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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
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 41
To the best of our knowledge, there is scarcely any report on the Table 1
Fe3O4/ENR nanocomposites. In these composites, it is believed that The Tg, exponent (n), pre-exponential factor (A) and linear regression (r) values for
ENR and the various Fe3O4/ENR nanocomposites.
the ENR matrix affects the Fe3O4 particle size while the particles
also exert electrical, magnetic or optical properties. Hence, these Base Fe3O4 contenta (wt.%) Tg (°C) n A r
composites may have potential applications in electronic devices, ENR 0 19 0.97 1.75 1012 0.9995
sensors, radiation absorbers, recording media and the likes. Thus, 2.8 16.8 0.88 7.98 1012 0.9998
in this article, we report a simple in situ synthesis of Fe3O4/ENR 3.9 18.4 0.87 1.73 1011 0.9997
5.1 17.6 0.79 2.93 1011 0.9996
nanocomposites and their electrical properties as studied via 9.4 17.3 0.78 3.66 1010 0.9996
impedance spectroscopy. 16.3 17.3 0.78 3.03 1010 0.9986
a
Determined using AAS.
2. Experimental
3. Results and discussion
2.1. Materials
All chemicals were used without further purification unless otherwise stated. 3.1. Synthesis and characterizations
The following chemicals were purchased; tetrahydrofuran, THF (J.T. Baker, USA),
toluene (Fisher Chemicals, UK), iron (II) sulfate heptahydrate, FeSO4.7H2O (99.5%) An in situ synthesis of Fe3O4 particles in the ENR matrix was car-
and potassium hydroxide, KOH (both from R & M Chemicals, UK) and ethanol (Sys- ried out in a medium of water–toluene–ethanol. The addition of
term, Malaysia). Epoxidized natural rubber with 50% epoxidation (ENR-50) was
supplied by Guthrie Polymer (Malaysia) Sdn. Bhd. and was purified according to lit-
ethanol into an immiscible mixture of ENR in toluene and aqueous
erature before use [26]. 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
2.2. Synthesis of Fe3O4/ENR nanocomposites and finally to black in color. This corresponds to the typical transi-
tion of the transient iron hydroxide to magnetite particles as pre-
The route to obtain the Fe3O4 nanoparticles was achieved according to our pre-
viously reported [27]. The conversion of FeSO4 to Fe3O4 is
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 according to Eq. (1). A black flexible film of the composite was ob-
one-pot preparation, a certain amount of FeSO4 7H2O was dissolved in 3 mL of tained via solvent casting method
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 6FeSO4 þ 12KOH þ O2 ! 2Fe3 O4 þ 6H2 O þ 6K2 SO4 ð1Þ
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 XRD analysis confirmed the existence of Fe3O4 particles. Fig. 1
slowly into the mixture. Upon completion, the reaction mixture was heated for an- shows the typical XRD pattern of the composite. The observed 2h
other 2 h while vigorously stirring. Upon cooling, the solvent was evaporated using values at 30.3°, 35.7°, 43.1°, 53.6°, 57.4°, 62.6° and 90.2° are in-
a rotary evaporator. The residue was rinsed several times with distilled water prior
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)
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
reflection planes attributed to the magnetite crystals (JCPDS File
50 °C overnight. The other Fe3O4/ENR nanocomposites of various amount of Fe3O4 No. 19-629) [29]. The average size of Fe3O4 particles is about
were prepared accordingly. 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).
2.3. Characterizations The peaks and their corresponding assignments are shown in Ta-
ble 2. The FTIR spectrum of ENR (Fig. 2a) shows characteristic
The FTIR spectra were recorded using a Thermo Nicolet IR200 spectrophotom-
eter. The sample was prepared by drop casting the redispersed residue as film peaks similar to that reported in several literatures [31,32]. The
onto a KRS-5 window. The spectra were collected in the region of 4000– peaks at 876 and 1253 cm1 are assigned to the respective asym-
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 metrical and symmetrical stretching of the epoxide ring ( ).
was placed on a 400 mesh carbon coated copper grid and the solvent was evapo- Whereas the carbon–carbon double bond (C@C) stretching and
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
the @CAH bending peaks are situated at 1659 and 836 cm1
System GmbH, Munster, Germany). The average particle size and size distribution respectively. The intense peaks at 2965, 2924 and 2862 cm1 are
were obtained from P300 particles. The Leo Supra 50VP Field Emission Scanning attributed to CAH stretching vibrations. The CAH bending peaks
Electron Microscopy (FE-SEM) equipped with X-mapping was utilized to deter- are located at 1377 and 1453 cm1. In addition, a broad peak also
mine the morphology and the distribution of components in the samples. The
appears at 3490 cm1 which may be due to the OAH of epoxide
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 ring opened derivative of ENR as well as the adventitious moisture.
