Dynamic Mechanical Behaviour of Banana-pseudostem-filled Unplasticised Polyvinyl Chloride Composites

Dynamic Mechanical Behaviour of Banana-pseudostem-filled

Unplasticised Polyvinyl Chloride Composites
E.S. Zainudin1*, S.M. Sapuan1, K. Abdan1, and M.T.M. Mohamad2
1
Faculty of Engineering, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
2
Faculty of Agriculture, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
Received: 15th February 2008, Accepted: 14 July 2008

SUMMARY
The dynamic mechanical behaviour of unplasticized polyvinyl chloride (UPVC) and its composites reinforced
with banana pseudostem (BPS) fibres has been studied, with special reference to the effect of filler loading and
temperature. Dynamic properties such as the storage modulus (E′) and damping behaviour (tan δ) were evaluated
as a function of BPS volume fraction. It was found that the storage modulus increased with increasing BPS
content in the samples. At lower temperatures (in the glassy region), the E′ values of the samples were highest in
both unmodified and acrylic-modified BPS/UPVC composites with 40% fibres. The glass transition temperature
(Tg) associated with the damping peaks of BPS/UPVC composites reached its highest value at 94.9 °C with
20% fibre loading for unmodified BPS/UPVC composites, whereas, in the case of acrylic-modified composites,
CA4 had the highest Tg at 98.7 °C.

INTRODUCTION
The increases in cost and the adverse
effect on the environment of synthetic-
fibre-reinforced polymers have
necessitated research into developing
alternative natural-based raw material
for the production of composite panels.
The inclusion of natural fibres in some
thermoplastic polymers is the right
solution. These composites not only
have altered mechanical and thermal
characteristics but also reduced
overall cost, making them more
environmentally and health friendly.
Advantages such as low weight and high
performance can also be developed to
meet specific performance properties.
The inclusion of fibre, especially
natural fibre, in polymers, affects the
thermal analysis and has been studied
by several researchers1-4. Techniques
used in the thermal analysis of
materials to determine changes in
weight can be divided into two types:
static and dynamic. In the present
study, dynamic thermal analysis was
employed, with the application of
an oscillatory pulsing force to the
sample. This type of technique is
called dynamic mechanical analysis
(DMA) and is used to study different
types of fibre-reinforced thermoplastic
materials undergoing various types
of dynamic stressing during service.
DMA is generally used to investigate
the dynamic mechanical properties
of composite materials in order to
determine their relevant stiffness and
damping characteristics for various
applications. It is also widely used to
evaluate the behaviour of composites
exposed to high temperatures up to
their breakdown point. The technique
separates the dynamic response of
materials into two distinct components:
an elastic component (E′) and a
viscous or damping component (E″).
The elastic process describes the
energy stored in the system, whereas
the viscous component describes the
energy dissipated during the process.
In a ‘natural fibre–thermoplastic’
composite, both phases exhibit
viscoelastic behaviour. DMA provides
rapid assessment of the viscoelastic
properties of such materials.
As the dynamic mechanical properties
of composite materials play an
important role during their service
at high temperatures, studies of the
dynamic mechanical properties of
these materials are of great importance.
Furthermore, because of the highly
temperature-dependent mechanical
properties of such composites, the
application of a method that monitors
property changes over a range of
temperatures is critical5-9. The objective
of the present study is to evaluate the
dynamic mechanical characteristics
of samples manufactured with various
contents of BPS as filler in UPVC–resin
composites.

*
Corresponding author. Tel.: ++603 89466317; fax: ++603 86567122
E-mail address: edisyam@eng.upm.edu.my
©
Smithers Rapra Technology, 2009

