Applied Surface Science 374 (2016) 213–221

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Applied Surface Science

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

Synthesis and characterization of polyaniline–Fe@C magnetic

nanocomposite powder
C.T. Fleaca a,b,∗ , F. Dumitrache a,b , I. Morjan a , A.-M. Niculescu a , I. Sandu a , A. Ilie a,c ,
I. Stamatin d , A. Iordache d , E. Vasile e , G. Prodan f
a
National Institute for Lasers, Plasma and Radiation Physics (NILPRP), Atomistilor 409, R-077125 Magurele, Romania
b
“Politehnica” University of Bucharest, Faculty of Applied Sciences, Physics Department, Independentei 313, Bucharest, Romania
c
University of Bucharest, Physics Faculty, Atomistilor 405, Magurele, Romania
d
3NanoSAE Research Center, University of Bucharest, Atomistilor 405, Magurele, Romania
e
“Politehnica” University of Bucharest, Faculty of Applied Chemistry and Materials Science, Gh. Polizu. 1-7, Bucharest, Romania
f
“Ovidius” University, Nanotechnology and Alternative Energy Sources Institute, Mamaia 124, Constanta, Romania

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

Article history: We report the synthesis of novel magnetic nanocomposite based on polyaniline (PANI) matrix and
Received 21 June 2015 Fe–C nanoparticles. These hydrophobic Fe–Fex C@C nanoparticles (having diameters under 20 nm)
Received in revised form 29 October 2015 were synthesized by laser pyrolysis from Fe(CO)5 and C2 H4 /H2 and dispersed in water using sodium
Accepted 5 November 2015
carboxymethylcellulose, followed by the PANI coating using ultrasonication-assisted oxidative poly-
Available online 17 November 2015
merization of aniline hydrochloride. The structure of the resulted composite was characterized by
Transmission Electron Microscopy, X-ray diffraction and also by Raman and Infrared spectroscopy. The
PACS:
composite powder shows ferromagnetic behavior with low coercivity and 6.4 emu/g saturation magne-
81.16.Mk
75.50.Bb tization, having also electric and electrochemical behavior similar with pure PANI reference.
72.80.Le © 2015 Elsevier B.V. All rights reserved.
82.80.Fk

Keywords:
Laser pyrolysis
Magnetic nanocomposite
Polyaniline

1. Introduction polyacetylenes. They have a wide area of applications from electro-

The research in the field of multifunctional materials have been
accelerated in the recent years due to their ability to respond
to different stimuli and/or to perform multiple tasks required
for modern applications. An important class of such systems
is the organic/inorganic nanocomposites or hybrids based on
organic conductive polymers and various inorganic nanoparticles.
The intrinsically conductive polymers are organic polymers that
conduct electricity due to their conjugated ␲ electrons, having
metallic or semiconducting behavior, good environmental stability
and also interesting optical, mechanical and electronic proper-
ties. Polyaniline is one of the most known conductive polymers,
along with polypyrrole, polythiophene, polypenylenevinylene and
∗ Corresponding author at: National Institute for Lasers, Plasma and Radiation
Physics (NILPRP), Atomistilor 409, R-077125 Magurele, Romania.
Tel.: +40 21 4574489; fax: +40 21 4574243.
E-mail address: claudiufleaca@yahoo.com (C.T. Fleaca).
magnetic shielding or electrostatic materials, conducting adhesives
to artificial nerves, diodes, transistors or electrochemical supercap-
acitors [1,2]. By combining the qualities of the conducting polymer
with those of the nanoparticles, the resulting nanocomposites can
have improved properties and/or multiple functionalities based
on the synergistic interaction of the two components. One exam-
ple is the nanometric SnO2 –TiO2 loaded with PANI material for
the photocatalytic oxidation of long-chain alkenes [3] and another
is the Pt nanoparticle/carbon black – PANI based nanocomposite
which demonstrated high catalytic activity for fuel cell technology
[4]. An important class of this kind of composites are those PANI-
based which contain magnetic nanoparticles that allow them to
be manipulated and recovered from liquid dispersions under the
action of magnetic fields for various applications. The environmen-
tal remediation – decontamination of the polluted/wastewaters
was proved with these nanocomposites for inorganic contaminants
such as Cr(VI) [5,6], As (V) [7] or nitrate [8] by absorption/ ion
exchange/reduction/trapping mechanisms. Moreover, the nano-
magnetic/PANI materials were also successfully tested for the