(XRD) equipped with a monochromatic Cu Ka radiation filter. The samples were The typical FTIR spectrum of the composite is shown in Fig. 2b. The
scan in the 2h range of 0–100°. The glass transition temperature (Tg) of the sam- composite still inherits the characteristic peaks of ENR and the
ples were obtained using a Perkin Elmer Pyris Differential Scanning Calorimeter peak positions were similar to that of ENR as shown in Table 2.
(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
An additional peak however, appears at 574 cm1 in the spectrum
for 3 min at 120 °C and then quenched to 50 °C at a cooling rate of 100 °C min1. of the composite. This peak is attributed to FeAO stretching [27]
The temperature was again held for another 3 min at 50 °C. The sample was and is similar to the FeAO stretching in pristine Fe3O4 as shown
then heated to 120 °C at a heating rate of 20 °C min1. The electrical conductivity by the spectrum in Fig. 2c.
of the samples was studied using EIS, GAMRY instrument at ambient conditions.
In order to understand the effect of KOH on ENR, an experiment
The samples were sandwiched between two stainless steel disks that function
as working and counter electrode [11] and scanned over a frequency range of was carried out under similar conditions and procedure but with
1 Hz–1 MHz at 10 mV amplitude. The samples were placed in a vacuum oven at the exclusion of Fe salt. The obtained spectrum is shown in
50 °C for 2 h prior to the EIS analyses. The Nyquist plot was fitted using a Fig. 2d. The main difference between spectra of Fig. 2a and d is
ZSimDemo 3.22d software to obtain the equivalent circuit. The Fe content in the broadening and intensifying of the OAH peak for the later. This
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
may be attributed to the presence of diol resulting from the ring
digested prior to AAS analyses. The AAS results were expressed in terms of wt.% opening of epoxide in the ENR under alkaline condition [33,34]
of Fe3O4 as tabulated in Table 1. 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.
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 particles were more dispersed (Fig. 3f(i)). From Fig. 3e(ii) and
distributed in the entire matrix. Even so, from Fig. 4a(ii), some par- f(ii), the particles are mostly sphere-like. Especially at high wt.%
ticle agglomerates are also visible at high magnification. of Fe3O4 loading some rod-like and cube shape particles are also
The size and morphology of Fe3O4 particles in the various Fe3O4/ observed. The average particle size is 4.0 ± 1.0 nm and 4.1 ±
ENR nanocomposites as well as the bare Fe3O4 particles were 1.2 nm for composites with Fe3O4 loadings of 2.8 and 3.9 wt.%
investigated. The TEM micrographs are shown in Fig. 3d–f. Without respectively. These values increased slightly to 4.9 ± 1.0 nm,
the protection of ENR, the bare Fe3O4 particles were highly agglom- 5.3 ± 1.3 nm and 4.8 ± 2.1 nm for the respective composites con-
erated as shown in Fig. 3d(i). These particles have an average size taining 5.1, 9.4 and 16.3 wt.% of Fe3O4. The particle size and size
of 33.3 ± 21.9 nm with a broad size distribution exhibiting various distribution for Fe3O4 particles synthesized in the presence of
geometries. Some of these particles show distinctive outlines like ENR were much smaller compare to the bare Fe3O4. The reduction
circle, square, rod or hexagon as shown in Fig. 3d(ii). This observa- in particle size of Fe3O4 when incorporated in the ENR matrix is
tion is similar to previous reported work and is attributed to the explainable as follows. During synthesis, the metal precursors are
un-inhibited crystal growth [35]. enclosed within the nanovoids formed within the entanglement
The TEM micrographs of the representative Fe3O4/ENR nano- of the polymer chains. These nanovoids serve as nanoreactors for
composites are shown in Fig. 3e–f. As inferred from Fig. 3e(i), the the formation of Fe3O4 particles [36]. The confinement within the
distribution of Fe3O4 particles in the composite with lower wt.% cavity of the voids inhibits the growth of particles and simulta-
(ca. 2.8 wt.%) were isolated congregates. However, as the Fe3O4 neously protects the particles from serious aggregation. This inev-
