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Hybrid composites of short acetylated kenaf bast fiber and conducting polyaniline nanowires in epoxy
resin
Saiful Izwan Abd Razak, Wan Aizan Wan Abdul Rahman and Mohd Yazid Yahya
Journal of Composite Materials published online 20 February 2013
DOI: 10.1177/0021998313476527

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kenaf bast fiber and conducting DOI: 10.1177/0021998313476527
jcm.sagepub.com
polyaniline nanowires in epoxy resin

Saiful Izwan Abd Razak1, Wan Aizan Wan Abdul Rahman1 and
Mohd Yazid Yahya2

Abstract
This article reports the preparation and characterization of newly developed hybrid composites consisting of epoxy resin
(EP) matrix, acetylated kenaf bast fiber (AKF) and conducting polyaniline (PANI) nanowires. Initially, the EP/AKF com-
posites were prepared by varying the AKF loading (5–30 wt%). The EP/AKF displayed an optimum tensile strength at
20 wt% AKF loading which was higher than that of untreated kenaf fiber EP composites (EP/UKF). The hybrid composites
of EP/AKF/PANI were then prepared by using 20 wt% AKF loading with PANI inclusions from 2 to 14 wt%. The addition
of PANI into EP/AKF induced positive electrical properties without considerably sacrificing its mechanical integrity. It was
found that the electrical percolation threshold of these hybrid composites was at 11 wt% of PANI loading. PANI inclu-
sions at above the percolation loading resulted in reduction of tensile and flexural strength. Meanwhile, no significant
mechanical loss was observed below the threshold. The fracture morphological analysis revealed the occurrences of
PANI nanowires pull out from the matrix. The Fourier transform infrared spectroscopy showed that the PANI com-
ponent still maintained its doped condition inside the EP/20AKF. Water absorption and thermal analysis indicate that the
PANI incorporation induced lower water uptakes and greater thermal stability to the EP/20AKF, respectively.

Keywords
Kenaf fiber, polyaniline, epoxy resin, electrical conductivity, mechanical properties, hybrid composites

It is possible to chemically reduce the hydrophilicity

Introduction
of the inherent cellulose surface by removing the sur-
Natural fibers are suitable candidates to replace syn- face OH groups by means of acetylation.10 It has been
thetic fibers for the preparation of fiber reinforced poly- shown that acetylated natural fiber had good mechan-
mer composites.1 The various advantages of natural ical properties and interaction with various polymer
fibers over man-made glass and carbon fibers are low matrices.11,12
cost, low density, comparable specific tensile properties, Conducting polymers are the new class of materials
less health risk, renewability, recyclability and bio- used for fabrication of many electronic devices.
degradability.2,3 Kenaf (Hibiscus cannabinus L., Polyaniline (PANI) is one of the most promising can-
Malvaceae) is a warm season annual fiber crop. It is a didates for industrial applications mainly for its easy
fiber plant native to east-central Africa where it has preparation, low cost, excellent electrical, optical,
been grown for several thousand years for food and
fiber.4 Various applications had been explored to utilize 1
Polymer Engineering Department, Faculty of Chemical Engineering,
the use of kenaf fiber (KF) including as adsorbent Universiti Teknologi Malaysia, Malaysia
2
material, feed stock, insulation board, paper and as Center for Composites, Universiti Teknologi Malaysia, Malaysia
reinforcement in polymer composites.5–9 However, cer-
tain drawback of natural fibers/polymers composites is Corresponding author:
Wan Aizan Wan Abdul Rahman, Polymer Engineering Department,
the incompatibility between the hydrophilic natural Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310
fibers and the hydrophobic polymer matrices. This Skudai, Johor, Malaysia.
leads to undesirable properties to the composites. Email: w.aizan@cheme.utm.my