http://dx.doi.org/10.1016/j.apsusc.2015.11.043
0169-4332/© 2015 Elsevier B.V. All rights reserved.
214 C.T. Fleaca et al. / Applied Surface Science 374 (2016) 213–221
extraction/elimination of various classes of organic contaminants,
from phenol and polychlorinated phenols [9] to various toxic dyes
such as Amido Black 10B [10] or Bromopyrogallol [11]. Other
important area of recent applications of these materials is the
biomedicine in the form of films for electrochemical sensing of
catechol [12] or, in combination with carbon nanotubes, as plat-
forms for bacterial detection [13] or for protein digestion using
immobilized trypsin enzyme [14]. Magnetite nanoparticles coated
with poly[aniline-co-N-(1-one butyric acid)aniline] were success-
fully used for Magnetic Resonance Imaging (MRI) contrast agents
[15] and for delivery of brain-targeted anticancer molecules like
epirubicin [15] or carmustine [16]. The Fe3 O4 nanoparticles coated
with PANI (by plasma polymerization) presented a large enhance-
ment of dielectric permittivity, a property which can be very
useful for energy storage in capacitors [17]. Also, the composite
from Ni–Zn–Mn ferrite nanoparticles mechanically milled/blended
with PANI was reported to have enhanced microwave absorption
properties for electromagnetic shielding applications [18]. Also,
it is worth noting that spinelic ferrite nanoparticles (␥Fe2 O3 and
MgFe2 O4 ) in combination with PANI as nano-composites were
used as sensor for volatile organic compounds (such as acetone,
ethanol and light hydrocarbons) vapor detection [19]. Recently, a
carbon nanoparticles-PANI (impregnated with iron species) com-
posite was transformed by pyrolysis in a porous FeNx C/C catalyst
material for oxygen reduction reaction (ORR) with high activity as
cathode in Polymer Electrolyte Fuel Cell (PEFC) and better stability
than commercial Pt/C in acid medium [20].
The great majority of the magnetic nanoparticles in these
PANI-based composites has an oxidic composition (magnetite,
maghemite or various ferrites), being usually obtained before the
aniline polymerization by different discontinuous liquid-based
techniques which requires multiple steps. Metallic iron nanocrys-
tals were also deposed on pre-synthesized PANI fibers using NaBH4
reduction of Fe salts [7]. The combination of the magnetic oxidic
particles with carbon for PANI-based composites was reported in
[5] as iron oxide nanoparticles inside mesoporous carbon (obtained
from ethanolic solution of Fe(NO3 )3 , oxalic acid and furfuryl alco-
hol impregnation in synthetic zeolite followed by annealing under
N2 and NaOH solution boiling), in [9] as Fe3 O4 submicron spheres
coated with conformal carbon layer (by solvothermal precipita-
tion from FeCl3 and CH3 COONa in ethylene glycol followed by
hydrothermal glucose carbonization) and in [14] as magnetite
nanoparticles decorating multiwall carbon nanotubes (from di- and
trivalent Fe ammonium sulfates in NH3 solution in presence of
suspended MWCNTs). Magnetic carbon-coated metallic nanopar-
ticles can be obtained by various gas-phase methods such as: arc
discharge (from graphite mixed with Fe, Co or Ni powders) [21],
radio-frequency plasma torch (from Fe/Co alloy microparticles)
[22], thermal disproportionation of CO in the presence of Fe(CO)5
with H2 and C2 H2 addition [23], Fe(C5 H5 )2 pyrolysis in H2 [24],
CVD (chemical vapor deposition) of CH4 on fumed SiO2 -supported
FeCo nanoparticles followed by HF solution etching [25], flame
spray pyrolysis in oxygen-depleted environment from iron 2-
ethyhexanoate and C2 H2 [26] or decomposition of CH4 or C4 H10
in presence of Fe or Ni metal vapors [27]. Also, liquid phase meth-
ods such as sonochemical decomposition of Fe(CO)5 in (C6 H5 )2 CH2
solvent [28] and even solid state approaches using high energy ball
milling and annealing of soot with Fe or Ni powders [29] or car-
bothermic reduction of ␣Fe2 O3 , Co2 O3 and NiO nano-/submicron
powders under N2 using carbon black [30] were reported. In this
paper, we obtained the magnetic carbon-coated metallic/carbidic
iron nanoparticles in one step by gas-phase laser pyrolysis method,
followed by their rapid dispersion in water with the aid of a polyan-
