Journal of Alloys and Compounds 561 (2013) 40–47

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Journal of Alloys and Compounds

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

Synthesis, characterization and impedance spectroscopy study

of magnetite/epoxidized natural rubber nanocomposites
W.L. Tan, M. Abu Bakar ⇑
Nanoscience Research Laboratory, School of Chemical Sciences, Universiti Sains Malaysia, 11800 Penang, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: The magnetite (Fe3O4) particles were synthesized in situ in the presence of epoxidized natural rubber
Received 4 June 2012 (ENR) to produce the various Fe3O4/ENR nanocomposites. The X-ray diffraction (XRD) analysis confirmed
Received in revised form 30 November 2012 the existence of Fe3O4 particles in the composites. The FTIR and DSC studies suggested that no chemical
Accepted 20 January 2013
interactions between the particles and the matrix. The SEM and X-mapping micrographs revealed that
Available online 10 February 2013
the Fe3O4 particles were distributed within the ENR matrix. The ENR matrix exerts control on the
Fe3O4 particles with a size of <20 nm in the composites. The Fe3O4 particles also affect the electrical prop-
Keywords:
erties of the composites. Impedance spectroscopy studies show that the electrical conductivity of the
Magnetite
Epoxidized natural rubber
nanocomposites increases with the increase in Fe3O4 loading in the composite. The equivalent circuit
Nanocomposite for the Fe3O4/ENR nanocomposites is proposed and discussed.
Impedance spectroscopy Ó 2013 Elsevier B.V. All rights reserved.
Conductivity

1. Introduction L-lysine [6], poly(N-vinyl pyrrolidone) (PVP) [7] and poly(lactic-

Magnetite (Fe3O4) is an interesting type of iron oxide and has
been extensively studied. Fe3O4 differs from other iron oxides as
it contains both divalent Fe2+ and trivalent Fe3+ ions in the intersti-
tial tetrahedral and octahedral sites [1]. This facilitates electron(s)
migration within the Fe3O4 lattice and thus exhibits high electronic
conductivity. The band gap of Fe3O4 semiconductor is 0.1 eV. This
makes it almost a metal-like semiconductor [1]. Fe3O4 also displays
other unique properties including optical, magnetic, catalytic and
thermal properties. Due to these interesting properties, Fe3O4 has
been used in a broad range of industrial applications including
catalysis, magnetic storage devices, colorants, and ferro-fluids
[1,2].
In the recent decade, polymer–inorganic nanocomposites have
become one of the emerging classes of advanced materials. Inor-
ganic nanoparticles such as transition metal oxides have been
incorporated into polymers affording various multifunctional
materials [3] with adopted properties of the respective constitu-
ents. Numerous reports on the Fe3O4/polymer composites are
found in literatures. The Fe3O4 particles have been combined with
suitable polymers of desired properties to produce a composite
that holds potential applications. Thus, Fe3O4 particles has been
incorporated into non-toxic, biocompatible and biodegradable
polymers such as poly(D,L-lactide) (PDLLA) [4], alginic acid [5],
⇑ Corresponding author. Tel.: +60 4 653 3888; fax: +60 4 657 4854.
E-mail address: bmohamad@usm.my (M. Abu Bakar).
co-glycolic acid) (PLGA) [8]. This has resulted in the utilization of
the nanocomposites in several biomedical fields including mag-
netic resonance imaging (MRI), drug delivery, and hyperthermia
as well as cell separation. Other polymers such as polyurethane
(PU) [9], polyaniline (PANI) [10], polypyrrole (Ppy) [11], polyethyl-
ene oxide (PEO) [12] and natural rubber [13], have also been used
to prepare the respective Fe3O4/polymer composites. These com-
posites have potential use in batteries, capacitors, fuel and solar
cells, electromagnetic wave absorbers and magnetic materials.
The electrical characteristics of Fe3O4/polymer nanocomposites
have also attracted the interest of researchers recently due to their
potential applications particularly in electronic packaging. Bakyal
and co-workers [5,6,14–18] have reported the electrical conductiv-
ity characteristics of several corresponding Fe3O4/polymer nano-
composites. In most of the cases, they found that the composites
exhibit high conductivity at high temperature and the composite’s
conductivity was less dependent on frequency.
Epoxidized natural rubber (ENR) is a modified natural rubber
with epoxide and alkene groups randomly distributed in its back-
bone [19]. It possesses low glass transition temperature (Tg), high
polarity and flexibility, good elastomeric and adhesion properties.
Due to these characteristics, it has therefore been applied in gas
membrane [20], lithium cell [21,22] and so on. Our group has suc-
cessfully prepared ENR-metal (Au [23,24], Pt [24] and Ag [25])
nanocomposites recently. The role of ENR as stabilizing agent to
control the size and dispersion of metal nanoparticles in the com-
posite was evident by these works.

