Iran Polym J

DOI 10.1007/s13726-017-0520-6

ORIGINAL PAPER

Improvement in mechanical and thermal properties

of unsaturated polyester‑ based hybrid composites
Tahir Ahmad1 · Syed Shehzad Raza1 · Ehsan Aleem1 · M. Kamran1 · Umar Manzoor1 ·
Atif Makhdoom1 · Rafiq Ahmad1 · Sehrish Mukhtar1

Received: 18 November 2016 / Accepted: 5 March 2017

© Iran Polymer and Petrochemical Institute 2017

Abstract Polymer matrix composites are used in auto- Keywords Unsaturated polyester resin · Silica
mobile, structure and aerospace industries due to their nanoparticles · Glass fiber · Mechanical properties ·
light weight and high strength. The present research has Microstructure · TGA
an aim to reinforce locally developed silica nanoparticles
and glass fibers in unsaturated polyester to produce poly-
mer-based hybrid composites. Composites were synthe- Introduction
sized by hand lay-up method with 1, 2, 3 and 4 wt% of
silica sand nanoparticles and glass fiber. Mechanical tests Several modern technologies require materials, with unique
like tensile, impact and micro-hardness were performed combinations and superior properties than a material with
on the obtained polymer hybrid composites. The results limited performance. Fiber reinforced composites are such
of mechanical properties of the hybrid polymer matrix materials, which have revolutionized the conception of high
composites revealed an increasing trend. The SEM analy- strength. Composite materials are formed by an amalgama-
sis was performed on the developed and fractured tensile tion of two or more separate materials. The combination
testing samples. The SEM analysis showed the presence of two or more materials is defined as composite, a solid
of silica nanoparticles in the samples and pulling action of material, in which specific components keep their separate
fibers were seen under fractured tensile tests. The pulling identities [1]. Ajay et al. [2] reinforced glass/polyester lam-
actions of fibers from polymer matrix delayed the fractured inates by different sizes of fillers and studied the mechani-
mechanism and enhanced the mechanical properties. Silica cal properties of the developed composites. The results
nanoparticles filled the cavities generated during tensile showed that the composites have very good load bearing
test and extensive enhancement was revealed in tensile as capacity with the addition of fillers. A research was con-
well as impact energy. Toughness of the hybrid composite ducted to inspect the outcome of silica on different prop-
was also enhanced as a result. The thermal properties of erties possessed by polyester composites reinforced with
the hybrid polymer composites were analyzed using ther- natural fiber. Composites were made by silica and without
mogravimetric analysis. Thermal stability of the compos- silica through adding 100% recyclable reinforcement as
ite has been marginally increased with increasing wt% of natural fibers in polyester medium [3]. Outcomes showed
reinforcement. an increase in tensile strength of silica-based composites
and found to be 1.5 times better as compared to compos-
ites which were made without silica. Tensile modulus of
a composite made with silica was also 1.8 times better as
compared to a composite which were made without silica.
* Tahir Ahmad Composites impact energy was also studied and found to
[email protected] be 1.36 J which was 1.8 times greater than the composite
1 without silica. Inceoglu et al. [4] studied the effect of clay
Department of Metallurgy and Materials Engineering,
College of Engineering and Emerging Technologies, addition in glass fiber in polymer-based composites. The
University of the Punjab, Lahore, Pakistan result showed that ultimate tensile strength, elastic modulus