ionic electrolyte, able thus to attract the polycationic polyanilne
chains formed by aniline oxidative polymerization, resulting the
PANI-based magnetic nanocomposite.
2. Experimental
For the Fe-based nanoparticles synthesis we employed iron
pentacarbonyl (99.999%, from Fluka), ethylene (3.5), hydrogen
(3.0) and argon (5.0) from Linde. Distilled water, CMCNa (car-
boxymethylcellulose sodium salt medium viscosity, from Fluka),
hydrochloric acid (37% aqueous solution, from Silal), aniline
hydrochloride (analytical grade, from Reactivul) and (NH4 )2 S2 O8
ammonium peroxydisulfate (>98%, from Merk) were used for the
obtaining of magnetic PANI-based composite.
The laser pyrolysis synthesis installation was described in [31]
and the process parameters in [32]. Briefly, the reactive gas/vapor
mixture is introduced in the reaction zone situated in the middle
of the reaction chamber with the aid of a concentric multitubular
injector which delivers Fe(CO)5 vapors carried by C2 H4 (33 sccm)
through the central nozzle and a mixture of C2 H4 (43 sccm)–H2
(43 sccm) through the coaxial annular nozzle. The reactive inner
flows were surrounded by the third annular argon (2500 sccm)
flow for shielding and confinement, while the system pressure was
maintained at 500 mbar using a throttle valve and a vacuum pump.
Also, the two ZnSe windows of the reaction chamber were flushed
each with 500 sccm argon for their protection. A continuous car-
bon dioxide laser beam ( = 10.6 ␮m) was focused through a ZnSe
lens, orthogonally intersecting the reactive flows (focal spot diam-
eter 1.5 mm, power density above the injector 3900 W/cm2 ). Due to
laser infrared photons absorption by C2 H4 molecules followed by
decomposition of the precursors, a confined sooting flame appears
in the reaction zone, resulting Fe–C nanoparticles [32] which were
collected downstream using a porous filter.
The obtained hydrophobic Fe–C nanopowder was dispersed
in 100 ml distilled water (1 g/l) in the presence of CMCNa (3 g/l)
using short time (5 min) sonotrode ultrasonication (Hielscher
UIP 1000hd Homogenizer). Then, 0.52 g aniline hydrochloride
(C6 H5 NH3 + Cl− ) was dissolved in the suspension also under ultra-
sonication, followed after few minutes by the adding of 1.6 g
(NH4 )2 S2 O8 oxidative agent. After transferring the mixture into a
cooled (∼15 ◦ C) Elmasonic S40H ultrasonic bath, the sonication was
continued for another hour, then stopped and the resulted disper-
sion was left overnight for the finalization of the polymerization
process. Next day, a mixture of 200 ml water and 5 ml HCl 37% was
added under sonication, followed by magnetic separation using a
NdFeB magnet (2 × 2 × 4 cm3 ). After discarding the non-magnetic
PANI suspension, the magnetic wet slurry was diluted with 200 ml
water, the new suspension was ultrasonicated again and the mag-
netic separation was repeated. Finally, the magnetic composite was
naturally dried and finely pulverized using mortar and pestle.
The Raman spectra were recorded with a Jasco NRS 7200
MicroRaman Spectrometer using a green laser with a 532 nm
wavelength, whereas for the obtaining of the infrared spectrum,
a Shimadzu 8400S Fourier Transform Infrared (FTIR) Spectroscope
was employed. The structure and morphology of raw Fe@C pow-
der was examined with Tecnai F30 G2 (300 kV) and those of the
composite with Philips CM 120ST (120 kV) Transmission Electron
Microscopes. The crystallinity of raw nanoparticles, PANI and mag-
netic composite was evaluated using a PANalytical X’Pert MPD
theta–theta X-ray diffraction (XRD) apparatus using a Cu K␣ source
(0.15418 nm).
Composite’s magnetic properties were investigated using a
superconducting quantum interference device (SQUID) by recor-
ding the room-temperature magnetic hysteresis curve.
For the evaluation of the electrical properties, fine powders
of PANI, Fe@C and magnetic composite were introduced inside
of a glass tube (inner diameter 6 mm) and gradually pressed
between two conductive electrolytic graphite cylinders (which act
as pistons). The electrical resistance of the powders at different
compacting degrees was measured using a commercial ohmmeter.
 C.T. Fleaca et al. / Applied Surface Science 374 (2016) 213–221 215