0925-8388/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2013.01.135
 W.L. Tan, M. Abu Bakar / Journal of Alloys and Compounds 561 (2013) 40–47
To the best of our knowledge, there is scarcely any report on the
Fe3O4/ENR nanocomposites. In these composites, it is believed that
the ENR matrix affects the Fe3O4 particle size while the particles
also exert electrical, magnetic or optical properties. Hence, these
composites may have potential applications in electronic devices,
sensors, radiation absorbers, recording media and the likes. Thus,
in this article, we report a simple in situ synthesis of Fe3O4/ENR
nanocomposites and their electrical properties as studied via
impedance spectroscopy.
2. Experimental
2.1. Materials
All chemicals were used without further purification unless otherwise stated.
The following chemicals were purchased; tetrahydrofuran, THF (J.T. Baker, USA),
toluene (Fisher Chemicals, UK), iron (II) sulfate heptahydrate, FeSO4.7H2O (99.5%)
and potassium hydroxide, KOH (both from R & M Chemicals, UK) and ethanol (Sys-
term, Malaysia). Epoxidized natural rubber with 50% epoxidation (ENR-50) was
supplied by Guthrie Polymer (Malaysia) Sdn. Bhd. and was purified according to lit-
erature before use [26].
2.2. Synthesis of Fe3O4/ENR nanocomposites
The route to obtain the Fe3O4 nanoparticles was achieved according to our pre-
vious work [27] while the synthesis of the Fe3O4/ENR nanocomposites was carried
out in a medium of toluene/water/ethanol according to Wen et al. [28]. In a typical
one-pot preparation, a certain amount of FeSO4 7H2O was dissolved in 3 mL of
deionized water in a round-bottomed flask. Then 5 mL of 50 mg mL1 ENR in tolu-
ene was added slowly with vigorously stirring. This was followed by the addition of
1 mL ethanol and the mixture was left to stir for an hour. The mixture was then
heated to 75 °C. After attaining the temperature, 0.5 mL of 2.5 M KOH was added
slowly into the mixture. Upon completion, the reaction mixture was heated for an-
other 2 h while vigorously stirring. Upon cooling, the solvent was evaporated using
a rotary evaporator. The residue was rinsed several times with distilled water prior
to redispersion of the residue in THF. A film with a thickness of 1 mm was ob-
tained by solvent casting the redispersed residue and drying under vacuum at
50 °C overnight. The other Fe3O4/ENR nanocomposites of various amount of Fe3O4
were prepared accordingly.
2.3. Characterizations
The FTIR spectra were recorded using a Thermo Nicolet IR200 spectrophotom-
eter. The sample was prepared by drop casting the redispersed residue as film
onto a KRS-5 window. The spectra were collected in the region of 4000–
400 cm1. The micrographs of the samples were obtained using a Philip CM 12
transmission electron microscope (TEM) operating at 80 kV. A drop of the colloid
was placed on a 400 mesh carbon coated copper grid and the solvent was evapo-
rated off. The particle sizes were measured from the TEM micrographs and ana-
lyzed using a computer software ‘‘analySis Docu’’ Version 3.2 (Soft Imaging
System GmbH, Munster, Germany). The average particle size and size distribution
were obtained from P300 particles. The Leo Supra 50VP Field Emission Scanning
Electron Microscopy (FE-SEM) equipped with X-mapping was utilized to deter-
mine the morphology and the distribution of components in the samples. The
samples were coated with a layer of gold prior to the analysis. Sample purity
and crystallinity were characterized using a SIEMENS D5000 X-ray diffractometer
(XRD) equipped with a monochromatic Cu Ka radiation filter. The samples were
scan in the 2h range of 0–100°. The glass transition temperature (Tg) of the sam-
ples were obtained using a Perkin Elmer Pyris Differential Scanning Calorimeter
(DSC). About 10 mg of the sample was sealed in an aluminium pan and heated
from room temperature to 120 °C at a heating rate of 20 °C min1. This was held
for 3 min at 120 °C and then quenched to 50 °C at a cooling rate of 100 °C min1.
The temperature was again held for another 3 min at 50 °C. The sample was
then heated to 120 °C at a heating rate of 20 °C min1. The electrical conductivity
of the samples was studied using EIS, GAMRY instrument at ambient conditions.