Polymers & Polymer Composites, Vol. 17, No. 1, 2009 55

 E.S. Zainudin, S.M. Sapuan, K. Abdan, and M.T.M. Mohamad

EXPERIMENTAL Table 2. Properties of UPVC4

Specification Value Units
Materials
Specific gravity 1.4–1.43 g/cm3
The matrix used in this study was Specific heat 0.25 kcal/kg °C
UPVC (IR064) supplied by Polymer
Thermal conductivity 0.13 kcal/(h cm oC)
Resources Sdn. Bhd., Kelang, Selangor,
o
Malaysia. This UPVC was a medium- Coefficient of linear expansion 5.0 × 10−5 C−1
molecular-weight resin designed Tensile strength at 20 °C 500 kg/cm2
for general-purpose application. Elongation (min) 80 %
It was a rigid polymer with an Modulus of elasticity 1200–1500 MPa
amorphous structure. Some additives Water absorption <4 mg/cm2
were introduced into the neat PVC to
make it unplasticised. The BPS filler
used in this study was taken from the Table 3. Formulation blend of the BPS/UPVC composite
banana tree trunk, and is known as Constituent Weight for each blending process (g)
‘pseudostem’. Tables 1 and 2 show the
UPVC C1 C2 C3 C4
important properties of the BPS filler
UPVC 44.0 39.6 35.2 30.8 26.4
and UPVC respectively. The blending
process for the incorporation of BPS BPS filler — 4.4 8.8 13.2 17.6
filler was calculated on the basis of the
maximum capacity of the high-speed
mixer. The full capacity of this machine Table 4. Formulation blend of the BPS/UPVC composite with acrylic
was 44 g for each blending process. Constituent Weight for each blending process (g)
Table 3 shows the blend formulation UPVC CA1 CA2 CA3 CA4
of the BPS/UPVC composite for the UPVC 44.0 36.9 32.8 28.7 24.6
incorporation of BPS filler. BPS/ BPS filler — 4.1 8.2 12.3 16.4
UPVC composites were denoted by
Acrylic FM50 — 2.95 2.63 2.30 2.00
the symbols C1, C2, C3, and C4 (see
Table 3), while the addition of acrylic
FM50 (also supplied by Polymer
Resources Sdn. Bhd., Selangor,
Malaysia) were denoted by CA1, Incorporation of BPS Filler immediately after the sheets were
CA2, CA3, and CA4 (see Table 4). with Acrylic FM50 removed after blending to avoid
In these notations, C represents the hardening of the composite. The milled
Acrylic FM50, which consists of
BPS filler and UPVC composite, CA sheet was then placed on the mould for
poly(methyl methacrylates) (PMMAs),
represents a BPS/UPVC composite fabrication of a composite panel. The
is often used to blend UPVC. Table 4
with the addition of acrylic FM50, mould was placed on the hot-press/
shows the formulation blend with the cold-press machine. The milled sheet
and the number denotes the weight addition of acrylic FM50.
percentage of filler. was then pressed by the 150 × 150 ×
3 mm3 mould at a temperature of 180 °C
Sample Fabrication for DMA and a pressure of 124 kg/m2. The whole
The UPVC matrix in powder form process took 15 min: the first 4.5 min
was blended in the dry state for 10 min was taken up by preheating, with 30 s
3
Table 1. Properties of BPS filler for venting, followed by 5 min during
using a high-speed Haake machine.
Property Value which the milled sheet was fully hot
For the first 1.5 min, the UPVC was
3
Density (g/cm ) 1.35 pressed. For the last 5 min the milled
dry-blended, and in the next 1.5 min
Elongation at break (%) 5–6 sheet was fully cold pressed, at which
the BPS filler was added to the dry-mix
point the composite panel was ready
Cellulose content (%) 63 – 64 polymer. The homogeneous mixed
to be removed from the mould.
Lignin content (%) 5 composite was used to produce sheets
Tensile strength (MPa) 550 ± 6.7 on the laboratory’s two roll mills at a
temperature of 170 °C. Dynamic Mechanical Analysis
Young’s modulus (GPa) 20
Diameter (μm) 120 ± 5.8 The specimen used was rectangular
0
The milled sheets were then cut into in shape and measured 17.0 mm ×
Microfibrillar angle ( ) 11
smaller pieces after removal from 14.0 mm × 3.0 mm. A Q800 Dynamic
Lumen size (μm) 5 the mixer. The cutting was done Mechanical Analyzer-7 instrument was

