peak temperature at all cooling rates
as compared with other nanocomposites and virgin polymer. The
high Tp value at low cooling rates indicates that crystallization initiates at early stage. Lower cooling rate helps in the crystallization
of small chains followed by crystallization of the longer chains to
align themselves.

Fig. 10. DSC thermo gram of PTT/m-LLDPE (70/30): (a) 10 C/min, (b) 20 C/min, and
(c) 30 C/min.

The time of crystallization (Tc ) that is required for its temperature to drop from melting temperature to crystallization peak
temperature depending on the cooling rate applied, has been calculated using the following equation:
Tc =

Tm Tc


where Tm , Tc and  are the melting temperature, crystallization

temperature and cooling rate. The reciprocal value of time of crystallization (Tc ) as function of cooling rate is represented in Fig. 13. It
is evident that the rate of crystallization representing the reciprocal
value of peak time (Tc ) increases for PTT/m-LLDPE with the increase
in the cooling rates. Similar phenomenon was also noticed in
case of PTT/m-LLDPE/C20A blend nanocomposites system with an
optimum increase in case of PTT/m-LLDPE/C30B nanocomposites
system, thus indicating that the crystallization process proceeds

Fig. 11. DSC thermogram of PTT/m-LLDPE (70/30)/C20A 5%: (a) 10 C/min, (b)
20 C/min, and (c) 30 C/min.

Table 5
Crystallization temperatures of PTT/m-LLDPE blend and blend nanocomposites.
Scanning rate
( C/min)

Compositions

10
10
10
20
20
20
30
30
30

PTT/m-LLDPE (70/30)
PTT/m-LLDPE (70/30)/C 20A 5%
PTT/m-LLDPE (70/30)/C 30 B 5%
PTT/m-LLDPE (70/30)
PTT/m-LLDPE (70/30)/C 20A 5%
PTT/m-LLDPE (70/30)/C 30 B 5%
PTT/m-LLDPE (70/30)
PTT/m-LLDPE (70/30)/C 20A 5%
PTT/m-LLDPE (70/30)/C 30 B 5%

Tc ( C)
PTT

m-LLDPE

176.40
187.41
191.55
174.52
180.10
182.79
161.94
177.57
179.76

110.50
108.98
109.12
107.58
101.43
102.59
102.95
102.59
101.60

Fig. 12. DSC thermogram of PTT/m-LLDPE (70/30)/C30B 5%: (a) 10 C/min, (b)
20 C/min, and (c) 30 C/min.

582

S.K. Nayak, S. Mohanty / Materials Science and Engineering A 527 (2010) 574583

temperature (Tfd ) 503.47 C. Incorporation of m-LLDPE decreases

Tid of matrix from 352.12 to 345.97 C and Tfd of matrix from 503.47
to 495.90 C. This is predominantly attributed to lower degradation
temperature of ethylene linkage due to weak bonding between
them and presence of side chain branching (510%) in m-LLDPE.
Further addition of organoclays substantially increases the thermal
stability (Tid , Tfd ) of the blend matrix. Blend nanocomposites with
C20A organoclay has highest thermal stability due to higher modier concentration and gallery spacing. It is believed that higher
modier concentration renders higher hydrophobic characteristics
[37]. The stable morphology of the dispersed phase and the presence of intercalated silicate layers may be the primary reason for
the enhanced thermal stability of the blend nanocomposites. Furthermore, as referred by Lim and co-workers [19], the improvement
in the thermal stability for polymer blend nanocomposites due to
formation of char, which hinder the out diffusion of volatile decomposition products, as direct result of decrease in permeability.
Fig. 13. TGA thermogram of (a) virgin PTT, (b) m-LLDPE virgin, (c) PTT/m-LLDPE
(70/30), (d) PTT/m-LLDPE (70/30)/C 20A 5%, and (e) PTT/m-LLDPE (70/30)/C 30B 5%.
Table 6
Crystallization peak time and activation energy (E) of PTT/m-LLDPE blend and
nanocomposites.
Scanning rate
( C/min)

Compositions

Tc (min)

E (kJ/mol)

10
10
10
20
20
20
30
30
30

PTT/m-LLDPE (70/30)
PTT/m-LLDPE (70/30)/C 20A 5%
PTT/m-LLDPE (70/30)/C 30 B 5%
PTT/m-LLDPE (70/30)
PTT/m-LLDPE (70/30)/C 20A 5%
PTT/m-LLDPE (70/30)/C 30B 5%
PTT/m-LLDPE (70/30)
PTT/m-LLDPE (70/30)/C 20A 5%
PTT/m-LLDPE (70/30)/C 30B 5%

6.183
4.308
4.221
3.123
2.546
2.409
2.471
1.811
1.807

1028.11
716.33
701.87
1038.41
846.53
801.31
1232.43
970.08
901.74

via a nucleation controlled process based on cooling rates [39,40].