The samples were sandwiched between two stainless steel disks that function
as working and counter electrode [11] and scanned over a frequency range of
1 Hz–1 MHz at 10 mV amplitude. The samples were placed in a vacuum oven at
50 °C for 2 h prior to the EIS analyses. The Nyquist plot was fitted using a
ZSimDemo 3.22d software to obtain the equivalent circuit. The Fe content in
the composite samples was determined using a Perkin–Elmer Analyst 200 atomic
absorption spectroscopy (AAS). Typically, 20 mg of each of the samples was acid
digested prior to AAS analyses. The AAS results were expressed in terms of wt.%
of Fe3O4 as tabulated in Table 1.
41
Table 1
The Tg, exponent (n), pre-exponential factor (A) and linear regression (r) values for
ENR and the various Fe3O4/ENR nanocomposites.
Base Fe3O4 contenta (wt.%) Tg (°C) n A r
ENR 0 19 0.97 1.75  1012 0.9995
2.8 16.8 0.88 7.98  1012 0.9998
3.9 18.4 0.87 1.73  1011 0.9997
5.1 17.6 0.79 2.93  1011 0.9996
9.4 17.3 0.78 3.66  1010 0.9996
16.3 17.3 0.78 3.03  1010 0.9986
a
Determined using AAS.
3. Results and discussion
3.1. Synthesis and characterizations
An in situ synthesis of Fe3O4 particles in the ENR matrix was car-
ried out in a medium of water–toluene–ethanol. The addition of
ethanol into an immiscible mixture of ENR in toluene and aqueous
salt solution afforded a homogenous milky white solution. The eth-
anol has a mutual solubility in water and toluene solvent. Upon
addition of KOH, the milky solution gradually changed to green
and finally to black in color. This corresponds to the typical transi-
tion of the transient iron hydroxide to magnetite particles as pre-
viously reported [27]. The conversion of FeSO4 to Fe3O4 is
according to Eq. (1). A black flexible film of the composite was ob-
tained via solvent casting method
6FeSO4 þ 12KOH þ O2 ! 2Fe3 O4 þ 6H2 O þ 6K2 SO4 ð1Þ
XRD analysis confirmed the existence of Fe3O4 particles. Fig. 1
shows the typical XRD pattern of the composite. The observed 2h
values at 30.3°, 35.7°, 43.1°, 53.6°, 57.4°, 62.6° and 90.2° are in-
dexed to the (2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), (4 4 0) and (5 3 3)
reflection planes attributed to the magnetite crystals (JCPDS File
No. 19-629) [29]. The average size of Fe3O4 particles is about
16 nm based on the Scherrer analysis [30].
Fig. 2 depicts the FTIR spectra of ENR, typical Fe3O4/ENR nano-
composite, pristine Fe3O4 and ENR treated with KOH (ENR/KOH).
The peaks and their corresponding assignments are shown in Ta-
ble 2. The FTIR spectrum of ENR (Fig. 2a) shows characteristic
peaks similar to that reported in several literatures [31,32]. The
peaks at 876 and 1253 cm1 are assigned to the respective asym-
metrical and symmetrical stretching of the epoxide ring ( ).
Whereas the carbon–carbon double bond (C@C) stretching and
the @CAH bending peaks are situated at 1659 and 836 cm1
respectively. The intense peaks at 2965, 2924 and 2862 cm1 are
attributed to CAH stretching vibrations. The CAH bending peaks
are located at 1377 and 1453 cm1. In addition, a broad peak also
appears at 3490 cm1 which may be due to the OAH of epoxide
ring opened derivative of ENR as well as the adventitious moisture.
The typical FTIR spectrum of the composite is shown in Fig. 2b. The
composite still inherits the characteristic peaks of ENR and the
peak positions were similar to that of ENR as shown in Table 2.
An additional peak however, appears at 574 cm1 in the spectrum
of the composite. This peak is attributed to FeAO stretching [27]
and is similar to the FeAO stretching in pristine Fe3O4 as shown
by the spectrum in Fig. 2c.
In order to understand the effect of KOH on ENR, an experiment
was carried out under similar conditions and procedure but with
the exclusion of Fe salt. The obtained spectrum is shown in
Fig. 2d. The main difference between spectra of Fig. 2a and d is
the broadening and intensifying of the OAH peak for the later. This
may be attributed to the presence of diol resulting from the ring
opening of epoxide in the ENR under alkaline condition [33,34]
as well as the inter-chain hydrogen bondings that occur between
42 W.L. Tan, M. Abu Bakar / Journal of Alloys and Compounds 561 (2013) 40–47