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and rupture modulus of unsaturated polyester have been used unmodified (Si-Un) and commercially modified with
enhanced by adding clay to maximum 5 wt%. The ten- octylsilane (Si–OS) and polydimethylsiloxane with 5, 10,
sile and flexural properties were decreased above 5 wt% and 15 wt% as fillers to prepare polyurethane (TPU) nano-
of clay. Kornmann et al. [5] also reported while studying composites. Nanocomposites containing treated nanoparti-
the effect of clay addition in glass fiber that the stiffness cles showed much better thermal stability as compared to
of material and cracking resistance has been improved by untreated particles. Tufan et al. [14] prepared wood-plastic
increases in clay loading. Though, being brittle is a disad- composites (WPCs) using different types of fillers such
vantage to nanocomposites in limiting their application. as mixtures of carpenter waste and recycled high-density
Hulugappa et al. [6] used graphite, silicon carbide as fillers polyethylene (R-HDPE). It was found that wood-waste
in plain weave woven glass fabric reinforced epoxy (G-E) flour filled composites showed better mechanical proper-
composite. Hand layup process and compressed hot press ties as compared to particle board waste flour. Wang et al.
were used to develop composites and the mechanical prop- [15] prepared flame-retarded expanded polystyrene (EPS)
erties were studied. The results showed that the mechanical foams by reinforcing ammonium polyphosphate (APP)
properties increased by increasing filler contents and ten- and nano-zirconia (nano-ZrO2) using phenolic resin binder.
sile strength were increased from 305 MPa to 404.2 MPa. An improvement in compressive and flexural strengths
Bazli et al. [7] studied the viscoelasticity and morphol- has been observed. Flame-retardant properties have been
ogy of nanocomposites developed by adding nanoclay in increased by adding a little amount of nano-ZrO2 into the
silicone rubber (SR) and ethylene propylene diene mono- APP flame-retarded EPS foams. Harsha et al. [16] rein-
mer (EPDM). The SR contents during the curing process forced neat polyetherimide (PEI) with glass fibers, carbon
increased vulcanization rate and cross-linking density of fiber and solid lubricant and studied the tribological proper-
the blends. Maxwell model showed a good fitting between ties. The results showed that friction and wear properties
tensile properties of samples and that of experiments. Sut- were reduced with increases in temperature and at elevated
tivutnarubet et al. [8] utilized zirconocene/MAO catalytic temperature carbon fibers have shown less wear rate.
system to develop polyethylene/coir dust hybrid filler by Going through the literature review, it is found that there
in situ polymerization and produced biocomposites. Cata- is an insufficient research on using local sand and rein-
lytic activities were decreased as increasing coir dust con- forcements with glass fibers in unsaturated polyester com-
tents. The SEM analysis showed that the presence of PE/ posites. This research work has an aim to investigate the
coir dust filler in natural rubber showed more compatibility effects of silica sand nanoparticles and glass fibers addition
as compared to pure coir dust. Onuegbu et al. [9] used 0–40 in unsaturated polyester-based hybrid composites. It also
wt% snail shell powder with particles sizes of 0.150, 0.30, focuses on the mechanical and thermal properties of the
and 0.42 µm and talc of particle size, 0.150 µm to prepare developed hybrid polymer composites.
polypropylene composites. The mechanical properties such
as tensile modulus, flexural strength and impact strength
were improved by increasing filler contents. The compos- Experimental
ites reinforced with talc showed brittleness by increasing
the filler contents. Datta et al. [10] used a laboratory two- The development of silica sand nanoparticles used in
roll mill to prepare natural rubber vulcanized composites this research has been explained in our previous research
with 15, 25, 45, and 85 wt% of titanium dioxide loadings. works [17, 18]. Glass fiber, unsaturated polyester resin, fine
The results of natural rubber-based composites showed an methyl ethyl ketone peroxide (MEKP) and cobalt acetate
improvement in mechanical properties as well as thermal were purchased from Qartaba market, Lahore, Pakistan.
stability as compared with addition of titanium dioxide The hand layup process was used to develop the hybrid
loading. Zhong et al. [11] chemically grafted accelerator composites with a mold in the form of plain container,
ethylene thiourea (ETU) onto the surface of silane modified made up of galvanized steel. Mold was made just like a
silica and obtained ETU-modified silica (silica-s-ETU). tray with the dimensions of 12 inch length, 6 inch width
Silica-s-ETU was homogeneously dispersed into styrene- and 1 inch height. The mold was washed carefully with hot
butadiene rubber (SBR) and found that SBR/silica-s-ETU water to remove dirt, grease and finger marks, and it was
nanocomposites showed excellent mechanical properties. completely dried and has been reserved for easy removal
Tangudom et al. [12] used bagasse ash silica (BASi) and of product. Glass fibers and silica sand nanoparticles were
precipitated silica (PSi) as filler in natural rubber (NR) and reinforced in unsaturated polyester resin. Varying amounts
styrene-butadiene rubber (SBR) to achieve hybrid compos- of finely ground silica sand nanoparticles (1, 2, 3 and 4
ites. It was found that BASi showed better tensile strength wt%) were added to unsaturated polyester resin, respec-
and wear properties as co-reinforcing filler with PSi for tively, keeping, the quantity of unsaturated polyester resin
SBR and NR/SBR compounds. Hassanajili et al. [13] constant. Nano-silica sand particles were preheated before