Fig. 1. Up row: TEM images at higher (left) and lower (right) magnification of the raw Fe@C nanopowder (left inset shows an HR-TEM image of a single nanoparticle). Down
row: TEM images at higher (left) and lower (right) magnification from the Fe@C(CMCNa)/PANI composite.

The electrochemical behavior of PANI and PANI/Fe@C com-
posite was evaluated by Cyclic Voltammetry using VoltaLab 40
(PGZ301 & VoltaMaster 4) Dynamic Electrochemical Laboratory
from Radiometer Analytical SA in a three-electrode cell working in
0.1 M HClO4 electrolyte. The voltage was registered using Dynamic
Hydrogen Electrode (DHE) as reference electrode in the potential
window ranged from 0 to 1.4 V at scan rates of 50, 100 and 200 mV/s.
3. Results and discussions
The synthesis of iron/carbon nanoparticles by the laser pyroly-
sis technique was optimized by our group, allowing us to obtain
ultrafine particles with increased magnetization and resistance
against ambient air oxidation [32,33]. Those core–shell nanopar-
ticles start forming by the decomposition of Fe(CO)5 vapors in the
hot environment provided by the laser-heated C2 H4 molecules. The
freshly formed iron clusters act also as catalysts, promoting the
cracking of the hydrocarbons on their active surface. The result-
ing carbon will be dissolved in the hot iron nanoparticles up to
saturation. Finally, after leaving the reaction zone and cooling,
those ultrafine iron-based will be covered by a carbonaceous shell
formed by the precipitation of the excess carbon, while the inner
remained carbon atoms will form iron carbides [32]. The resulted
round nanoparticles (under 20 nm) with core–shell morphology
can be seen in Fig. 1. The HRTEM inset allows the estimation of the
disordered/turbostratic carbonaceous shell thickness to few nm
and also to distinguish the ∼0.2 nm interplanar distance inside the
core, attributable to ␣Fe, Fe3 C and/or Fe3 C7 , phases also indentified
by XRD (Fig. 3). The presence of all these phases in the nanoparti-
cles synthesized by laser pyrolysis from Fe(CO)5 and C2 H4 (in a
different configuration) was reported before [34]. Various degrees
of aggregation as clusters and chains (see Fig. 1 TEM images) are
a consequence of their relative high formation temperature in the
laser pyrolysis reaction zone that allows the formation of solid con-
nections between certain nanoparticles. The nanoparticles carbon
shell protective role against air oxidation is proven by the presence
of the very weak ␥Fe2 O3 peak in the Fe@C diffractogram from Fig. 3
and of the intense peaks of metallic/carbidic iron, which is known
to be pyrophoric in the unprotected ultrafine form. Raman spec-
trum (Fig. 5) confirms the defective structure of the carbon shells
in the Fe–Fex C@C nanoparticles showing (after deconvolution
with Gaussian functions) the presence of broad D (at 1359 cm−1 )
and G (at 1582 cm−1 ) major peaks (with ID > IG ) attributed to
defects (related to electron–phonon coupling) and to trigonal sp2
hybridized carbon atoms in graphitic structures, respectively [35].
The minor band D1 (at 1484 cm−1 ) was attributed to amorphous
carbon [36], or by its association with the other weak D2 band
(at 1093 cm−1 ), to trans-polyacetylene oligomers [37], possibly
resulted in our case from ethylene dehydrogenation to acetylene
and subsequent heterogeneous polymerization on the Fe-based

Fig. 2. Proposed mechanism for the formation of the Fe@C(CMCNa)/PANI composite.

216 C.T. Fleaca et al. / Applied Surface Science 374 (2016) 213–221

Fig. 3. X-ray diffractograms of raw Fe@C nanopowders and the superposed ones of pure PANI and Fe@C(CMCNa)/PANI composite (presented as inset).

nanoparticles surface. The D1 peak (located between D and G bands)
which become more visible upon deconvolution, was also present
in other Fe–C nanostructures synthesized by laser pyrolysis (yet,
in these articles the Raman spectra were not deconvoluted), with
lower intensity in [38] (where a Raman laser beam with wavelength
exc = 488 nm was used) and [39] (exc = 787 nm) or even with
higher intensity – in [40] (exc = 514 nm) than those presented here.
Similar highly convoluted D and G bands were observed in Raman
spectrum (exc = 532 nm) of tetrahedral hydrogenated amorphous
film (taCH) film annealed in vacuum at 1000 ◦ C were sp3 to sp2 con-
version happened [41]. The presence the two small D1 and D2 peaks
(noted there with D4 and D3 ) was also revealed upon deconvo-
lution of Diesel soot Raman spectrum (exc = 514 nm) [36]. The high
degree of disorder and amorphization of the carbonaceous shells in
our raw Fe@C nanoparticles can also be related with the absence of
the (0 0 2) graphitic peak (around 2 = 26◦ ) from the corresponding

Fig. 4. Superposed FT-IR spectra of PANI and Fe@C(CMCNa)/PANI composite.