Fig. 1. Typical XRD pattern of Fe3O4/ENR nanocomposite and the corresponding reference peak profile (JCPDS File No. 19-629).

Table 2
FTIR peak positions and assignments for ENR, typical Fe3O4/ENR nanocomposite,
Fe3O4 and ENR reacted with KOH.

Assignment Peak position

ENR Fe3O4/ENR Pristine Fe3O4 ENR/KOH
tas (CAH) 2965, 2924 2964, 2925 – 2962, 2923
ts (CAH) 2862 2861 – 2860
CAH bending 1377, 1453 1379, 1453 – 1379, 1447
1253 1255 – 1256
ts ( )

876 877 – 877

tas
tas (C@C) 1659 1657 – 1652
@CAH bending 836 837 – 838
OAH 3489 3490 – 3400
t (FeAO) – 574 577 –

ENR is 1.18 and 0.43 respectively. These are respectively 1.12

and 0.74 in the Fe3O4/ENR composite and 1.02 and 1.18 in the
ENR/KOH sample. Obviously, some epoxide ring opening reactions
have taken place in the composite and the ENR/KOH sample. Nev-
ertheless, the extent of the epoxide ring opening reaction in the
Fe3O4/ENR was less than that in ENR/KOH sample. This may mean
that most of the KOH was involved in the formation of Fe3O4 par-
ticles instead of acting as catalyst for the epoxide ring opening
reaction of the ENR in the composite. Therefore, FTIR results sug-
gest that, in the Fe3O4/ENR composite, there were occurrence of
epoxide ring opening in the ENR and there is no evidence of chem-
Fig. 2. Typical FTIR spectra of (a) ENR, (b) Fe3O4/ENR nanocomposite, (c) pristine
ical interactions between ENR and Fe3O4 particles.
Fe3O4 and (d) ENR reacted with KOH. The surface morphology of ENR and Fe3O4/ENR nanocomposites
were investigated by SEM and the micrographs are shown in
Fig. 3a–c. From Fig. 3a, ENR shows a smooth and clean surface.
the diol derivatives of ENR. Other peaks including CAH stretching The surface is however, rougher for Fe3O4/ENR nanocomposites
and bending, ( ) stretching, C@C stretching and @CAH bending due to the distribution of Fe3O4 particles even in the composite
containing low wt.% of Fe3O4 as shown by the composite in
remain similar to those of ENR.
Fig. 3b. This surface roughness was more pronounced for compos-
To further evaluate the extent of ring opening in the samples,
ites containing a higher wt.% Fe3O4 as shown in Fig. 3c.
the relative peak height of tas( ) or OAH to the @CAH bending X-mapping analysis was performed in order to determine the
was monitored [34]. The @CAH bending peak was selected as ref- distribution of Fe3O4 particles in the composite. The micrographs
erence because it does not involve in the ring opening reaction. The of the surface and cross section of the Fe3O4/ENR nanocomposite
as well as the respective distribution of Fe are presented in
ratio of [tas( )/@CAH bending] and [OAH/@CAH bending] for Fig. 4a and b correspondingly. It is clearly seen that the Fe of
 W.L. Tan, M. Abu Bakar / Journal of Alloys and Compounds 561 (2013) 40–47 43