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using as reinforcement in unsaturated polyester matrix to

reduce the agglomeration of nanoparticles. Weighing of
polyester and silica sand was performed using digital bal-
ance. Proper mask, glasses and gloves were used to han-
dle unsaturated polyester resin and silica nanoparticles.
Mixture was stirred thoroughly while adding cobalt acetate
(accelerator) and MEKP (hardener). Accelerator and hard-
ener were added in the ratio of 1:1 wt% to the mixture of
unsaturated polyester and silica sand. Mixture was poured
onto the mold with the help of brush. After pouring mix-
ture on mold surface, chopped glass fiber was applied to
mold with top and bottom layers of unsaturated polyes-
ter sand mixed mixture. Hand rolling process was carried
out by a steel roller to ensure uniform thickness and com-
paction. After achieving uniform thickness, one layer of
woven glass fiber was placed on chopped glass fiber layer
with top and bottom layers of unsaturated polyester resin.
Hand rolling process was used again to achieve maximum
compaction and uniform thickness. As the whole process
was being carried out in an open environment there was a
large possibility of entrapping air on the surface and inside
to some extent. Therefore, great care was taken to ensure
that no air bubble exists during curing process. The hybrid
composite combinations were left at room temperature for Fig. 1  a Prepared tensile samples and b fractured tensile samples
curing process for 24 h. Tensile and impact test samples
of the composites were prepared according to ASTM D
638-97 and ASTM 6110 D (08.03), respectively. Universal
Tensile testing machine of (5kN) Lloyd Instrument, LR5 K
was used to perform tensile tests. Three tensile tests were
performed for each wt% sample of reinforcement to check
the repeatability of the test. The fracture surfaces of tensile
samples were analyzed using scanning electron micros-
copy (SEM, Jeol Company). The thermal properties of the
polymer hybrid composites have been observed using TGA
(Q600SDT, TA Instruments, USA). In TGA analysis nitro-
gen environment with flow rate of 100 mL/min and heating
rate of 10 °C/min was used. The microhardness testing of
the hybrid composites were performed using Vickers hard-
Fig. 2  Tensile curve for 4 wt% of reinforcements
ness machine (Shimadzu, Japan, model HMV-ZE) with
diamond pyramid indenter (136º angel between opposing
faces) using 50 g load for 10 s. glass fibers and Fig. 3 shows the overall behavior in ten-
sile properties of hybrid composites. Figure 2 shows that
increasing percentage of reinforcement first affects ductile
Results and discussion behavior and increases the toughness behavior of the com-
posite. Increasing percentage of reinforcements increases
Tensile properties of polymer matrix hybrid composites tensile strength and maximum strength has been achieved
by addition of 4 wt% silica sand nanoparticles and glass
The prepared tensile samples according to ASTM are fibers as shown in Fig. 3. It was also observed during ten-
shown in Fig. 1a and the fractured tensile sample is shown sile test that the delayed fracture was due to pulling and
in Fig. 1b. It was found that all the fractured tensile sam- fracturing mechanism of the fibers. When the tensile tests
ples were broken within the gauge length. started, fibers distended from the polymer matrix and dur-
Figure 2 shows the evaluated tensile strength of hybrid ing this process, small cavities were generated while being
composite with 4 wt% of silica sand reinforcement and filled by silica nanoparticles. This mechanism of pulling