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2 Journal of Composite Materials 0(0)

magnetic properties and environmental stability.13–15 the electron conducting features of PANI. It will be
PANI in its undoped state is an insulator. Doping of shown that the advantages and characteristic of the
PANI causes the delocalization of charge along the KF and PANI will not be significantly lost by such
polymer backbone thus becoming an excellent con- hybridization. So far, no such attempt has been done
ductor. PANI’s mechanical properties are low16 and to combine these two fillers (KF and PANI nanowires)
therefore they are usually used as conducting fillers in with EP matrix. This research work reports for the first
polymer matrices, mainly due to their lightweight and time the preparation of EP/KF/PANI hybrid compos-
electronic properties. Furthermore, it has been demon- ites, investigating the effect of PANI incorporation on
strated that PANI could induce controllable hydropho- the surface interactions, electrical, mechanical, mor-
bicity17 and good biocompatibility.18 Combining PANI phological, thermal properties and percentage of
with epoxy resin (EP) is a good strategy to obtain water uptakes.
thermosetting composites having good mechanical
and electrical properties. The issue to address in this
type of EP containing PANI composites is usually the Experimental
attainment of effective percolation to achieve the con-
ducting pathways for the composites. Percolation refers
Sample preparations
to a situation where randomly distributed conducting PANI nanowires doped with formic acid were synthe-
filler particles form percolating paths inside the insulat- sized using two face interfacial polymerization method
ing matrix, which leads to a sharp change in composite as described elsewhere.28 Briefly, the monomer, dopant
conductivity. Furthermore it has been reported that and oxidizing agent used were aniline, formic acid and
PANI in its nanowire form could reduce the percola- ammonium persulfate (Merck) of analytical grade,
tion concentration.19 There are many reports in the respectively. Untreated kenaf bast fiber (UKF) supplied
literature that described the possibility of imparting by Everise Crimson (M) were pulverized and sieved to
electronic properties to EP resin by the use of PANI 150 mm sized short fibers. Detailed preparation method
filler.20–23 However, the focal point of these works is of obtaining acetylated kenaf bast fiber (AKF) was
on the composites electronic properties, forgoing its described elsewhere.27 In short, the acetylation reagents
mechanical properties. It has been described by some used were glacial acetic acid (Merck), acetic anhydride
that the introduction of PANI reduces the mechanical (Sigma) and few drops of concentrated sulphuric acid.
properties of EP resin.22,24 Tsotra and Friedrich25 These prepared PANI nanowires and AKF were used
attempted to overcome this predicament by reinfor- for the preparation of EP/AKF/PANI hybrid compos-
cing the EP/PANI blend with short carbon fibers ites. The synthesized PANI nanowires were mixed with
and found out that the flexural properties improved toluene with a magnetic stirrer for 48 h to create a 5%
but minimally. The demand for materials having com- solution of required PANI. The mixture was treated in
bination of wide range of desirable properties is an ultrasonic bath for 3 h to obtain a green transparent
always increasing. The development of hybrid com- low viscosity polymer solution. In the mean time, the
posite (two or more filler types in a single matrix) is EP resin, DGEBA (Sigma) was mixed with AKF with a
still in its infancy. It is generally accepted that the mechanical stirrer for 10 min. The PANI suspension
behavior of hybrid composites appear to be simply a was then transferred into the EP resin containing
weighted sum of the individual components in which AKF and was then mixed under vacuum, until the
there is a more favorable balance between the advan- whole toluene was evaporated from the premixed
tages and disadvantages inherent in any composite hybrid composite. The hardener, trifluoroboron
material. Most of the natural/synthetic fiber hybridiza- (4-chlorobenzeneamine) (Air Products) was finally
tion aims on improving mechanical properties and added (10 phr to EP) and mixed at room temperature.
reducing water absorption of the composites, this is The precured hybrid composites were cast into silicone
mainly by limiting the loading fraction of the natural rubber molds of required dimensions and left for cure
fiber component.10,26 at room temperature covered with Mylar film on top.
It is interesting to combine the advantages of envir- The schematic preparation of the sample is depicted in
onmental friendly, low cost, high specific strength of Figure 1. Following this procedure, EP/AKF/PANI
KF with the electronic properties of PANI in a polymer hybrid composites with required AKF and PANI load-
matrix. It has been shown earlier that the combination ing were prepared. This hybrid composites preparation
of such material is synergetic, provided by the use of was preceded by the preparation of EP/UKF and EP/
suitable dopants and fiber treatment.27 Therefore, by AKF composites with varying fiber loading. This was
hybridizing KF and PANI nanowires in an EP resin, done in order to investigate the effects of acetylation
one can expect a hybrid composite having the mechan- and to determine the optimum loading for tensile
ical properties of natural fiber reinforced EP including strength.