Fig. 3. SEM micrographs (350 magnification) of (a) ENR and the ENR/Fe3O4 composites containing (b) 2.8 wt.% and (c) 9.4 wt.% Fe3O4 and the TEM micrographs of (d) Fe3O4
particles and the ENR/Fe3O4 composites containing (e) 2.8 wt.% and (f) 9.4 wt.% Fe3O4.

Fe3O4 particles which are presented by the brighter area are well
distributed in the entire matrix. Even so, from Fig. 4a(ii), some par-
ticle agglomerates are also visible at high magnification.
The size and morphology of Fe3O4 particles in the various Fe3O4/
ENR nanocomposites as well as the bare Fe3O4 particles were
investigated. The TEM micrographs are shown in Fig. 3d–f. Without
the protection of ENR, the bare Fe3O4 particles were highly agglom-
erated as shown in Fig. 3d(i). These particles have an average size
of 33.3 ± 21.9 nm with a broad size distribution exhibiting various
geometries. Some of these particles show distinctive outlines like
circle, square, rod or hexagon as shown in Fig. 3d(ii). This observa-
tion is similar to previous reported work and is attributed to the
un-inhibited crystal growth [35].
The TEM micrographs of the representative Fe3O4/ENR nano-
composites are shown in Fig. 3e–f. As inferred from Fig. 3e(i), the
distribution of Fe3O4 particles in the composite with lower wt.%
(ca. 2.8 wt.%) were isolated congregates. However, as the Fe3O4
particles loading is increased (ca. 9.4 wt.%) in the composite, the
particles were more dispersed (Fig. 3f(i)). From Fig. 3e(ii) and
f(ii), the particles are mostly sphere-like. Especially at high wt.%
of Fe3O4 loading some rod-like and cube shape particles are also
observed. The average particle size is 4.0 ± 1.0 nm and 4.1 ±
1.2 nm for composites with Fe3O4 loadings of 2.8 and 3.9 wt.%
respectively. These values increased slightly to 4.9 ± 1.0 nm,
5.3 ± 1.3 nm and 4.8 ± 2.1 nm for the respective composites con-
taining 5.1, 9.4 and 16.3 wt.% of Fe3O4. The particle size and size
distribution for Fe3O4 particles synthesized in the presence of
ENR were much smaller compare to the bare Fe3O4. The reduction
in particle size of Fe3O4 when incorporated in the ENR matrix is
explainable as follows. During synthesis, the metal precursors are
enclosed within the nanovoids formed within the entanglement
of the polymer chains. These nanovoids serve as nanoreactors for
the formation of Fe3O4 particles [36]. The confinement within the
cavity of the voids inhibits the growth of particles and simulta-
neously protects the particles from serious aggregation. This inev-
itably governs the size of the as-formed Fe3O4 particles [24,25].
44 W.L. Tan, M. Abu Bakar / Journal of Alloys and Compounds 561 (2013) 40–47

Fig. 4. SEM and X-mapping micrographs of ENR composited with 5.1 wt.% Fe3O4 showing the (a) surface at (i) low (100) and (ii) high (2500) magnification and (b) low
(100) magnification cross sectional profiles.

