Proceedings of the 4th International Conference on Nanostructures (ICNS4)

12-14 March, 2012, Kish Island, I.R. Iran

Characterization of Carbon Nanotubes Decorated with -Zink Ferrite (ZnFe2O4) Nanoparticles

by Citrate-gel method
M. Zolfaghari*, R. Sepahvand ,H. Zolfaghari
Department of Physics, Faculty of Science, Lorestan University, Khoramabad
*omid0652@yahoo.com

Abstract
A magnetic nanocomposite of multiwalls carbon nanotube (MWCNT), decorated with ZnFe2O4 nanoparticles, was
synthesized successfully by citrate sol-gel method. The structural, morphological and magnetic properties of the
nanocomposite were characterized by XRD, FT-IR, TEM and vibrating sample magnetometer (VSM). The results from
these techniques showed that CNTs and ZnFe2O4 were coexisted in the nanocomposite and the ZnFe2O4nanoparticles
were successfully attached on the surface of CNTs. Also the magnetization curve of the decorated CNTs at room
temperature showed that the saturated magnetization (Ms), remanence (Mr) and coercivity (Hc) values are 132/49
emu/g, 12/37 emu/g and 48/35, respectively.

Keywords: MWCNTs, Zink Ferrite; nanocomposite; Citrate-gel

Introduction
Composites, formed by two or more distinct materials,
have desirable combinations of properties that are not
found in the individual component [1]. Carbon nanotubes
[2, 3] are attracting much interest due to their potential
applications as high-performance nanoscale materials [4,
5] and electronic devices [6, 7]. More specifically, metalfilled carbon nanotubes may also have a variety of
industrial applications [8]. Different methods of synthesis
have been attempted and various materials encapsulated
have been tested [9]. The spinel ferrite of nanoparticles
and composition MFe2O4 (M = Co, Ni, Mn, Mg, Fe or
Zn) exhibit interesting magnetic, magetoresisitive, and
magneto-optical properties that are potentially useful for
a broad range of applications [10-12]. The most widely
used technique for the production of CNTs is the direct
current (DC) arc-discharge, because it can yield ructurally
excellent high quality CNTs. This process produces
carbon soot on the cathode surface containing nanotubes
[13], nanoparticles [14], fullerenes [15], nanocapsules
[16], nanowires [17], nanorods [18], and nanofibers [19].

Experimental
MWCNTs (formed by CVD process) were provided
by Sun Nano Company (China) and the purity was
claimed to be 95% by the producer. The outer diameters
of CNTs were 10 to 20 nm. Fe(NO3)3,Zn(NO3)2 and
C6H8O7 were purchased from Merck.
MWCNTs were first opened according to the
procedure reported in literature. Briefly, MWCNTs was
milled and dispersed in a 3/1 mixture of H2SO4/ HNO3 by
an ultrasonic shaker. The mixture was refluxed for 10h at
120C. Then it was cooled, filtered and washed by
distilled water adjusted at pH 5. Finally, the oxidized
carbon nanotubes (o-MWCNTs) were dried at 120 C for
6 h before use. An insitu chemical citrate-gel method was

developed to obtain the ZnFe2O4/MWCNTs precursor. A

proper amount of o-MWCNTs was first added to a
solution of citric acid (C6H8O7.H2O) and ultrasonicated in
distilled water for 10 min. Afterward, this suspension was
mixed with an aqueous solution of Zn(NO3)2.6H2O and
Fe(NO3)3.9H2O, in which the Zn:Fe molar ratio was
maintained at 1:2. In order to reach the PH of the solution
to 9, ammonia solution was drop wisely added to the
mixture with vigorous stirring. The mixture was also
stirred at 30 C for 48 h and dried in an oven at 80 C for
24 h, followed by calcination at temperature 700 C for
2h in an Argon atmosphere. Also we synthesized
magnesium ferrite (ZnFe2O4) nanoparticles by citrate-gel
method. To synthesize nanoparticle, Fe(NO3)3 and
Zn(NO3)2.6H2O mixed solution was added to citric acid
dissolved in distilled water. The solution was stirred and
then was concentrated until a viscous liquid was obtained.
The liquid was dried in an oven at 120 C and calcined at
temperature 700 C for 2h in an Argon atmosphere.
The XRD of the synthesized composites were
obtained by an X-ray powder diffractometer (XRD,
D8ADVANCE, Bruker, Germany) with Cu K radiation
(= 1. 5406 ) and a Ni-filter. IR spectra were recorded
on an FT-IR, Nicolet 320. The morphologies of the
samples were observed through transmission electron
microscopy (TEM, Philips CH 200, LaB6 Cathode160
kv). Magnetic properties of the samples were measured
by vibrating sample magnetometers (VSM) with a
maximal applied field of 10 kOe.