56 Polymers & Polymer Composites, Vol. 17, No. 1, 2009

 Dynamic Mechanical Behaviour of Banana-pseudostem-filled Unplasticised Polyvinyl Chloride Composites

used to evaluate the dynamic modulus
and damping behaviour (tan δ). The
experiments were carried out in the
temperature range 30–140 °C with a
heating rate of 5 °C/min in an ambient
environment. The tests were carried
out with different filler loadings, using
a single-cantilever clamp. The test
method used was the dynamic stress–
strain method with a frequency of 1 Hz.
Graphs were generated after all the
properties of the sample, including size
and heating range, had been entered in
the monitoring computer. Each of the
sample formulations was run twice,
with each sample taking 50 min.
RESULTS AND DISCUSSION
Storage Modulus (E′)
According to Lee et al.10, the storage
modulus of the polymer matrix and
the thermomechanical stability are
markedly improved with increasing
natural fibre content, showing a
maximum storage modulus value at
50 wt.% fibre loading. In terms of mixed-
fibre composites, it was found that the
storage modulus above Tg was found to
be increased with a fibre volume fraction
up to 40% 11. In the case of glass-fibre
composites, Hameed et al.12 found that
the storage modulus increased with
increase in fibre loading, which was due
to the reinforcement effect imparted by
the stiff glass fibre.
The modulus in the glassy region can
be determined primarily by the strength
of the intermolecular forces and by the
way the polymer chains are packed3.
In neat UPVC, E′ falls with increasing
temperature owing to an increase in
segmental mobility3. An increased
temperature means a decrease in
stiffness of neat UPVC and composites.
During transition in amorphous
materials such as PVC, the constituent
parts undergo segmental motion. The
segmental motion is due to the chains
in the amorphous regions beginning
to perform large-scale motion9. From
Figure 1 it is also evident that E′ is
affected by temperature: the higher the
temperature, the lower the E′ value will
be. The addition of BPS filler causes E′
to increase gradually. Composites C1 to
C4 have a higher glass transition which
may be due to the rising movement of
adjacent atoms with the addition of
different percentages of filler.
Put more simply, the higher glass
transition temperatures T g of
composites compared with the UPVC
matrix with increase in filler loading
may be attributed to the restriction
imposed by the filler through molecular
Figure 1. Plots of storage modulus (E′) for the UPVC matrix and 10, 20, 30, and
40% filler loading as a function of temperature
motion in the matrix6. At the initial
temperature, Figure 1 shows that the
storage modulus of the composite
increased substantially with the
addition of filler. The higher stiffness
of the composite can be attributed
to evaporation of water molecules
adhering to the filler during processing.
When the temperature is increased,
the fall in the modulus of the matrix is
compensated for by the filler stiffness.
In this case, the modulus is controlled
by the filler volume and hence increases
with filler loading.
BPS Filler–UPVC–Acrylic FM50
Figure 2 shows the variation in the
storage modulus of acrylic-modified
UPVC and CA1, CA2, CA3, and
CA4 composites as a function of
temperature. The storage modulus
of these composites was found to
be 3000 MPa lower than that of an
unmodified BPS/UPVC composite.
The glass transitions were shifted to
higher temperatures by comparison
with non-acrylic and neat UPVC, as
shown in Figure 3. Only the CA4
composite was found to have a higher
storage modulus than neat UPVC in the
glassy state. Above the glass transition,

BPS Filler–UPVC Composites

Dynamic mechanical properties such
as the storage modulus (E′) and the
damping behavior (tan δ) of neat UPVC
and BPS–UPVC composites were
evaluated at temperatures ranging from
30 to 140 °C. The storage modulus was
studied with different filler contents at
various temperatures and a frequency
of 1 Hz. Figure 1 shows plots of E′ for
the UPVC matrix and for BPS filler
loadings of 10, 20, 30, and 40% as a
function of temperature. This figure
also shows that the E′ values of the
UPVC matrix and composites form a
plateau up to 45 °C and then fall steeply
as the temperature increases.

Polymers & Polymer Composites, Vol. 17, No. 1, 2009 57

 E.S. Zainudin, S.M. Sapuan, K. Abdan, and M.T.M. Mohamad

the storage modulus of neat UPVC was Figure 2. Variation in the storage modulus of acrylic-modified UPVC and CA1,
lower than that of composites because CA2, CA3, and CA4 composites with temperature
of the improvement clearly seen before
reaching the melting point. The value
for CA4 was found to be higher than
the values for neat UPVC and other
composites owing to a closed gap and
higher filler–matrix adhesion. The same
explanation was given by Pothan et
al.3 and Manikandan Nair et al.9. The
higher value of Tg for BPS/UPVC/
acrylic composites compared with the
non-acrylic BPS/UPVC composite may
be attributed to more restricted slippage
and avoidance of material flow as a result
of the addition of acrylic.

