Dynamic Mechanical Performances

of Polyester–Clay Nanocomposite
Thick Films

CARMINE LUCIGNANO,* FABRIZIO QUADRINI AND LOREDANA SANTO

Department of Mechanical Engineering
University of Rome Tor Vergata, Via del Politecnico n 1, 00133 Rome, Italy

ABSTRACT: Dynamic mechanical properties of polyester–montmorillonite nano-

composite thick films, prepared by the in situ intercalative polymerization method,
were evaluated in a tensile mode. A fast fabrication procedure was chosen to allow
industrial applications. A total time less than 1 h was sufficient to obtain a thick
film which could be cut for the specimen preparation. The final films had a thickness
of 250 mm and a nano-clay content ranging from 0 to 10 wt%. A differential scanning
calorimeter was used to investigate the effect of the clay content on the resin
polymerization kinetics whereas tensile tests were performed to make a comparison
with dynamic mechanical results. The maximum in the mechanical performances was
obtained at the clay content of 1 wt% at which an increase of about 55% for the
storage modulus was measured in comparison with the unfilled resin.

KEY WORDS: nanocomposite, thick films, DMA.

INTRODUCTION

ANOCOMPOSITES ARE A relatively new class of materials with unique properties

N typically not shared by conventional microcomposites. In 1996, Giannelis discussed
polymer nanocomposites with layered silicates as an inorganic phase [1]. In his study,
special emphasis was given to a new synthesis approach by direct polymer melt
intercalation. The process involves mixing the layer silicate with the polymer and heating
the mixture above the softening point of the polymer. In 1998, Kornmann et al. studied
the properties of montmorillonite–unsaturated polyester nanocomposites by means of
mechanical tests on bulk specimens [2]. The interest in this class of nanocomposites
depends on the medical and sanitary applications. Dealing with flexible or rigid films,
packaging is a further potential application because of the material transparency and the
oxygen-barrier properties.
In 2000, Suh et al. investigated the effect of the fabrication method on the property and
formation mechanism of the same kind of nanocomposite [3]. They also used a dynamic

*Author to whom correspondence should be addressed. E-mail: lucignano@ing.uniroma2.it

Journal of COMPOSITE MATERIALS, Vol. 42, No. 26/2008 2841

0021-9983/08/26 2841–12 $10.00/0 DOI: 10.1177/0021998308096953
ß SAGE Publications 2008
Los Angeles, London, New Delhi and Singapore
2842 C. LUCIGNANO ET AL.