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Razak et al. 3

Characterizations Results and discussion

The DC conductivity, sDC was measured on samples of Effects of KF acetylation on tensile strength
circular dimension using a resistance meter (Advantest)
of EP resin
by the four-probe method under ambient condition.
The sDC, was calculated using L/RA, where R is the Figure 2 depicts the tensile strength of EP/UKF and
resistance, L is the thickness and A is the area of EP/AKF composites at different loading. The tensile
sample. Samples were stored in a desiccator filled strength of the EP composites increases with increasing
with silica gels for approximately 24 h prior to testing filler loading. Both type of composites (untreated and
to remove adsorbed moisture. Five measurements were acetylated) revealed an optimum value at 20 wt% load-
made on each sample. The tensile test (ASTM D638) ing. These increases show that the fibers are capable of
was performed using a computer-controlled Instron acting as a stress transfer agent for the EP matrix, par-
machine with crosshead speed of 5 mm/min at a stand- ticularly at 20 wt% and below. It can be seen that the
ard laboratory atmosphere of 23 C. The width and composites with AKF had higher strength than the
thickness of the dumbbell shaped specimens were composites with UKF. The changes are attributed to
about 10.00 and 3.50 mm, respectively. Flexural test the acetylation of the fiber surfaces. Acetylation reduces
(ASTM D790) was performed by 3-point bending con- the polar hydroxyl groups by replacing it with less polar
figuration at 3 mm/min under ambient condition. At
least five replicates for each sample were tested.
Fourier transform infrared (FTIR) spectra of the sam-
ples were obtained using a model 2000 Perkin Elmer
spectrometer with a resolution of 0.4 cm 1. The water
absorption measurement was done according to ASTM
D570. The samples were dried at 80 C until a constant
weight was achieved prior to immersion in water at
27 C. The test was performed for 40 days. Weight
gains were recorded by periodic removal of the speci-
mens from the water bath and weighing on a balance
with a precision of 1 mg. The percentage of water
uptake, Mt (%) was calculated using (Ww–Wd)/
Wd  100. Where Ww and Wd are the weights of the
sample before and after immersion in water, respect-
ively. Thermal analysis was performed by TGA7
Perkin Elmer Pyris. Samples were heated from 30 C
up to 550 C with a heating rate of 10 C/min. The ten- Figure 2. Tensile strength of EP/UKF and EP/AKF composites
sile fractured surface morphology of the hybrid com- with varying fiber loading.
posites were analyzed using scanning electron EP: epoxy resin; AKF: acetylated kenaf bast fiber; UKF: untreated
microscope (SEM), Leo Supra 50VP. kenaf bast fiber.

Figure 1. Schematic preparation of EP/AKF/PANI hybrid composites.

EP: epoxy resin; AKF: acetylated kenaf bast fiber; PANI: polyaniline.

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4 Journal of Composite Materials 0(0)

acetyl groups, thus their interaction between the EP path throughout the composite. Majority of the com-
matrix is enhanced, resulting in higher tensile strength. posite’s volume at below the percolation concentration
Furthermore the surface of UKF contains significant is governed by the insulating EP matrix and the micron-
amounts of surface lignin, waxy substances and impu- sized AKF. In this case, finite segregated PANI
rities than AKF that prohibit favorable adhesion with
the EP matrix. The schematic interaction between AKF
and the EP matrix are shown in Figure 3. It can be
noted that the strength of EP/AKF composites of
above 20 wt% loading revealed declining trend and
slight reduction compared to neat EP. This can attrib-
uted to the poor matrix wetting at high fiber volume
fraction. Meanwhile the tensile strength of EP/30UKF
composites drops considerably reaching reduction of
22% compared to neat EP. This decrease may due to
the high fiber volume fraction plus the poor surface
interaction between EP and UKF that leads to poor
crosslinking reaction between the resin and the curing
agent. Based on these findings, composites with 20 wt%
AKF (EP/20AKF) are chosen to investigate the effect
of PANI inclusions, forming EP/AKF/PANI hybrid
composites.