The highest Tg value, obtained for

CA4 in the glassy state, may be due
to the addition of acrylic, which
reduces stiffness compared with that
of neat UPVC. The stiffness of the
CA4 composite is also reduced, but it
is still higher than the stiffness of the
neat UPVC. The stiffness in the glassy Figure 3. (a): (i) glass transition (Tg) and (ii) peak height and peak width at half-
state can be placed in the following height of the tan δ curve of BPS/UPVC composites
decreasing order: CA4 > UPVC >
CA3 > CA2 > CA1 (as shown in
Figure 2). The higher value for the
CA4 composite formulation is due
to the much higher filler contribution
than in the other formulations. It
could also be stated that the adhesion
contributes to improvement of the
composite. Compared with the BPS/
UPVC composite without acrylic,
the composite has a lower stiffness at
initial temperature. This shows that the
addition of acrylic does not enhance
the storage modulus or stiffness
characteristics of the samples.

The fall in modulus when passing

through the glass transition temperature
is clearly evident after 70 °C. There is
a sharp fall in the modulus of the neat
UPVC, more so than in reinforced
BPS/UPVC, after reaching the glass
transition temperature, and the order
of stiffness changes to CA4 > CA3
> CA2 > CA1 > UPVC. Thus, the
incorporation of BPS filler has a large
effect on the modulus after Tg up to
the rubbery plateau before reaching
the melting temperature.

58 Polymers & Polymer Composites, Vol. 17, No. 1, 2009

 Dynamic Mechanical Behaviour of Banana-pseudostem-filled Unplasticised Polyvinyl Chloride Composites

Figure 3. (b): (i) glass transition (Tg) and (ii) peak height and peak width at half- Damping Behaviour
height of the tan δ curve of acrylic-modified BPS/UPVC composites
BPS Filler–UPVC Composites
The effect of damping on filler mass
fraction of composites at a frequency of
1 Hz is shown in Figure 4. The curve
shows that the peak of tan δ decreases
with increasing filler content. It is clear
that the Tg of composites is shifted
towards a slightly higher temperature
than that of the neat UPVC. This
corresponds to an increased restriction
on molecular motion when compared
with the neat UPVC matrix acting
alone. In Figure 4, the C2 composite
has the highest glass transition
compared with neat UPVC and the
other reinforced composites. As stated
in the previous section, the storage
modulus with the addition of acrylic
FM50 results in a reduced stiffness
compared with that without acrylic. In
Figure 5, with the addition of acrylic,
the glass transition temperature for this
composite increases from 93.5–95 °C
(Figure 3a) to 95–98 °C (Figure 3b).
The order of decreasing glass transition
is known to be C2 > C4 > C3 > C1 >
UPVC. The incorporation of acrylic
might affect the chemical reaction and
raises the glass transition temperature,
as shown in Figure 3b.

The C2 composite can be considered to

transfer stress effectively through the
Figure 4. Effect of tan δ or damping on filler mass fraction of composite at a
fibre as reinforcing agent. This study
frequency of 1 Hz
shows that the peak of curves tends
to decrease with the incorporation of
filler for both acrylic-modified and
unmodified composites (see Figures 2
and 4). In this case, better interfacial
interaction occurs through the width of
the tan δ peak. As stated by Manikandan
Nair et al.9, the peak width at half-
height is one of the criteria used to
indicate interaction between phases
and homogeneity of the amorphous
phase.

Tan δ is a damping term that can also

relate to the impact resistance of a
material. The effect of the mechanical
loss factor, tan delta (tan δ), or damping,
on fibre volume fraction as a function
of temperature at a frequency of 1 Hz