Thus size control of Fe3O4 particles can be achieved using ENR as
the matrix where the particles in the composites are in the size
range of 3–6 nm based on TEM observations.
It was also noted that there is a discrepancy in the average par-
ticle size obtained based on XRD and TEM analyses. The former is
based on the peak width of the most intense diffraction plane while
the later is based on direct visual measurement from micrograph
images. In the former, there are some factors that may contribute
to the inaccuracy including shape factor, strain, broad size distribu-
tion and polycrystallinity [37,38]. According to Calvin and co-work-
ers [38], TEM is the most accurate method to estimate the size of
the particles provided that sufficient data is available, while XRD
method tends to encompass the largest crystal size in the sample.
The Tg of ENR and ENR treated with KOH is 19 °C [24] and
16.4 °C respectively. A decrement in the number of epoxide
groups in the ENR treated with KOH and the simultaneous forma-
tion of inter-chain hydrogen bondings by diol derivatives of ENR
have resulted in higher Tg. As shown in Table 1, the Tg for the com-
posites fall within the range of 18.4 to 16.8 °C. This increment
was marginal (ca. <2 °C) as compared to ENR. The addition of inor-
ganic fillers into a polymer matrix reduces the free volume of the
polymer and this tends to restrict the flexibility or movement of
the polymer segments that consequently resulted in an increase
in Tg of the polymer [39]. Any shiftment in Tg of a composite with
respect to their parent components can be used as an indication to
evaluate the extent of interaction [40]. In this current study, the
 W.L. Tan, M. Abu Bakar / Journal of Alloys and Compounds 561 (2013) 40–47
-3
-4
log ( σAC)/ Scm -1
-5
-6
-7
-8
-9
-10
-11
0 1 2 3 4 5 6 7
-1
log (w)/ s
Fig. 5. Plot of AC conductivity versus angular frequency for ENR and Fe3O4/ENR
nanocomposites with various wt.% of Fe3O4.
small difference in Tg values between the ENR of the composites
and ENR suggests that, in the composite, there is no chemical
interaction between the Fe3O4 particles and the ENR matrix. This
is supported by the FTIR results discussed previously where the
difference in the wavenumber due to the FeAO stretching in bare
and composited Fe3O4 is <5 cm1. Similar attribute has also been
reported previously [40–42]. For instance, Kuljanin et al. [41,42]
has incorporated lead sulfide (PbS) and cadmium sulfide (CdS)
nanoparticles into polyvinyl alcohol (PVA) and polystyrene (PS)
respectively. The FTIR and DSC techniques were employed to
determine the possible interactions between the particle and poly-
mer. They found that there is no difference between the FTIR spec-
tra of the pristine polymer and the composite while the change in
Tg is <2 °C. They conclude that the interaction between the particle
and polymer in the respective composites as insignificant.
3.2. Electrical conductivity
The correlation between the alternating current (AC) conductiv-
ity (rAC) and the direct current (DC) conductivity (rDC) at a con-
stant temperature can be expressed via the following [39]:
rAC ¼ rDC þ AðxÞn
In Eq. (2), A and n are parameters dependent on temperature
and filler content. Thus the rAC is a summation of actual ohmic
conductivity (rDC) and the dielectric dispersion [29,43]. The latter
is mainly due to the polarization and dielectric relaxation in the
system. The rDC is related to frequency-independent conductivity.
It is characterized by the movement of the charge carriers and is
limited by the conducting path provided in the system [29].
The rAC of ENR and ENR filled with various amount of Fe3O4 was
studied as a function of angular frequency and the results are pre-
sented in Fig. 5. Generally, the conductivity of ENR steadily increases
with the increase in frequency and is in the order of 1011–107 -
S cm1. This increase is also commonly observed for organic materi-
als like L-lysine [6], poly(2-thiophen-3-yl-malonic acid) [16] and
poly(1-vinyl-1,2,4-triazole) (PVTri) [17]. The Fe3O4/ENR nanocom-
posites however, exhibit a conductivity plateau at low frequency
but the conductivity increases at high frequency. The range of fre-
quency encompass by the plateau increases upon increasing in