The activation energy for isothermal crystallization of PTT virgin, blend matrix and nanocomposites were calculated using the
Kissenger model [43] and depicts in Table 6. The Kissenger method
is given as follows:
d[ln (/Tp 2 )]
E
=
R
d(1/Tp )
where R is a gas constant and Tp the peak temperature. Incorporation on nanoclay shifts the activation energy to lower value.
This indicates the promotion of nucleation in the PTT matrix
and provides the conrmation that nanoclay functions as effective nucleating agents. Negative activation energies imply that
crystallization mechanisms are accelerated by decreasing the temperatures. Similar type of behavior has also been reported by Mulla
et al. [44].
3.2.6.2. Thermogravimetric analysis (TGA). Table 7 and Fig. 13
shows TGA results of virgin polymer blend and blend nanocomposites at different compositions. Virgin PTT exhibits an initial
degradation temperature (Tid ) of 352.12 C with nal degradation
Table 7
TGA results of PTT virgin, PTT/m-LLDPE blend and nanocomposites.

4. Conclusions
PTT/MA-m-LLDPE blend nanocomposites were prepared employing melt compounding technique.
Incorporation of m-LLDPE to the PTT matrix, resulted in increase
in the impact strength of the virgin matrix while reducing the
tensile properties. However, incorporation of C30B and C20A
nanoclays resulted in increase in impact strength and also compensated the loss of tensile and exural properties in the blend
matrix.
Morphological observations conrmed efcient dispersion of
nanoclays and intercalation of the polymer segments in the
gallery space in case of organically modied nanocomposites.
The particle size in the blend matrix reduced with addition of
nanoclays and the interparticle distance reduced.
The blend nanocomposites also displayed a mixed nanomorphology, with the nanoparticles preferentially distributed in PTT
phase of the blend. Few stacks of intercalated clay layers were
also observed in PTT/m-LLDPE/C20A nanocomposites where as in
PTT/m-LLDPE/C30B ternary system, a uniform, but random clay
dispersion was observed.
DSC measurements revealed that, the blend nanocomposite system displayed two distinct Tm , which reveals phase-separated
morphology. Incorporation of organically modied nanoclays
increased the Tm of the PTT phase in blend matrix, while reducing
the Tm of the m-LLDPE phase. This indicates improved compatibility of nanoclay in the PTT matrix.
In case of blend nancomposites, the storage modulus increased
with the incorporation of the nanoclays. The tan of the blend
matrix displayed two distinct transitions corresponding to PTT
and m-LLDPE.
The Tg of the blend matrix shifted to high temperature regions
with the incorporation of clays.
TGA thermograms also revealed a higher thermal stability of the
blend matrix in the presence of nanoclays.
For the rubber toughened PTT (PTT/m-LLDPE blend), a good balance of properties in terms of stiffness and strength can be
achieved at an optimal concentration of clays and maleation.
References

Composition (wt%)

Tid ( C)

Td at 50%
( C)

Tfd ( C)

%Ash
content

PTT virgin
m-LLDPE virgin
PTT/m-LLDPE (70/30)
PTT/m-LLDPE (70/30)/C20A 5%
PTT/m-LLDPE (70/30)/C30B 5%
PTT/m-LLDPE (70/30)/B109 5%

352.12
326.86
345.97
358.70
357.84
358.60

413.80
423.30
495.90
433.40
427.50
420.60

503.47
490.10
495.90
531.30
512.80
498.80

0.00
9.97
0.49
3.90
4.99
3.69

[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

S.P. Mishra, L. Deopure, Polym. Bull. 26 (1985) 5.

Y. Yu, K. Choi, Polym. Eng. Sci. 37 (1997) 91103.
D. Nabisaheb, J.P. Jog, J. Polym. Sci.: Part-B: Polym. Phys. 37 (1999) 24392445.
N. Avramova, Polymer 36 (1995) 801810.
J.M. Wfer, US Patent 4,485,212, 1984.
C.F. Pratt, S.V. Phadke, E. Olivier, US Patent 4,965,111, 1990.
S. Wu, Polymer 26 (1985) 1855.
Z.Z. Yu, Y.C. Qu, G.H. Hu, J. Appl. Polym. Sci. 69 (1998) 17111718.
H. Chen, B. Yang, H. Zhang, J. Appl. Polym. Sci. 77 (2000) 928933.