DC conductivity and percolation threshold

Figure 4 presents the logarithmic electrical conductivity
of EP/20AKF/PANI hybrid composites as function of
PANI content. It shows that the conductivity increase
is insignificant from 2 to 10 wt% inclusion of PANI.
However, at 11 wt% loading, the conductivity jumps
drastically to 3.7  10 8 S/cm. Below the percolation
threshold (2–10 wt%), the PANI nanowires acted as Figure 3. Schematic interaction between AKF and EP resin.
fillers with no network formation and no conductive EP: epoxy resin; AKF: acetylated kenaf bast fiber.

Figure 4. Electrical conductivity of EP/20AKF/PANI as a function of PANI loading.

EP: epoxy resin; AKF: acetylated kenaf bast fiber; PANI: polyaniline.

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Razak et al. 5

nanowires could not induce any significant electrical composite shows slight reduction (8% drop) with the
pathways within the polymer matrix. Thus the incre- inclusion of 2 wt% PANI. This drop is caused by the
ment in electrical conductivity is only marginal. At brittle nature of PANI that acts as non-reinforcing fil-
11 wt%, a 3D network of the PANI nanowires is lers due to the significant difference in polarity and
formed. When percolation is reached, the conductivity crystallinity between PANI and EP. Though one
increased abruptly because the network has created might expect a substantial reduction once PANI is
conductive pathways throughout the EP/AKF matrix. introduced into the composite, this is avoidable due
This can be shown by the illustrative diagram in the to the favorable interaction of PANI dopant moieties
insert of Figure 4. Though the conductivity increment (formate ion) with the EP and AKF components.27,28
at percolation concentration is evident, it became stable The interactions between the three components are dis-
thereafter. However, the maximum conductivity cussed in the FTIR spectroscopy. Meanwhile, further
obtained is of four orders of magnitude lower than addition up to 8 wt% PANI revealed minimal changes
composite of EP/PANI.28 This can be associated with in the tensile strength. At low PANI loading, the mech-
the presence of AKF that might hinder the formation anical properties of the hybrid composites are preserved
of additional conducting PANI networks with good by the high strength of EP/AKF. However, the pres-
percolation quality. It has been reported that PANI ence of 10–14 wt% PANI in the composite leads to a
nanowires doped with formic acid achieved its percola- progressive fall in the tensile strength values. This
tion state at 8 wt% loading in that of similar EP behavior could be due to two main reasons: (1) the
matrix.28 In this case, the presence of AKF dominated large presence of PANI that might retard the curing
the volume of the matrix thus increasing its percolation reactions of the EP resin and (2) disrupts the load trans-
concentration up to 11 wt%. It can be said that the fer process from the EP to the reinforcement compo-
increase in conductivity and defined percolation thresh- nents (AKF). On the other hand, hybrid composite of
old indicates a possible way of using PANI nanowires 14 wt% PANI displays a loss in tensile strength of
as conducting component in natural fiber filled EP about 35% compared to EP/20AKF. This is related
composites. Lower conductivity percolation threshold to the highly percolated PANI within the matrix. The
is an important factor for preparing conductive com- flexural properties of the composites are presented in
posites, because low percolation lowers the cost and Figure 6. Both, flexural strength and modulus of the
minimize influences on the mechanical properties of hybrid composites exhibit similar trend with the tensile
the conductive composites. deformation mode. The decrease at high loading is
owed to the percolated PANI components that reduce
the EP/AKF resistance to shearing. In this case, the
Mechanical test utilization of AKF provide sufficient mechanical sup-
The tensile strength of EP/20AKF/PANI with increas- port to the hybrid composites revealing tensile and flex-
ing amount of PANI is shown in Figure 5. The ural strength values of several magnitudes higher

Figure 5. Tensile strength of EP/20AKF/PANI as a function of PANI loading.

EP: epoxy resin; AKF: acetylated kenaf bast fiber; PANI: polyaniline.

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6 Journal of Composite Materials 0(0)

Figure 6. Flexural strength and modulus of EP/20AKF/PANI as a function of PANI loading.