 C.T. Fleaca et al. / Applied Surface Science 374 (2016) 213–221
Fig. 5. Superposed Raman spectra of raw Fe@C nanoparticles and Fe@C(CMCNa)/
PANI composite.
X-ray diffractogram (Fig. 3). Also, due to the involving of hydrogen
(introduced in the precursors mixture and also provided by C2 H4
decomposition) in the pyrolysis process, the presence of various
CHx (x = 1, 2, 3) groups can also be expected in the carbonaceous
shells surrounding the Fe-based cores. The disordered/amorphous
carbon can undergo an incipient oxidation (easier than in the
case of crystalline graphite) during the strong horn ultrasonica-
tion treatment in aqueous suspension, and thus the freshly formed
oxygenated groups can interact with the hydrophylic groups of
the carboxymethlylcellulose polyanion, enhancing thus the water
dispersibility of Fe@C nanoparticles.
The synthesis of the magnetic PANI-composites was possible in
our case due to the utilization of carboxymethylcellulose sodium
salt which is an excellent dispersant for hydrophobic carbon-based
nanomaterials such as single-walled carbon nanotubes (SWCNTs)
in aqueous media [42]. Moreover, the polyanionic structure of
this substance allows the electrostatic binding of the polycationic
chains of PANI in the emeraldine protonated forms, as schemati-
cally shown in Fig. 2. Thus, the negatively charged CMCNa-coated
Fe@C nanoparticles, dispersed and disaggregated/deagglomerated
in water with the aid of strong ultrasounds can form a composite
in which the fine particles are homogeneously distributed in the
polycationic PANI matrix resulted from the oxidative polymeriza-
tion of anilinium chloride, as can be seen in the TEM images from the
lower part of Fig. 1. Thus, in the lower definition down-right TEM
image, the Fe@C nanoparticles are visible as dark spots surrounded
by/dispersed in a low density polymeric matrix (having a light grey
color) with irregular morphology (clearly visible at the compos-
ite edges) which should be composed mainly from PANI cationic
polymer (and some carboxymethylcellulose polyanion). The high
magnification down-left figure reveals the apparent disordered
217
porous structure of the polymeric matrix and the round shape of
high contrast (more dense) Fe-based nanoparticles trapped inside.
The formation of a porous matrix in the presence of CMCNa-coated
Fe@C nanoparticles was previously reported by us for the cases
of disordered silica or titania anorganic matrices [32]. Both these
images show that the polymeric part in this nanocomposite forms
a real matrix, extending dozens of nanometers away from the near-
est iron-based nanoparticle, a picture which differs from those of
a collection of thin conformal shells. This high percent of PANI
loading can be explained by the using of high molecular weight
cellulose-derivate anionic polymer (due to their long hydrophilic
chains, 2% of this polymer increases the water viscosity up to one
thousand times, as indicated in the product description) which can
electrostatically bind a large amount of PANI macropolycations.
Also, the aggregation degree of Fe@C nanoparticles seems to be
diminished in the nanocomposite compared with those from raw
nanopowders. This tendency can be attributed to the strong horn
ultrasonication (1000 W ultrasonic power in 100 cm3 liquid vol-
ume) treatment in the presence of CMCNa, able to disrupt part of
the fractal Fe@C aggregates due the intense shear forces produced
by the high speed fluid jets formed after the collapse of ultrasound
cavitation-induced bubbles [43].
The characteristic infrared vibration bands of PANI are found
also in the magnetic PANI composite, as shown in Fig. 5. The
broad absorption bands in the 3400–2800 cm−1 are attributed to
nitrogen-containing groups of PANI emeraldine forms as proton-
ated imine NH+ and secondary amine NH which interact via
hydrogen bonds between aligned polymeric chains [44]. The two
narrow peaks found at 1615 cm−1 and 1495 cm−1 are considered a
signature for the ring-stretching vibrations of the hexagonal carbon
rings from PANI in their quinoid (Q) and benzenoid (B) structure,
respectively [44]. Another sharp peak located around 1305 cm−1
was assigned to ␲-electron delocalization induced in the PANI chain
by protonation [45]. The peak visible as a shoulder at 1240 cm−1 can
be assigned to the stretching of carbon–nitrogen bond which can
be seen as a superposition of two limit-structures: C N•+ and
C N+ [46]. The next intense band, localized at 1140 cm−1 , has
been attributed to protonated NH+ structure vibrations in both
types of structural units: Quinoid NH+ Benzenoid (Q NH+ B)
and Benzenoid NH•+ Benzenoid (B NH•+ B). This band has