particles loading is increased (ca. 9.4 wt.%) in the composite, the 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 Tg of ENR and ENR treated with KOH is 19 °C [24] and
the matrix where the particles in the composites are in the size 16.4 °C respectively. A decrement in the number of epoxide
range of 3–6 nm based on TEM observations. groups in the ENR treated with KOH and the simultaneous forma-
It was also noted that there is a discrepancy in the average par- tion of inter-chain hydrogen bondings by diol derivatives of ENR
ticle size obtained based on XRD and TEM analyses. The former is have resulted in higher Tg. As shown in Table 1, the Tg for the com-
based on the peak width of the most intense diffraction plane while posites fall within the range of 18.4 to 16.8 °C. This increment
the later is based on direct visual measurement from micrograph was marginal (ca. <2 °C) as compared to ENR. The addition of inor-
images. In the former, there are some factors that may contribute ganic fillers into a polymer matrix reduces the free volume of the
to the inaccuracy including shape factor, strain, broad size distribu- polymer and this tends to restrict the flexibility or movement of
tion and polycrystallinity [37,38]. According to Calvin and co-work- the polymer segments that consequently resulted in an increase
ers [38], TEM is the most accurate method to estimate the size of in Tg of the polymer [39]. Any shiftment in Tg of a composite with
the particles provided that sufficient data is available, while XRD respect to their parent components can be used as an indication to
method tends to encompass the largest crystal size in the sample. 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 45
-3 1.00E-04
-4 1.00E-05
log ( σAC)/ Scm -1
-5 0 wt%
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 ysis. The FTIR spectra of ENR and Fe3O4/ENR nanocomposites show
due to the range of particle sizes as well as distribution of Fe3O4 no significant change or shift in peak wavenumber. This suggests
particles within the composite. Even so, in the case of composites that there was no chemical interaction between ENR and Fe3O4
with higher Fe3O4 content (i.e. 9.4 and 16.3 wt.%), a Warburg ele- particles. This is supported by the Tg value of nanocomposites that
ment (Zw) may also be added in series to the (QRQ) circuit to suit only marginally shifted (i.e. 2 °C) as compared to ENR. The aver-
the low frequency spike feature of the plots. This contribution ac- age particle size of the Fe3O4 particles in the composites was with-
counts the ionic diffusion along the Fe3O4 particle paths and at the in 3–6 nm based on TEM results. Therefore, the ENR matrix was
electrode interfaces [46]. able to control the particle size at ca. <20 nm. SEM and X-mapping
images demonstrate that the Fe3O4 particles were distributed
4. Conclusion throughout the ENR matrix. The electrical conductivity of Fe3O4/
ENR nanocomposites shows a plateau at low frequency but in-
The Fe3O4 particles were successfully synthesized in situ in the creased steadily at high frequency. Incorporating and increasing
presence of ENR. XRD results support the formation of Fe3O4 crys- the amount of Fe3O4 particles in the composite increased the con-
tals and no trace of impurities in the composites was observed. The ductivity of the composite as more conduction paths are provided
calculated particle size was around 16 nm based on Scherrer anal- for the migration of charge carrier(s).
W.L. Tan, M. Abu Bakar / Journal of Alloys and Compounds 561 (2013) 40–47 47
Acknowledgements [19] C.S.L. Baker, Chapter 3: modified natural rubber, in: A.K. Bhowmick, H.L.
Stephens (Eds.), Handbook of Elastomers, second ed., Marcel Dekker Inc., New
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The authors acknowledge the Universiti Sains Malaysia for the [20] T. Johnson, S. Thomas, Polymer 40 (1999) 3223.
respective Grants: 1001/PKIMIA/811025 and 1001/PKIMIA/ [21] S.N. Mohamed, N.A. Johari, A.M.M. Ali, M.K. Harun, M.Z.A. Yahya, J. Power
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[22] R. Idris, M.D. Glasse, R.J. Latham, R.G. Linford, W.S. Schlindwein, J. Power
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[23] M. Abu Bakar, J. Ismail, C.H. Teoh, W.L. Tan, S. Ong, J. Rubber Res. 11 (2008)
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