EP: epoxy resin; AKF: acetylated kenaf bast fiber; PANI: polyaniline.

than EP/PANI composites without any mechanical base is presented in insert of Figure 7. Hybrid compos-
reinforcements.22,24,28 ites of 12 wt% PANI (Figure 7(f)) exhibits similar pat-
tern to the 4 wt% PANI composites except for the
existence of the 3230 cm 1 peak and more distinct
FTIR spectroscopy 1140 cm 1 peak. The slight emergence of N–H stretch-
Spectrum of neat EP (Figure 7(a)) is the characteristic ing might suggest that charge-transfer activity between
of cured bisphenol-A epoxy. FTIR spectrum of PANI the conducting PANI chains can occur, resulting in an
(Figure 7(b)) exhibits the presence of benzoid and qui- appearance in the N–H stretching.15 The more pro-
noid ring vibration at 1530 and 1575 cm 1, respectively. nounced 1140 cm 1 peak is attributed to the presence
These indicate the oxidation state of the conducting salt of more conducting PANI nanowires (above the perco-
of PANI. The strong peak at 1140 cm 1 is the charac- lation threshold) inside the matrix. Figure 8 depicts the
teristic peak of PANI conductivity and is a measure of interaction between the three components. It has been
the degree of delocalization of electrons.29 The weak described previously27,28 that the interactions between:
and small peak at 3230 cm 1 is assigned to the N–H (1) PANI-AKF is by the p interactions of the formate
stretching mode. EP/20UKF in Figure 7(c) exhibits ions and acetyl group of AKF, (2) AKF-EP is by the
the OH band of free cellulose that of kenaf at methyl groups affinity plus the polarity between
3400 cm 1. Peak of 1734 cm 1 (as shown by the black the carbonyl and the EP chain and (3) EP-PANI is by
arrow) represent the acetyl group of hemicellulose and the charge-transfer and relatively small formate ions
ester linkage of lignin. EP/20AKF sample (Figure 7(d)) that facilitate mixing between the two.
shows decreased in 3400 cm 1 and increased of
1734 cm 1 peak intensities. This signifies that the
acetylation of fibers had occurred.27 Hybrid composite
Equilibrium water absorption
with 4 wt% PANI (Figure 7(e)) revealed that the Figure 9 shows that the water absorption of EP reaches
1140 cm 1 peak still exists, which essentially indicates saturation after 33 days with water uptake of about
that the PANI nanowires still keeps the doped conduct- 2.4%. This indicates that the absorption reaches
ing condition in the mechanically reinforced matrix. quasi-equilibrium condition.30 In EP, water molecules
This condition is vital to ensure that the incorporated couple strongly with hydrophilic functional groups
PANI nanowires do not deprotonate either by AKF or such as hydroxyl. Composite of EP/20UKF shows
hardener. Schematic of the PANI deprotonation by water uptake of about 3.7% upon immersion of

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Razak et al. 7

Figure 8. Schematic interaction between EP resin, AKF and

PANI.
EP: epoxy resin; AKF: acetylated kenaf bast fiber; PANI:
polyaniline.

turn will preserve their functional, structural and mech-

Figure 7. FTIR spectra of: (a) EP, (b) PANI (c) EP/20UKF, (d) EP/ anical properties.
20AKF, (e) EP/20AKF/4PANI and (f) EP/20AKF/12PANI.
FTIR: Fourier transform infrared; EP: epoxy resin; AKF: acety-
lated kenaf bast fiber; UKF: untreated kenaf bast fiber; PANI: TGA analysis
polyaniline.
TGA thermograms of cured EP, EP/KF and hybrid
composites are presented in Figure 10. Neat EP
(curve a) exhibits the features of cured EP that under-
40 days. This is attributable to the hydrophilic charac- went thermal degradation at 380 C. Both the TGA
teristic of the surface of natural fiber provided by the curves of EP/20UKF and EP/20AKF (curve b and c,
hydroxyl groups that interact with water through respectively) show first stage of weight loss around
hydrogen bonding.31 Furthermore, impurities on the 110 C, which correspond to water evaporation. The
UKF surface contribute to the water absorption of weight loss between 250 C and 300 C is attributed to
the composite. It can be seen that the EP/20AKF com- degradation of the KF. The third degradation at
posite reduces the water uptake compared to EP/ around 350 C is attributed to the degradation of the
20UKF. The acetylation process replaces the hydroxyl EP matrix. This shows that the reinforcement of KF
groups with acetyl groups, thus leaving fewer accessible decreases the thermal stability of the EP composite.
hydroxyl groups on the fiber and resulting in lower However, the composites with AKF show higher sta-
equilibrium water uptakes. Addition of 4 wt% PANI bility than composites with UKF. This is mainly due to
seems to have similar water uptake trend to that of the removal of easily hydrolyzed low thermal stability
neat EP. This behavior can be due to the hydrophobic impurities contained in the UKF. The hybrid compos-
features of PANI.17 Meanwhile, EP/20AKF/12PANI ites (4 and 12 wt% PANI inclusion) tend to maintain
revealed reduction in equilibrium water uptakes com- the stability of the EP/20AKF at higher temperature.
pared to EP. This indicates that the surface of the AKF Higher thermal stability of PANI27 than the natural
and the EP matrix had been dominated by the perco- fiber provide increased thermal barrier to the EP
lated hydrophobic PANI. These findings indicate that matrix as opposed to the EP/KF composites without
PANI inclusions in the composite could reduce the PANI inclusions. This shows that the inclusion of con-
degree of moisture absorption of EP/AKF which in ductive PANI increases the thermal stability of