mechanical analyzer (DMA) but always on bulk specimens and in a dual cantilever
bending mode.
In 2002, in their study on the polyester–clay nanocomposites, Bharadwaj et al. observed
that storage modulus and loss factor were monotonically shifted toward high frequency
values and tensile modulus was found to decrease with increasing clay content [4]. In 2003,
Chen and Curliss obtained better results by using an epoxy matrix [5]. Also in this case,
DMA tests were carried out on bulk specimens in the bending mode. In the same year,
optimal results, in terms of increase in tensile strength, impact strength, heat resistance,
and swelling resistance were also obtained with an unsaturated polyester resin by
Zhang et al. [6]. They prepared nanocomposites by dispersing polymerizable qua-
ternary ammonium-modified montmorillonite in the resin matrix. In 2004, Hu et al.
studied the viscoelastic properties and the thermal degradation kinetics of silica/PMMA
nanocomposites by means of DMA and TGA (thermo-gravimetric analysis) [7]. In the
same year, Fu and Qutubuddin investigated the synthesis of unsaturated polyester–clay
nanocomposites [8]. They used reactive organoclays and employed also a DMA technique
in the bending mode. Avlar and Quiao prepared nylon 6-silicate nanocomposites. They
studied the effect of cooling rate on fracture resistance. They found that the addition of
silicate nanolayers, while increasing the cooling rate, has a beneficial effect to the fracture
toughness [9]. In 2005, Wang et al. studied the mechanical properties and thermal stability
of polyethylene terephtalate/montmorillonite nanocomposites, finding that the composite
has the optimum comprehensive mechanical property when organo-montmorillonite
content is 1%. At the same montmorillonite content the thermal degradation onset
temperature of nanocomposite increases by 128C [10]. In 2006, Vlasved et al. prepared a
three-phase thermoplastic composite consisting of a main reinforcing phase of woven glass
fibers and a polyamide 6-silicate nanocomposite. The nancomposite used in their study has
a modulus that was much higher than unfilled polyamide 6. They discovered that the fiber
composites with a nanocomposite matrix have a more than 40% increase in flexural and
compressive strength at an elevated temperature [11]. In the same year, Bao and Tjong
prepared polypropylene/organo-montmorillonite nanocomposites via melt compounding
toughened with maleated styrene–ethylene–butylene–styrene, they found that the presence
of organo-montmorillonite increases the storage modulus and a balance between the
stiffness and toughness of the nanocomposites can be achieved by properly controlling
their elastomer and clay content [12]. In one of the most recent contribution on polymer–
clay nanocomposites, in 2006, Meneghetti and Qutubuddin employed DMA on bulk
samples in the bending mode [13].
Despite the discussed applications, nanocomposite films are rarely mentioned in
scientific literature, especially dealing with polyester–clay nanocomposites. Nevertheless
they could be produced on a large scale if the processing time would be reduced. In this
article the authors investigate this kind of nanocomposite and propose a DMA testing
procedure by means of a tensile mode. In fact, new characterization procedures
are necessary to study new processes and materials, and to find new applications.
The mentioned studies provide useful information about the fabrication of nanocomposite
specimens but they do not focus on films.
Generally, scientific papers mention bulk specimens and therefore DMA tests are
carried out in the bending mode. Unfortunately film stiffness is generally low and do not
allow a correct characterization by the bending mode. In thicker films, small distortions
may affect significantly the measure due to the bad contact between the sample and the
supports. Therefore the bending mode needs thick bulk samples but they are expected to
Dynamic Mechanical Performances of Polyester–Clay Nanocomposite Thick films 2843

behave differently from films. Moreover, in-plane tensile properties are often preferred to
compare the properties of different nanocomposites due to the application of a uniform
stress field: in the scientific works, mechanical tensile tests are generally performed instead
of flexure tests. In conclusion, the tensile mode seems to be more appropriate for films but
the application of DMA in the tensile mode to nanocomposite films was never discussed
before in the scientific literature. The obtained correlation between DMA results and
tensile tests will be useful to show the validity of this choice.

EXPERIMENTAL

Materials

The nanocomposite films were fabricated by dispersing a nanoclay powder into an

unsaturated polyester (UP) matrix. The employed nanofiller was montmorillonite (MMT)
(Dellite 43B by Laviosa Chimica Mineraria). This nanoclay derived from especially
purified and natural montmorillonite (MMT) which was modified with quaternary
ammonium salt (dimethyl benzylhydrogenated tallow ammonium). The composite matrix
was made of a commercial polyester resin which was catalyzed by means of 2 wt% of
methylethylketone.
From manufacturer’s data, particle size, in dry conditions, was expected about 7–9 nm
with a density of 1.6 g/cm3. However, nano-clay was characterized by means of SEM
analysis (FEG-SEM Leo Supra 35 in secondary electron mode). A distribution curve of the
MMT size was obtained by dispersing the powder in water and by utilizing an engine
exhaust particle sizer spectrometer TSI 3000 and a fine particle sampler DEKATI FPS 4000.

Preparation of Thick Films

The nanocomposite films were prepared by the in situ intercalative polymerization

method [14]. The nano-clay was added to the uncatalyzed polyester resin and the mixture
was stirred for 30 min by a magnetic stirrer. The catalyzer was then added and mixed for
another 30 s. Subsequently, a drop of the mixture was dripped by a stepper on an
aluminum flat support and spun by a spin-coater (Chemat Technology Spin Coater
KW-4A). A two stage spin process was used to guarantee a uniform thickness of the film.
In the first stage a speed of 1000 rpm was applied for 10 s whereas in the second stage a
speed of 2500 rpm was applied for 3 s. After spinning the support was placed on a heater
plate for 30 min at a temperature of 808C. The films were left to cool at room temperature.
In order to detach the film from the metallic support, the same support was rapidly cooled
by liquid nitrogen. A final thickness of 250 mm was measured at the end of the fabrication.
Five filler contents (0.5, 1, 3, 5, 10 wt%) were chosen for the nanocomposite fabrication
and five films were fabricated for each content.