been correlated with both electron delocalization and N H+ · · ·N
interchain hydrogen bonding [44]. Finally, the peaks in the
900–700 cm−1 region correspond to aromatic out-of plane C H
deformations in para-disubstituted rings of PANI [44].
The Raman spectrum of the iron–PANI composite from the
upper part of Fig. 5 shows multiple peaks in the 1100–1700 cm−1
region, at 1184, 1227, 1332, 1393, 1468 (shoulder), 1490 (shoulder),
1546, 1583 and 1623 (shoulder) cm−1 . The latest was attributed
to C C stretching in the benzenoid PANI rings, whereas a peak
at 1590 cm−1 (near our 1583 cm−1 peak) was associated with the
C C stretching vibrations in the quinoid and semiquinoid PANI
rings [44]. The 1490 cm−1 shoulder was assigned to C N stretch-
ing vibrations in the units with quinoid structure [47]. The band at
1332 cm−1 is very near to those at 1336 cm−1 reported in [47] and
attributed to semi-double C∼∼N+ bond vibration in the delocal-
ized polaronic structures of protonated form of polyaniline. Also, a
band at 1250 cm−1 (near our 1227 cm−1 peak) was ascribed to the
C N stretching vibrations of various quinoid, benzenoid or pola-
ronic forms in PANI chains [44]. In the Raman spectrum of our
composite, the broad D and G bands provided by the carbon of
the Fe@C nanoparticle are superposed and masked by the aniline
peaks, similar with the case of PANI-carbon multiwalled nanotube
composite reported in [48]. Also, a series of CNT-PANI composites
loaded with various amount of nanotubes show a Raman peak at
1171 cm−1 attributed to protonated PANI [49], which is close to
those observed in our Raman spectra at 1184 cm−1 . The authors
218 C.T. Fleaca et al. / Applied Surface Science 374 (2016) 213–221
Fig. 6. Room temperature magnetic hysteresis curve of and Fe@C(CMCNa)/PANI
composite.
from [50] reported the observation of a peak with the same Raman
shift with those observed by us (1393 cm−1 ) in the spectrum of
PANI–camphorsulfonic acid film doped with metacresol, ascribed
to “phenazine-like” structures formed by interchain interactions in
reticulated (cross-linked) PANI.
By comparing the X-ray diffractograms of pure PANI and mag-
netic composite (the inset from Fig. 3) one can observe the presence
of three large peaks around 2-theta 15, 21 and 26◦ correspond-
ing to large molecular weight polyaniline. These peaks can be
found at the same angles in the diffractograms of pure PANI and
nano-Fe3 O4 /PANI composite [51]. The 26◦ intense peak was asso-
ciated with paraphenylene dense-packed rings interacting by their
extended ␲ orbitals which overlaps due to their close vicinity
[52]. The peaks of metallic/carbidic iron phases observed between
36 and 46◦ in the Fe@C nanopowder diffractogram from Fig. 4
can be found also in the X-ray diffractogram of the composite,
which suggests that those phases resisted to harsh aqueous envi-
ronment provided by strong ultrasonication and by persulfate
oxidizing agent. Thus, the protective role of carbonaceous shell in
the Fe–Fex C@C nanoparticles was again confirmed.
The magnetic hysteresis curve of the composite recorded at
room temperature (Fig. 6) shows a saturation magnetization (MS )
Fig. 7. Electrical resistivity variation with the apparent density of pure PANI, Fe@C
and Fe@C(CMCNa)/PANI composite powders.
around 6.4 emu/g and a ferrimagnetic behavior close to a super-
paramagnetic one with a low coercivity – 15.4 kA/m. This value
is smaller than the 40.5 kA/m extracted from the hysteresis curve
of nanometallic Fe/PANI fibers composite prepared by sodium
borohydride reduction of Fe ions on presynthesized PANI from
[53], where a greater magnetization saturation of 22.6 emu/g was
reported. The magnetic properties of our composite is very similar
with those of microemulsion-fabricated Fe3 O4 /PANI nanocompos-
ite from [51] with a MS = 3.95 emu/g and quasi-superparamagnetic
behavior. The relative low magnetization saturation value of our
nanocomposite compared with the high value of the starting Fe@C
nanoparticles (110 emu/g [32]) can be explained by multiple fac-
tors. One of them is the high percent of the non-magnetic PANI
polymer loading due to the oxidative polymerization of aniline pre-
cursor on the long chains of carboxymethylcellulose polyanions
surrounding the Fe@C nanoparticles. Moreover, even if the poly-
merization started from a situs near an anionic macromolecule,
due to the high concentration of anilinium cations, it is possible
that the growing PANI polycation to extend away from this nega-
tive polymer, being neutralized by small anions like Cl− and SO4 2− .
Other factor can be the partial oxidation of the iron-based cores
with the formation of non-magnetic and amorphous (non visible at