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Figure 9. Water uptake of EP, EP/20UKF, EP/20AKF, EP/20AKF/4PANI and EP/20AKF/12PANI.

EP: epoxy resin; AKF: acetylated kenaf bast fiber; UKF: untreated kenaf bast fiber; PANI: polyaniline.

matrix is relatively poor. The fractured surface of the

EP/20AKF (Figure 11(b)) revealed much smaller fiber–
matrix gap with traces of the EP matrix on the AKF
surface. This is an indication that the adhesion is good
and favorable for load transfer. It is also noticed that
the fiber failed by tearing but no interfacial failure is
observed. The fractured surface of EP/20AKF/4PANI
(Figure 11(c)) revealed presence of small PANI par-
ticles on the AKF and EP matrix surfaces. This sug-
gests that PANI nanowire pull out occurred due to the
relatively poor interaction with the EP matrix. This is in
agreement with the reduction in mechanical properties
as discussed earlier. Though the PANI is synthesized in
its nanowire state, the pull out causes the nanowires to
Figure 10. TGA curves of: (a) EP, (b) EP/20UKF, (c) EP/20AKF, agglomerate and form particles of less than 1 mm. On
(d) EP/20AKF/4PANI and (e) EP/20AKF/12PANI. the other hand, it can be seen that the interaction
TGA: thermogravimetric analysis; EP: epoxy resin; AKF: acety- between the UKF and the EP matrix is still intact. It
lated kenaf bast fiber; UKF: untreated kenaf bast fiber; PANI: can be said that at low PANI loading (before the per-
polyaniline. colation threshold) the influence of PANI on the failure
mechanism of the hybrid composite is only by its pull
EP/20AKF and does not significantly affect the thermal out from the matrix, without causing any undesirable
stability of neat EP. effects on the AKF-EP matrix bonding. Meanwhile
hybrid composite at 12 wt% PANI (Figure 11(d))
revealed larger PANI particles including the distinct
SEM large gap between the AKF and matrix. The increased
Figure 11(a) shows the tensile fractured surface of EP/ in particle size is related to the percolated PANI nano-
20UKF. The matrix surface exhibit the typical frac- wires network within the matrix which increases the
tured surface of cured EP. It can be seen that there probability of the PANI nanowires to agglomerate
exists a small gap between fiber and matrix which during the failure process. Additionally, these particles
means that the adhesion between UKF and EP may result in fiber–matrix debonding as seen by the gap

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Razak et al. 9

Figure 11. SEM images of: (a) EP/20UKF, (b) EP/20AKF, (c) EP/20AKF/4PANI and (d) EP/20AKF/12PANI.
SEM: scanning electron microscopy; EP: epoxy resin; AKF: acetylated kenaf bast fiber; UKF: untreated kenaf bast fiber; PANI:
polyaniline.