Composite and Film Characterization

The nano-clay was characterized together with filled and unfilled samples by means of
X-ray diffraction (Philips PW1729) to evaluate the dispersion of clay layers. In diffraction
2844 C. LUCIGNANO ET AL.

Figure 1. DMA configuration for the tensile mode.

tests a Co-K radiation (l ¼ 0.179 nm) was used in the 2 range of 3–938. The un-cured
polyester-clay mixture and the unfilled polyester were also characterized by differential
scanning calorimetry (Netzsch DSC 200PC). A double scan was performed at the heating
rate of 108C/min to study the polymerization kinetics; the first scan from 150 to 2208C
and the second scan from 50 to 2008C. The lower initial temperature of the first scan
permitted to measure the glass transition temperature of the un-cured samples. After the
first scan the samples were completely hardened.
Time dependent properties of polyester–clay and unfilled polyester films were measured
by using a dynamic mechanical analyzer (Netzsch DMA 242C). The specimens were
approximately 10 mm in length and 5 mm in width. The tests were carried out in a tensile
mode (Figure 1) after the calibration procedure. This configuration was chosen to evaluate
the tensile behavior of the film under an oscillating load to allow a comparison with the
classic tensile test. The analyses were carried out at a frequency of 10 Hz and a heating rate
of 58C/min from room temperature to 508C. In the test set-up, a displacement range of
120 mm was set, as well as a maximum dynamic force of 4 N and a ratio of 2 between the
static and the dynamic force. The DMA samples were also used in tensile tests (by a MTS
Alliance RT/50 machine) up to the final break using a rate of 0.5 mm/min and the gage
length of 10 mm. As previously mentioned, five films were prepared for each filler content,
and they were all characterized by DMA and tensile test.

RESULTS AND DISCUSSION

Nano-clay and Composite Characterization

Figure 2 shows the SEM micrographs of the nanoclay with different magnifications. It is
evident the presence of agglomerates as well as the layered structure of the montmorillonite.
The size of the smallest particles is in the range of few nanometers. The spectrometer
provided a mean size of the particles about 35 nm (Figure 3) but this datum could be
dependent on the particular test conditions (i.e., the dispersion in water).
Dynamic Mechanical Performances of Polyester–Clay Nanocomposite Thick films 2845

20 μm EHT = 5.00 kV Signal A = Inlens Date : 15 Jul 2008

Mag = 1.00 K X WD = 3 mm Photo no. = 3885 Time : 9:34:32

2 μm EHT = 5.00 kV Signal A = Inlens Date : 15 Jul 2008

Mag = 10.00 K X WD = 3 mm Photo no. = 3882 Time : 9:32:29

1 μm EHT = 5.00 kV Signal A = Inlens Date : 15 Jul 2008

Mag = 50.00 K X WD = 3 mm Photo no. = 3881 Time : 9:30:47

Figure 2. SEM images of nanopowders at different magnifications.

2846 C. LUCIGNANO ET AL.

0.14

0.12

0.1

Frequency 0.08

0.06

0.04

0.02

0
06

.8

.3

.1

.5

34

.3

.4

.6

5
7.
10

14

19

25

45

60

80
8.

10
D (nm)

Figure 3. Distribution curve of MMT size.

5.65

23.4 MMT
Intensity (a.u.)

25.75
41.5

10 vol %

1 vol %
UP
0 20 40 60 80 100
2θ (deg)

Figure 4. Results from X-ray diffraction of nanopowder and samples.

The results from X-ray diffraction are reported in Figure 4 in the case of the nanoclay,
unfilled polyester, and two composites (the 1 and 10 wt% filled). In the nanoclay curve some
peaks are visible in the observed 2 range, and are indicated by arrows. The highest peak
(5.658) is relative to the basal spacing of modified MMT (according to Ref. [4]). The unfilled
polyester presents a large peak which is typical of amorphous thermosets. All the main peaks
of MMT are still visible in the curve of the 10 wt% clay filled composite even if partially
attenuated whereas they completely disappear in the 1 wt% clay filled composite. Evidently
a better dispersion of clay layers was obtained in the 1 wt% clay filled composite as the
presence of order could not be confirmed from the data also at higher d-spacing.
Figure 5 shows the DSC results for the unsaturated polyester and the nanocomposites
with 1 and 5 wt% clay content. In the first scan, an enthalpy relaxation peak is clearly visible
for all the samples near the monomer glass transition temperature (about 408C). At higher
temperatures (near 808C) an exothermic peak is visible due to the polymerization reaction.
In the same Figure 5, the second scans are also reported to show that the resin–glass
transition temperature seems to be independent of the filler content. In fact small variations
Dynamic Mechanical Performances of Polyester–Clay Nanocomposite Thick films 2847