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Fig. 3  Tensile strength of hybrid polymers composites Fig. 4  Hardness of hybrid polymer composites

fibers out from the matrix and filling of cavities by silica clearly shows the pulling length of fibers from polymer
nanoparticles caused delay in fracture process. Graphite matrix and pulling mechanism is in longitudinal directions.
and silicon carbide were used by Hulugappa et al. [6] with Some of the fibers, still embedded in matrix, need more
woven glass fabric in epoxy. He found that 10 wt% silicon energy and stretching forces to pull out from the matrix.
carbide showed better mechanical properties. He has used This mechanism coincides with the starting point of tensile
woven glass fabric and silicon carbide and reinforcement test, and until and unless all fibers are pulled out from the
but in our case short fibers and silica sand nanoparticles polymer matrix the process can delay fracture mechanism
were utilized. Similar work was also performed by Tangu- of hybrid polymer composites. In Fig. 5c, distribution of
dom et al. [12] but they used bagasse ash silica (BASi) and fibers and silica nanoparticles is evident in filling the cavi-
precipitated silica (PSi) as fillers in natural rubber (NR) and ties generated during tensile test. Some interstitial spaces
styrene–butadiene rubber (SBR). are generated during the tensile test and during this action,
silica nanoparticles present in the polymer matrix fill the
Hardness of polymer matrix hybrid composites spaces and cause delay in fracture mechanism as discussed
by Ahmad et al. [18]. Some of the filling interstitial places
The purpose of incorporating silica sand nanoparti- are shown in Fig. 5c. This whole mechanism of pulling
cles into the polymer matrix is to enhance its resistance action of fibers and filling interstitial places by silica nano-
against deformation. The nano-silica sand particles pos- particles has caused delay in fracturing polymer compos-
sess exceptional hardness when utilized as reinforcement ites. This development of hybrid polymer composites is
and has been confirmed by Ahmad et al. [18]. The results more suitable for safety point of view because delaying in
of microhardness test showed that increasing percentage of fracture formation provides some time to evacuate easily
silica sand nanoparticles increased the hardness of hybrid from that place.
composite due to dispersion of silica nanoparticles homo-
geneously in unsaturated polyester resin, along with glass Impact strength of polymer matrix hybrid composites
fibers which made the surface of hybrid composite harder.
The hard surface of the polymer composites did not allow The impact strength behavior of polymer hybrid com-
indenter to go deep in the polymer matrix. The microhard- posites is shown in Fig. 6. An increasing trend of impact
ness results are shown in Fig. 4. strength was seen with increasing wt% of reinforcements
in polymer matrix. Increasing behavior in strength is due
SEM analysis of polymer matrix hybrid composite to the presence of glass fibers and silica nanoparticles. The
fibers bear the load and increase the impact strength of
Scanning electron microscopy (SEM) results indicated the the polymer composites. When impact force is applied to
distribution and strengthening mechanism by silica sand composites, the tensile force causes fibers to pull out from
nanoparticles and glass threads in unsaturated polyester matrix and bear more energy until they break. This pulling
resin as shown in Fig. 5a. This figure shows the presence and breaking mechanism of fibers from polymer matrix
of glass fibers embedded in polymer matrix and these fibers delays the fracture in impact test and causes polymer to
provide strengthening mechanism to polymer in all direc- bear more energy. Such pulling action of fibers from matrix
tions. During tensile test the glass fibers are stretched and is shown in SEM analysis of hybrid composites. When
protruded from the polymer matrix (Fig. 5b). Figure 5b impact energy is applied to hybrid composites, protrusion

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Fig. 6  Impact strength of polymer hybrid composites

Fig. 7  TGA analysis for 1 wt% of reinforcement in hybrid compos-

ites

of the fibers from polymer matrix occurs and delays mech-

anism as discussed by Ahmad et al. [18].

TGA analysis of polymer hybrid composites

Figure 7 shows TGA analysis of 1 wt% reinforcements

and a change in slope of red line has been observed after
11 min at around 20 °C. Weight loss of about 98.25%
has been noticed and confirmed by a hump in pink line
in the curve at this temperature. After that the slope
of the curve remains constant up to 334 °C and then a
deviation in slope occurs after 26 min. A weight loss of
Fig. 5  a, b, c SEM and fracture analysis of hybrid polymer compos-
ites about 100.5% has been noticed. Above this temperature,
Fig. 7b (red) becomes constant which is an indication
of the residue. Figure 8 shows TGA analysis of 4 wt%

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Acknowledgements The authors are thankful to the University of the

Punjab for the financial support in conducting this research work.

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