between the AKF and EP which leads to reduction in occurred but nonetheless the EP–AKF interaction
mechanical properties. However, no AKF pull out was was retained. Meanwhile, failure of the composites at
observed. Indicating that the AKF still act as a stress above the percolation was influenced by the highly sig-
transfer medium to compensate the matrix mechanical nificant PANI pull out which led to reduction in
properties deterioration caused by the PANI pull out. EP–AKF interaction. The water absorption tests
showed that the hybrid composites had better water
absorption profiles than that of EP, EP/UKF and
Conclusions EP/AKF. This reduction in moisture uptake indicates
Novel hybrid composites made of EP, AKF and con- a positive effect, which makes PANI a suitable hygro-
ducting PANI nanowires were successfully developed scopic component. TGA results revealed that the inclu-
having favorable properties and synergizing effects. sions of PANI in the EP/20AKF increased its thermal
Tensile strength of EP/AKF was better than EP/UKF stability. FTIR spectroscopy of the hybrid composites
and achieved optimum values at 20 wt% AKF loading. showed that the electron delocalization peak of PANI
Furthermore the interaction between EP and AKF is was preserved. This newly developed hybrid composites
good, indicated by the reduction of hydroxyl groups show promise for multiple applications, which require
and more intense 1734 cm 1 peak of FTIR spectra. low conducting particulate content with good mechan-
Composites of EP/20AKF were used for the hybridiza- ical integrity.
tion with the PANI nanowires. It was shown that the
percolation of PANI nanowires inside the EP/20AKF Funding
occurred at 11 wt% PANI loading. This essentially
The financial support provided by the Universiti Teknologi
demonstrated the possibility of inducing electrical Malaysia through RUG grant is gratefully acknowledged.
properties towards natural fiber reinforced EP compos-
ites. Mechanical properties of the hybrid composites
Conflict of interest
were not considerably affected by the presence of
PANI at below percolation concentration but showed None declared.
reduction after the percolation has been reached.
However, the tensile strength and flexural values of References
these hybrid composites are higher than that of EP/ 1. Summerscales J, Dissanayake N, Virk A, et al. A review of
PANI from reported studies. It was shown that at bast fibres and their composites. Part 2 – Composites.
below the percolation concentration, PANI pull out Composites Part A 2010; 41(10): 1336–1344.