I scan
UP
1 wt %

0.5 5 wt %
Endothermic (W/g) ->

Baseline
correction

UP
1 wt %
5 wt %

5 wt %

1 wt %

UP
0.1

0 50 100 150 200

II scan

−200 −100 0 100 200

Temperature (°C)

Figure 5. DSC results.

were measured in the inflection point which is in the range of 50–558C without any
significant trend. In the small picture in Figure 5, a comparison between the polymerization
peaks is shown after the baseline correction. By increasing the MMT content, the cure
onset temperature significantly decreases whereas the reaction heat increases only for
the higher content of 5 wt%. This improvement in reaction kinetics is dependent on
the quaternary ammonium salt used to modify clays; in fact, the acidity of alkylammonium
ions catalyze the resin [15].

DMA Results

Figure 6 shows the comparison between the nanocomposites filled at 1 and 5 wt% in
terms of storage modulus. The comparison is made by averaging the five experimental
curves for each content. The higher performance of the 1 wt% clay filled polyester is clear
and the data dispersion is low at every temperature. Even if reaction kinetics improve with
higher clay content (Figure 5), this is not related to an increase of storage modulus.
Figure 7 shows the mean storage modulus (E0 ) dependence on the MMT content for six
temperature values. A similar trend is visible for all the curves, by increasing the MMT
content the storage modulus increases up to a maximum (at 1 wt%). After the maximum,
the nanocomposite storage modulus remains higher than the unsaturated polyester storage
modulus and a plateau is reached. The maximum occurrence in the reported set of
experiments lends credence to the hypothesis that the proposed process parameters allows
2848 C. LUCIGNANO ET AL.

4000
1 wt % clay
5 wt % clay

Storage modulus (MPa)

3000

2000

1000

0
25 30 35 40 45 50
Temperature (°C)

Figure 6. Comparison between DMA curves for two nanocomposites.

3000

2500
Storage modulus (MPa)

2000

1500

1000 25°C 30°C

35°C 40°C
45°C 50°C
500
0 2 4 6 8 10
Wt % Clay

Figure 7. Storage modulus dependence on the clay content.

the best nanoclay dispersion between 1 and 3 wt% content. By changing mixing
parameters (such as mixing time and temperature), other studies obtained an increase in
mechanical properties up to the 5 wt% content of clays. However, they discussed very long
preparation times, especially for the mixing stages, whereas in this study a fast procedure
was preferred. An erroneous choice in the mixing time and mode may affect the
nanocomposite properties; by reducing the mixing time the strong tendency of nano-
particles to agglomerate is hardly controlled [16], therefore the powder agglomerates even
at low contents. This is because conventional processing techniques can hardly control the
level of particle agglomeration due to the limited shear force during the mixing procedure.
At the maximum the improvement in storage modulus is about 55% in comparison with
unsaturated polyester, even if only 1 wt% of MMT is used.
As expected an increase in temperature leads to a decrease in storage modulus; however,
near the maximum the effect of the temperature on the storage modulus is less
pronounced. This occurrence is more visible in Figure 8, in which the dependence of the
Dynamic Mechanical Performances of Polyester–Clay Nanocomposite Thick films 2849
0.25

0.2
Loss factor

0.15

0.1 25°C
30°C
35°C
0.05 40°C
45°C
50°C
0
0 2 4 6 8 10
Wt % Clay

Figure 8. Loss factor dependence on the clay content.