Fe3O4 content in the composite. For example, the ENR composite
with 2.8 and 3.9 wt.% Fe3O4 showed a plateau ranged between 0.8
and 1.7 s1 while the plateau for ENR with 16.3 wt.% Fe3O4 is from
0.8 to 5.1 s1. Furthermore, increasing the wt.% of Fe3O4 in the ENR
has resulted in the rAC of the composites to increase. For instance,
the rAC of the ENR composites with 2.8 and 16.3 wt.% Fe3O4 is in
the order of 1010–107 and 106–104 S cm1 respectively. The
rAC curves at higher frequencies were fitted according to Eq. (2),
and the best fitted curves are shown as (red1) solid lines in Fig. 5.
1
For interpretation of color in ‘Figs. 5 and 7’, the reader is referred to the web
version of this article.
45
1.00E-04
1.00E-05
0 wt%
σDC (Scm -1)
2.8 wt% 1.00E-06
3.9 wt% 1.00E-07
5.1 wt%
9.4 wt% 1.00E-08
16.3 wt% 1.00E-09
1.00E-10
0 2 4 6 8 10 12 14 16 18
Fe 3O4 content (wt%)
Fig. 6. The plot of rDC conductivity against the wt.% of Fe3O4 in the composites.
The n and A as well as their linear regression (r) values extracted from
the fitted curves are tabulated in Table 1. The Fe3O4/ENR composites
exhibit lower n (i.e. 0.78–0.87) compare to ENR (0.97) and this falls
within the range of 0.5 < n < 0.9. This is typical for carrier transport
in disordered materials [44].
The rDC of the Fe3O4/ENR nanocomposites was derived from the
plateau region of Fig. 5 [14,15,17,29]. The plot of rDC of the compos-
ites versus wt.% of Fe3O4 in the composites is depicted in Fig. 6. The
rDC of the Fe3O4/ENR nanocomposites increases with the increase in
wt.% Fe3O4. Those composites with 2.8 and 3.9 wt.% Fe3O4 demon-
strate lower conductivity at 2.2  1010 and 4.5  1010 S cm1
respectively. This increases to 1.0  108 S cm1 for composite with
5.1 wt.% Fe3O4 and 1.1  107 S cm1 for composite with 9.4 wt.%
Fe3O4. The highest rDC was shown by the composite with
16.3 wt.% Fe3O4 and is at 1.4  106 S cm1. This rDC behavior of
the Fe3O4/ENR nanocomposites is probably due to the grain and/or
grain boundary charge carriers migration [15]. The composites with
low wt.% of Fe3O4 have particles mostly in isolated congregates and
thus conduction of these composites were relatively low. In the
composites with high wt.% of Fe3O4, the distance between the parti-
cles was closer and this facilitates the conduction across the poly-
mer and increase the conductivity in the composite [15].
ð2Þ
3.3. Equivalent circuit
The Nyquist plots for the various Fe3O4/ENR nanocomposites
and the fitted circuit are presented in Fig. 7. The respective red
and green markers represent the experimental and calculated val-
ues. The plot demonstrates an incomplete semicircle for compos-
ites containing low wt.% of Fe3O4 (Fig. 7a and b). This was
however, transformed into a slightly distorted semicircle as the
amount of Fe3O4 was increased to 5.1 wt.% (Fig. 7c). Further incre-
ment of Fe3O4 in the composite (ca. to 9.4 and 16.3 wt.% as shown
in Fig. 7d and e respectively) caused a small or shrinking semicircle
with a straight line tail. Although the feature of Nyquist plots was
transformed upon varying the amount of added Fe3O4 in the com-
posite, they are nevertheless, best-fitted into an equivalent circuit
as shown in Fig. 7f. As seen, an equivalent circuit with a combina-
tion of constant phase element, Qm that is parallel with another Qp
in series with resistor, Rm was fitted to the experimental data. The
Fe3O4 particles behave both as resistor and capacitor due to its
respective semiconducting and polarizing nature [1]. The intra-
particle (grain boundary) as well as the inter-particle (grain)
conduction dictates the Rm in the circuit. At the same time, Fe3O4
particles can also be polarized where the charge carrier(s) migra-
tion between the Fe2+ and Fe3+ respond to the direction of the ap-
plied field. In this case, Fe3O4 particles give a capacitive behavior,
Qm to the circuit. The ENR matrix around the Fe3O4 particles may
further contribute capacitive behavior, Qp, in the composite [15].
This is because the polymer may undergo polarization and relaxa-
tion in an applied electrical field [45]. Hence a Qp is in parallel to
Qm in the circuit. It should be noted that a non-ideal capacitor
(viz. constant phase element) is used to present the capacitance
46 W.L. Tan, M. Abu Bakar / Journal of Alloys and Compounds 561 (2013) 40–47