XRD) iron oxide/hydroxides in the presence of strong ultrasonica-
tion. Also, due to the natural drying of the PANI-composite aqueous
slurry, an important percent of water (which is diamagnetic)
remains embedded in the apparent dry composite, contributing
thus to the low MS value. The low coercivity value (15.4 kA/m)
of the as-synthesized PANI-based nanocomposite is very near to
those of our raw Fe@C nanoparticles (13 kA/m, reported in [32]) and
can be explained by the small size of the Fe-based nanoparticles.
Carbon-coated Fe nanoparticles with sizes around 50 nm, obtained
by calcination, carburization in CH4 and H2 reduction of hydrox-
ides show a 31 kA/m room temperature coercivity, independent of
carbon content [54], whereas the Fe3 C nanoparticles (10–100 nm)
embedded in carbon matrix from pyrolysis of ferrocene and maleic
anhydride (1:20 molecular weight ratios) present a 21.7 kA/m coer-
civity [55]. In the same article [55] the authors pointed out that
the amorphous carbon from organic precursor alone is diamag-
netic and thus they eliminated the background ferromagnetism due
to the carbon matrix. Regarding the dependence of the coercivity
(Hc ) to the particle size (d), the same authors cited the formula
HC = HC ∞ [1 − (d/d0 )], where HC ∞ = 2/ıMS and d0 = 24/MS 2 . The 
and ı parameters correspond to surface energy density of Block
wall and wall thickness, respectively [55]. Thus, the coercivity value
depends not only to the nanoparticle size but also to other fac-
tors such as magnetocrystalline surface energy, particle shape and
surface effect [55]. The magnetic properties of those PANI-based
nanocomposites allow them to be easily recovered with a perma-
nent magnet and then recycled/regenerated as demonstrated in [6]
for toxic hexavalent chromium removal.
For the electric measurements of the powders, we employed
a simple device that allows us to observe and compare the vari-
ation of the resistivity with their compaction degree provided
by their apparent densities (Fig. 7). It is well known that con-
tact resistivity between conductive particles is greater than those
intraparticle, and depends also to the contact area and to the
number of contact points between the neighboring particles [56].
For the pure protonated PANI dry powder the initial resistivity
is low, around 220  cm and slowly decreases with increasing of
the compaction degree. Due to their conductive carbon and metal-
lic content, the raw Fe@C nanopowder shows a similar trend,
yet starting from a higher resistivity value (750  cm) which
decreases with the increasing of the apparent density, near over-
lapping with those of PANI at high pressures. Here, the presence
of hydrogenated amorphous carbon in the carbonaceous shell
seems to have an important role in the limiting the electrical
 C.T. Fleaca et al. / Applied Surface Science 374 (2016) 213–221
Fig. 8. Cyclic voltammogram Fe@C(CMCNa)/PANI composite.
conductivity of the Fe@C raw nanoparticles. The initial resisti-
vity of the non-compacted Fe@C/PANI nanocomposite powder is
much higher (around 4300  cm), approaching to the values of the
pure components only at high apparent densities. This behavior
could be explained by the greater porosity of the dry composite,
which also contains non-conducting sodium carboxymethylcellu-
lose from the synthesis. Also, the nanoparticles themselves or the
morphological changes and defects induced by them can play a
role in the decreasing of composite conductivity vs. pure PANI by
charge carriers trapping [11]. For a system similar to ours, con-
sisting from carbon black (CB) nanoparticles and polypyrrole (PPy)
matrix, the authors show that at very low concentration (under
percolation threshold), the CB particles do not form continuous
conductive patterns, instead disrupting the interchain electronic
conduction of PPy and thus decreasing the electrical conductivity of
the nanocomposite compared with those of pure PPy [57]. The elec-
trical resistivity of our compacted nanocomposite (∼400  cm) can
be translated into a conductivity of 0.0025 S/cm. This value is hun-
dred times lower than those from HCl–PANI-based nanocomposite
filled with 1.66 wt.% Fe coated with amorphous Fex Oy nanoparti-
cles with sizes ∼100 nm deposed by magnetron sputtering followed
by grinding and pelletization; yet, their nanocomposite satura-
tion magnetization value was extremely low: 0.75 × 10−3 emu/g
[58] (four orders of magnitude lower than those found in our
PANI-based nanocomposite). The opposite situation can be found
in the high percentage iron oxide nanoparticles (85 wt.%) – PANI
– camphorsulfonic acid doped composite pellet which show a
high 80.4 emu/g MS value with the price of a dramatic decrease