3000
0 wt% clay
0.5 wt% clay
2550 1 wt% clay
Storage modulus (MPa)

3 wt% clay
5 wt% clay
2100 10 wt% clay

1650

1200

750
0.075 0.105 0.135 0.165 0.195 0.225
Loss factor

Figure 9. Correlation between storage modulus and loss factor.

mean loss factor on the montmorillonite content is shown for the same temperatures. The
curves reveal that the nanoclay content causes the decrease of the loss factor up to a
minimum at 1 wt%. The trend of loss factor with the clay content is the inverse of the trend
observed for the storage modulus (Figure 7). Higher values of storage modulus are related
to lower values of loss factor for all the samples (Figure 9). This correlation between the
time dependent properties confirms the high quality of DMA results.

Tensile Test Results

Figure 10 shows the dependence of the tensile strength on the nanoclay content. A very
low dispersion was obtained during experimentation in analogy to the DMA test .The curve
has also a trend similar to curves of Figure 7 where the dependence of the storage modulus
on the MMT content is shown. The tensile strength increases from the unsaturated polyester
2850 C. LUCIGNANO ET AL.

80

Tensile strength (MPa)

60

40

20

0
0 2 4 6 8 10
Wt % Clay

Figure 10. Tensile strength dependence on the clay content.

0.05

0.04
Elongation at break

0.03

0.02

0.01

0
0 2 4 6 8 10
Wt% Clay

Figure 11. Elongation at break as a function of the clay content.

to 1 wt% MMT nanocomposite and after it decreases. Also in this case a plateau is reached
after the maximum but at a value similar to the pure polyester. Elongation at break is
reported in Figure 11 as a function of the clay content. The trend is similar to the tensile
strength except for the datum of the unfilled polyester which presents the highest ductility.
However the elongation at break is very low for all the samples (always less than 3%) due to
the brittle nature of the polyester matrix.
The nanocomposite behavior under tensile test confirms that best-filled dispersion was
obtained with 1 wt% for the proposed process conditions. At higher contents the creation
of agglomerates from this concentration causes the decrease of tensile strength.
The particles are weakly linked and act as crack-primer. In this case, when relatively
large agglomerates would remain in the matrix a propagating crack could encounter a
stress concentration locally and then easily induce the initiation of the final failure [17].
This kind of nanocomposite is generally known as a low miscibility system in which the
nano-effect is strongly reduced.
Dynamic Mechanical Performances of Polyester–Clay Nanocomposite Thick films 2851

The value of tensile strength at the peak represents a considerable improvement, about
150% compared to unsaturated polyester; in spite of the very low content of nanoclay.

CONCLUSION

Unsaturated polyester–montmorillonite nanocomposite thick films were prepared at

various filler contents by the in situ intercalative polymerization method. A tensile DMA
mode was used to measure the viscoelastic properties of the film allowing the comparison
with tensile test results. The DMA results permitted the study of the complexity of the
interaction between nanofiller and matrix. The storage modulus had a significant
improvement at a low nanoclay content whereas it exhibits a progressive decrease by
increasing the clay concentration. The high modulus of nanocomposites is attributed to the
combination of dynamic effect of particles embedded in a viscoelastic medium, and
mechanical restraint introduced by the clay nanolayers that reduce the mobility and
deformability of the matrix [8].
In the proposed experimentation, a maximum in the nanocomposite mechanical
performance was observed at 1 wt% filler content. Both the tensile storage modulus and
the tensile strength have an increase about 150% in comparison with the unfilled polyester
resin. It is a noticeable increase as typically a micro-particle filled polyester composite with
a 20 wt% filler content exhibits an elastic modulus which is less than the double of the
unfilled matrix.
The trend of DMA results have been discussed by considering the difficulty of an ultra
fine dispersion of the filler at high levels of loading. However, the obtained increase in
mechanical performances at 1 wt% filler content is very attractive considering the fast
fabrication procedure employed. A similar improvement in conventional micro–filled
composite needs a much higher concentration which is in turn related to several
disadvantages (higher density, opacity, residual stress). In addition the loss factor
decreases at a low concentration of nanoclays and then exhibits an increase with increasing
clays, to support the previous hypothesis. The tensile strength was measured by an MTS
machine and also the results of this test show clearly an improvement of these properties at
a low concentration of MMT.

ACKNOWLEDGMENT

The authors want to acknowledge Prof. Roberto Montanari for his help in the
discussion of the X-ray results.

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