Fig. 7. Nyquist plot for Fe3O4/ENR nanocomposites containing (a) 2.8 wt.%, (b) 3.9 wt.%, (c) 5.1 wt.%, (d) 9.4 wt.%, (e) 16.3 wt.% Fe3O4 and (f) the equivalent circuit.

element in the system instead of an ideal capacitor (C). This may be
due to the range of particle sizes as well as distribution of Fe3O4
particles within the composite. Even so, in the case of composites
with higher Fe3O4 content (i.e. 9.4 and 16.3 wt.%), a Warburg ele-
ment (Zw) may also be added in series to the (QRQ) circuit to suit
the low frequency spike feature of the plots. This contribution ac-
counts the ionic diffusion along the Fe3O4 particle paths and at the
electrode interfaces [46].
4. Conclusion
The Fe3O4 particles were successfully synthesized in situ in the
presence of ENR. XRD results support the formation of Fe3O4 crys-
tals and no trace of impurities in the composites was observed. The
calculated particle size was around 16 nm based on Scherrer anal-
ysis. The FTIR spectra of ENR and Fe3O4/ENR nanocomposites show
no significant change or shift in peak wavenumber. This suggests
that there was no chemical interaction between ENR and Fe3O4
particles. This is supported by the Tg value of nanocomposites that
only marginally shifted (i.e. 2 °C) as compared to ENR. The aver-
age particle size of the Fe3O4 particles in the composites was with-
in 3–6 nm based on TEM results. Therefore, the ENR matrix was
able to control the particle size at ca. <20 nm. SEM and X-mapping
images demonstrate that the Fe3O4 particles were distributed
throughout the ENR matrix. The electrical conductivity of Fe3O4/
ENR nanocomposites shows a plateau at low frequency but in-
creased steadily at high frequency. Incorporating and increasing
the amount of Fe3O4 particles in the composite increased the con-
ductivity of the composite as more conduction paths are provided
for the migration of charge carrier(s).
 W.L. Tan, M. Abu Bakar / Journal of Alloys and Compounds 561 (2013) 40–47
Acknowledgements
The authors acknowledge the Universiti Sains Malaysia for the
respective Grants: 1001/PKIMIA/811025 and 1001/PKIMIA/
843032. The authors also thank the Universiti Sains Malaysia for
the USM Fellowship to TWL.
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