of the electrical conductivity to 4.6 × 10−7 S/cm due to the low
PANI content (under the electrical percolation threshold) [59],
which is four magnitude orders lower than those of our nanocom-
posite. The tendency of decreasing of the conductivity with the
increasing of magnetic filler content together with nanocompos-
ite saturation magnetization was also presented for the case of
oleic acid functionalized Fe3 O4 nanoparticles multiple cores coated
with PANI single shells via microemulsion polymerization when for
an increase of iron oxide content from 10 to 50 wt.%, the MS also
increases from 0.14 to 21.8 emu/g in parallel with the conductivity
decreasing from 5.4 × 10−2 to 6.5 × 10−4 S/cm [60].
The repetitive cyclic voltammetry tests of PANI-based magnetic
nanocomposite in acidic media recorded at 200 mV/s scan rates
are presented in Fig. 8. They present similar behavior with those
of pure PANI (not presented here), both voltammograms show-
ing the characteristic peaks corresponding the different oxidation
states of PANI. Thus, the first pair of peaks (C/A) reflect the PANI
transition between the acidified insulating leucoemeraldine form
and the conducting protonated emeraldine form, whereas the C /A
pair can be assigned redox transition between the emeraldine and
pernigraniline PANI forms as proposed for PANI/Pt microparticles
219
[61] or for PANI/SWCNTs [40] films. The anodic A and cathodic
C peaks from the nanocomposite are sharper, also occurring at
greater current absolute values that those of PANI reference (for
composite IA = 8 A/g and IC = −7 A/g whereas for PANI IA = 5 A/g and
IC = −5 A/g) indicating a more intense oxidation of leucoemeral-
dine and reduction of pernigraniline forms of PANI in the case
of nanocomposite. The shape of the cyclic voltammetry curves
of the Fe@C–PANI composite in HClO4 aqueous solution is very
similar to those recorded in more concentrated HCl/NaCl solution
(using Ag/AgCl reference electrode) from TiO2 –PANI nanocompos-
ite obtained with higher amount of aniline [62]. In their case, the
authors concluded that the main characteristics of PANI were not
significantly changed in the presence of the nanofiller, observa-
tion which can be also applied for our nanocomposite. The specific
capacitance values extracted from our measurements are simi-
lar, those of the magnetic PANI composite (12.9 F/g) being slightly
greater than those of pure PANI (11.5 F/g), yet smaller than those
of the PANI/SWCNTs composite films with different PANI content
(78–234 F/g) used for supercapacitors from [63].
The synergy between electrical conductivity, magnetization
and redox properties in the iron oxide–PANI nanocomposites was
proven for a material with low Fe3 O4 load density in PANI matrix
having both low remanent magnetization (5.27 emu/g) and intrin-
sic coercivity (∼10.2 kA/m) (values close to ours) and also higher
than ours conductivity (0.3 S/cm) using electrochemical (with
un/magnetized electrode) and zinc air fuel cell (ZAFC) tests, where
the tiny magnetic field can promote oxygen transfer, increase the
electric double layer capacitance, lower the charge-transfer resis-
tance and improve the ZAFC performance [64].
4. Conclusions
We successfully synthesized a new PANI magnetic nanocom-
posite using carbon-encapsulated iron/iron carbide nanoparticles
(obtained by one-step laser pyrolysis) via anilinium cation oxida-
tive polymerization in aqueous suspension/solution with sodium
carboxymethylcellulose additive. The presence of Fe-based par-
ticles in the composite was attested by TEM and XRD analysis,
whereas those of PANI were proved by Raman and FT-IR spec-
troscopy. The nanocomposite shows similar electrical conductivity
and electrochemical behavior with pure PANI, having in the same
time a sufficient magnetization required for their manipulation
using strong magnetic external fields. By comparing the morphol-
ogy and the magnetic, electric and electrochemical properties of our
PANI-based nanocomposite with those reported for similar mate-
rials, we can conclude that the Fe@C–PANI composite deserved to
be tested and improved for various applications such as sensors,
electrocatalysis or toxic ions or organic pollutants absorbents.
Acknowledgements
The work has been funded by the Sectoral Operational
Programme Human Resources Development 2007–2013 of the
Romanian Ministry of European Funds through the Financial Agree-
ment POSDRU/159/1.5/S/132395 and also by PN 09 39 2009,
PN-II-ID-PCE-2011-3-0815 (no. 64 from 05/10/2011) and PN-II-
PT-PCCA-2011-3.2-0509 (no. 113 from 05.07.2012) Projects of the
Romanian Ministry of National Education and Scientific Research.
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