Polymers & Polymer Composites, Vol. 17, No. 1, 2009 59

 E.S. Zainudin, S.M. Sapuan, K. Abdan, and M.T.M. Mohamad
Figure 5. Effect of tan δ or damping on filler mass fraction of acrylic-modified
composite at a frequency of 1 Hz
is delineated in Figure 4. It can be seen
that the tan δ peak occurs at 92.9 °C (Tg)
for the neat UPVC. This is associated
with the glass transition of the UPVC
resin. With the incorporation of fillers,
the tan δ peak is lowered, as expected.
This is due to a decrease in the volume
fraction of the matrix as a result of the
incorporation of fillers.
BPS Filler–UPVC–Acrylic FM50
Composites
The damping term (tan δ) can be defined
as the impact resistance of a material.
Glass transition is when the material
changes from a rigid to a more elastic
region; it is due to the tendency for the
damping peak to occur8. It is associated
with the movement of small groups
and states as chains in molecules in the
polymer structure, which are frozen to
begin. In composite material, damping
is one of the indicators that show change
through the incorporation of filler.
There are several factors that affect
the variation in tan δ, including the
interfacial bonding between filler and
matrix. Higher damping at the interfaces
implies poor interface adhesion3.
The effect of tan delta or damping on the
filler mass fraction of composites at a
60
frequency of 1 Hz is given in Figure 5.
According to this figure, above Tg of
the matrix, the peak of tan δ decreases
with increase in filler loading. Also
noteworthy is that the Tg of composites
is shifted towards a higher temperature
than the Tg of neat UPVC, which is
due to a greater restriction on molecular
motion or slippage. In this study, the
Tg of composite CA4 is the highest
among the composites owing to
closing of the gap between the filler
and the matrix and because of the good
adhesion bonding. The increase in Tg
(Figure 5) with increase in filler mass
fraction is due to increased packing of
the fillers.
CA4 filler loading can also be
considered to transfer stress effectively
from filler to matrix. Increase in filler
loading in the composite tends to reduce
the tan δ peak height by restricting the
movement of polymer molecules, as
stated by Pothan et al.3. The magnitude
of the tan δ peak indicates the nature
of the polymer system3,4. This is
different to an unfilled system, where
the chain segments are free from any
restraint because they are in the same
types of molecule. That is why the
highest peak has been obtained by the
Polymers & Polymer Composites, Vol. 17, No. 1, 2009
neat UPVC matrix. The variation can
clearly be seen in Figure 5, in terms
of decreasing peak rather than shifting
temperature. After all considerations,
the shift in Tg to higher temperatures
with increasing filler loading can be
defined as decreased mobility of the
chains as a result of the addition of
BPS filler.
Another factor inducing a shift in
Tg is the stress field surrounding the
particles. The increase in temperature
after glass transition shows that neat
UPVC only has a higher peak than
the composites because of the close
interaction in the composition of
the composites compared with the
UPVC matrix acting alone. The peak
width is found to be maximum for
the composite with CA4 filler loading
(see Figure 3b). The fact that the
composites have a lower peak height
and a greater peak width at half-
maximum compared with neat UPVC
can be attributed to the lower mobility
of the polymer chain and increased
homogeneity respectively.
CONCLUSIONS
The dynamic mechanical properties
(storage modulus and tan δ) of neat
UPVC and BPS filler–UPVC have
been studied at temperatures ranging
from 30 to 140 °C. In all cases, the
storage modulus decreases with
increase in temperature owing to
increased segmental mobility. The
glass transition of composites was
found to be shifted towards higher
temperatures compared with the neat
UPVC matrix. The gradual addition
of 10% filler to the neat UPVC matrix
increased the storage modulus of the
composites. Higher stiffness has been
obtained for C4 composites. This can
be attributed to the highly restricted
movement in the side chain or adjacent
atoms in the main chain. The damping
properties with the addition of acrylic
also decreased with the gradual
addition of 10% filler. It was found that
a decrease in peak height correlates
with an increase in width at half-
 Dynamic Mechanical Behaviour of Banana-pseudostem-filled Unplasticised Polyvinyl Chloride Composites
height. The glass transition is clearly
seen to increase as the filler content
increases, which is consistent with the
theory that the incorporation of filler
has a restricting effect on segmental
mobility of the molecular structure.
The glass transition temperature is
shifted towards higher temperatures
than in the case without acrylic. This
shows that slippage restriction is
shifted towards higher temperatures.
A higher peak width at half-height
was also determined for the CA4
formulation, and better interfacial
interaction and homogeneity have been
obtained, approaching those achieved
in theoretical research.
ACKNOWLEDGEMENTS
The author wishes to thank Universiti
Putra Malaysia for financial support
of this research.
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