S.K. Nayak, S. Mohanty / Materials Science and Engineering A 527 (2010) 574583
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]

A. Arostegui, M. Gaztelumendi, J. Nazabal, Polymer 42 (2001) 95659574.

A. Arostegui, J. Nazabal, Polymer 35 (2003) 5663.
A. Arostegui, J. Nazabal, J. Appl. Polym. Sci. 91 (2004) 260269.
A. Arostegui, J. Nazabal, J. Polym. Sci.: Phys. Ed. 41 (2003) 22362247.
F. Stricker, Y. Thomann, R. Mulhaupt, J. Appl. Polym. Sci. 68 (1998) 18911901.
M. Smita, K.N. Sanjay, J. Appl. Poly. Sci. 104 (2007) 31373144.
G. Guerrica Echevarria, J.I. Eguiazabal, J. Nazabal, Polym. Eng. Sci. 46 (2006)
172180.
B.B. Khatua, D.J. Lee, H.Y. Kim, J.K. Kim, Macromolecules 37 (2004) 24542459.
S.S. Ray, M. Bousmina, Macromol. Rapid Commun. 26 (2005) 16391646.
J.W. Lim, A. Hassan, A.R. Rahmat, M.U. Wahit, Polym. Int. 55 (2006) 204215.
Y.J. Li, H. Shimizu, Polymer 45 (22) (2004) 73817388.
Y.J. Li, H. Shimizu, Macromol. Rapid Commun. 26 (9) (2005) 710715.
M. Fena, F.L. Gong, Polym. Int. 53 (10) (2004) 15291537.
X.Y. Huang, S. Lewis, W.J. Brittain, R.A. Vaia, Polym. Prep. 41 (1) (2000) 589597.
X.Y. Huang, S. Lewis, W.J. Brittain, R.A. Vaia, Macromolecules 33 (2000)
20002010.
B.J. Chisholm, R.B. Moore, G. Barber, F. Khouri, A. Hempstead, M. Larsen, Macromolecules 35 (14) (2002) 5508.
J. Zhang, J. Appl. Polym. Sci. 91 (2004) 16571666.

[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]

583

M.L. Xue, Y.L. Yu, H.H. Chuah, E. Polym. J. 43 (2007) 38263831.

I. Aravind, P. Albert, Polymer 45 (2004) 49254932.
G. Guerrica Echevarria, E. Polym. J. 43 (2007) 10271033.
N.A. Mehta, D.D. Kale, J.G. Kim, B.W. Jo, Int. J. Plast. Tech. 5 (2002) 6571.
N. Dangseeyun, S. Pitt, N. Manit, Polym. Testing 23 (2004) 187194.
S.H. Zafari, Polym. Bull. 54 (2005) 417425.
T.K. Kang, Y. Kin, W.K. Lee, H.D. Park, J. Chow, C.S. Ha, J. Appl. Polym. Sci. 72
(1999) 989997.
L. Marquez, M.A. Sabino, I.A. Rivero, Polym. Bull. 41 (1998) 191198.
J.K. Mishra, Y.W. Chang, N.S. Choi, Polym. Eng. Sci. 47 (2007) 863870.
Z. Liu, K. Chen, D. Yan, E. Polym. J. 39 (2003) 23592366.
E.K. Drawn, A.K. Mohanty, Y. Parulker, D. Hasija, B.R. Harte, M. Misra, Compos.
Sci. Tech. 67 (2007) 31683175.
L. Priya, J.P. Jog, J. Polym. Sci.: Polym. Phys. 41 (2003) 31.
S.M. Lai, H.C. Li, Y.C. Liao, E. Polym. J. 43 (2007) 16601671.
S. Pitt, J. Appl. Polym. Sci. 78 (2000) 338354.
Y. Xu, W.J. Brittain, R.A. Vaia, G. Price, Polymer 47 (13) (2006) 45644570.
S. Hottaand, D.R. Paul, Polymer 45 (2004) 76397645.
H.E. issinger, J. Res. Nat. Bur. Stant. 57 (1956) 217225.
A.A. Mulla, J. Mathew, S.K. Yeh, R. Gupta, Compos: Part A 39 (2008) 204217.