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2. Gibson RF. A review on recent research on mechanics of corrosive environments. Adv Funct Mater 2006; 16(4):
multifunctional composite materials and structures. 568–574.
Compos Struct 2010; 92(12): 2793–2810. 18. Kim H, Hobbs HL, Wang L, et al. Biocompatible com-
3. Singleton ACN, Baillie CA, Beaumont PWR, et al. On posites of polyaniline nanofibers and collagen. Synth
the mechanical properties, deformation and fracture of a Metals 2009; 159(13): 1313–1318.
natural fibre/recycled polymer composite. Composites 19. Jia QM, Li JB, Wang LF, et al. Electrically conductive
Part B 2003; 34(6): 519–526. epoxy resin composites containing polyaniline with dif-
4. Mohanty AK, Misra M and Hinrichsen G. Biofibres, ferent morphologies. Mater Sci Eng A 2007; 448(1):
biodegradable polymers and biocomposites: an overview. 356–360.
Macromol Mater Eng 2000; 277(1): 1–24. 20. Jia W, Tchoudakov R, Segal E, et al. Electrically con-
5. Özturk S. Effect of fiber loading on the mechanical prop- ductive composites based on epoxy resin with polyani-
erties of kenaf and fiberfrax fiber-reinforced phenol-for- line-DBSA fillers. Synth Metals 2003; 132(3): 269–278.
maldehyde composites. J Compos Mater 2010; 44(19): 21. Liu CD, Lee SN, Ho CH, et al. Electrical properties of
2265–2288. well dispersed nanopolyaniline/epoxy hybrids prepared
6. Ibraheem SA, Ali A and Khalina A. Development of using an absorption-transferring process. J Phys Chem
green insulation boards from kenaf fibres and polyureth- C 2008; 112(41): 15956–15960.
ane. Polym Plast Technol Eng 2011; 50(6): 613–621. 22. Soares BG, Celestino ML, Magioli M, et al. Synthesis of
7. Symington MC, Banks WM, West OD, et al. Tensile conductive adhesives based on epoxy resin and polyani-
testing of cellulose based natural fibers for structural line-DBSA using the in situ polymerization and physical
composite applications. J Compos Mater 2009; 43(9): mixing procedures. Synth Metals 2010; 160(17):
1083–1108. 1981–1986.
8. Ho WM, Ang LH and Lee DK. Assessment of Pb uptake, 23. Jang J, Bae J and Lee K. Synthesis and characterization
translocation and immobilization in kenaf (Hibiscus can- of polyaniline nanorods as curing agent and nanofiller for
nabinus L.) for phytoremediation of sand tailings. J epoxy matrix composite. Polymer 2005; 46(11):
Environ Sci 2008; 20(11): 1341–1347. 3677–3684.
9. Supri AG, Tan SJ, Ismail H, et al. Effect of poly(methyl 24. Tsotra P and Friedrich K. Thermal, mechanical, and elec-
methacrylate) modified water hyacinth fiber on proper- trical properties of epoxy resin/polyaniline-dodecylbenze-
ties of low density polyethylene/natural rubber/water nesulfonic acid blends. Synth Metals 2004; 143(2):
hyacinth fiber composites. Polym Plast Technol Eng 237–242.
2011; 50(9): 898–906. 25. Tsotra P and Friedrich K. Short carbon fiber reinforced
10. Mishra S, Mohanty AK, Drzal LT, et al. Studies on epoxy resin/polyaniline blends: their electrical and mech-
mechanical performance of biofibre/glass reinforced anical properties. Compos Sci Technol 2004; 64(15):
polyester hybrid composites. Compos Sci Technol 2003; 2385–2391.
63(10): 1377–1385. 26. Rodrigues LPS, Silva RV and Aquino EMF. Effect of
11. Ismail H, Abdullah AH and Bakar AA. Influence of accelerated environmental aging on mechanical behavior
acetylation on the tensile properties, water absorption of curaua/glass hybrid composite. J Compos Mater 2012;
and thermal stability of (high-density polyethylene)/ 46(17): 2055–2064.
(soya powder)/(kenaf core) composites. J Vinyl Additive 27. Razak SIA, Rahman WAWA, Hashim S, et al. Enhanced
Technol 2011; 17(2): 132–137. interfacial interaction and electronic properties of novel
12. Bledzki AK, Mamun AA, Lucka-Gabor M, et al. The conducting kenaf/polyaniline biofibers. Polym Plast
effects of acetylation on properties of flax fibre and its Technol Eng 2013; 52(1): 51–57.
polypropylene composites. Exp Polym Lett 2008; 2(6): 28. Razak SIA, Rahman WAWA and Yahya MY.
413–422. Electrically conductive nanocomposites of epoxy/polya-
13. Mahmoud WE. A novel photodiode made of hybrid niline nanowires doped with formic acid: effect of loading
organic/inorganic nanocomposite. J Phys D 2009; on the conduction and mechanical properties. NANO
42(15): 155502. 2012; 7(5): 1250039.
14. Ebrahim SM. Fabrication of schottky diode based on Zn 29. Razak SIA, Zein SHS and Ahmad AL. MnO2-filled mul-
electrode and polyaniline doped with 2-acrylamido-2- tiwalled carbon nanotube/polyaniline nanocomposites:
methyl-1-propanesulfonic acid sodium salt. J Polym Res effect of loading on the conduction properties and its
2009; 16(5): 481–487. percolation threshold. NANO 2011; 6(1): 81–91.
15. Razak SIA, Ahmad AL, Zein SHS, et al. MnO2-filled 30. Popineau S, Rondeau-Mouro C, Sulpice-Gaillet C, et al.
multiwalled carbon nanotube/polyaniline nanocompo- Free/bound water absorption in an epoxy adhesive.
sites with enhanced interfacial interaction and electronic Polymer 2005; 46(24): 10733–10740.
properties. Scripta Mater 2009; 61(6): 592–595. 31. Najafi SK, Tajvidi M and Chaharmahli M. Long-term
16. Valentova H and Stejskal J. Mechanical properties of water uptake behavior of lignocellulosic-high density
polyaniline. Synth Metals 2010; 160(7): 832–834. polyethylene composites. J Appl Polym Sci 2006; 102(4):
17. Zhu Y, Zhang J, Zheng Y, et al. Stable, superhydropho- 3907–3911.
bic, and conductive polyaniline/polystyrene films for

Downloaded from jcm.sagepub.com at RYERSON UNIV on May 30, 2014