Results and Discussion

The FT-IR spectrum of the pristine, opened MWCNTs,
the
ZnFe2O4/MWCNTs
nanocomposites
and
ZnFe2O4nanoparticles in the range of 4000-400 cm-1 are
shown in (Fig. 1) and (Fig. 2) respectively. As it can be
seen, the IR spectra of the pristine CNTs (Fig. 1a) show

217

Proceedings of the 4th International Conference on Nanostructures (ICNS4)

12-14 March, 2012, Kish Island, I.R. Iran

no obvious absorbance bands due to the symmetrical

structure of carbon nanotube. Treatment of the carbon
nanotubes with acid in order to open their tips causes the
formation of functional groups on their surface. In the IR
spectra of the opened MWCNTs (Fig. 1b) and the
ZnFe2O4/MWCNTs nanocomposites (Fig. 2b) the
absorbance band at 3600-3100 is assigned to the O-H
bond of the carboxyl functional groups created on their
surface. Absorbance bands around at 1700, 1620 and
1500 cm-1 could be attributed to the stretching
frequencies of the C=O and C=C bonds, respectively.
The absorption bands around 1100 cm-1 could be
attributed to the stretching vibration of CCC group. In
addition (Fig. 2a, b) show two persistent absorption bands
corresponding to the vibration of tetrahedral and
octahedral complexes at 567 and 435 cm-1, respectively,
which are indicative of formation of spinel ferrite
structure. As is seen from (Fig. 2), the normal mode of
vibration of tetrahedral cluster (567 cm-1) is higher than
that of octahedral cluster (435 cm-1).

CNTs and can be indexed to the (002), (101) and (004)

reflection of CNTs, respectively. In (Fig. 4) and (Fig. 5)
well-resolved diffraction peaks revealed the good
crystallinity of the ZnFe2O4specimens, located at 2 of
30.15, 35.51, 37.14, 43.10, 53.49,56.88, 62.54 and
73.86,respectively.These
diffraction
peaks
corresponding to planes (111), (311), (400), (422), (333),
(440) and (620) provide a clear evidence for the
formation of spinel structure of the ferrite.The grain size
of ZnFe2O4/MWCNTs at 700 C are obtained using
Scherrers formula as 28/72 nm respectively.

Figure 1. FT-IR spectra of (a) Pristine MWCNTs (b)

opened MWCNs.

Figure 4. XRD pattern of the ZnFe2O4nanoparticles

calcined in Ar at 700 C/2h.

Figure 3. XRD pattern of the opened MWCNT.

Figure 5. XRD patterns of the ZnFe2O4/MWCNTs

nanocomposites calcined in Ar at 700 C/2h .

Figure
2.
FT-IR
spectrum
of
(a)
the
ZnFe2O4nanoparticles calcined in Ar at 700 C/2h. (b)
The ZnFe2O4/MWCNTs nanocomposites calcined in Ar
at 700 C/2h .
(Fig. 3) shows the XRD pattern of the opened
MWCNTs.
(Fig.
4)
show
XRD
of
the
ZnFe2O4nanoparticles calcined in Ar at 700 C/2h, show
ZnFe2O4/MWCNTs nanocomposites calcined in Ar at
700C/2h. The XRD peaks correspond with the reported
values of ZnFe2O4 (PDF card: 360398), CNTs (PDF
card: 01-0640) and ZnO (PDF card: 08-0415). The
diffraction peaks at 2= 25.8, 43.08 and 53.8 in (Fig.
3) and (Fig. 5) are the typical Bragg peak of pristine

218

(Fig. 6) shows the TEM images of (a) the pristine, (b)

opened,(c)decorated
MWCNTs
and
(d)
ZnFe2O4nanoparticles, respectively. In (Fig. 6c) the
ZnFe2O4 nanoparticles can be seen clearly on the surface
of the MWCNTs.

Figure 6. TEM images of (a) the pristine MWCNTs, (b)

MWCNTs after acid treatment,(c)the ZnFe2O4/MWCNTs

Proceedings of the 4th International Conference on Nanostructures (ICNS4)

12-14 March, 2012, Kish Island, I.R. Iran

nanocomposites calcined in Ar at 700 C/2h and (d) )

ZnFe2O4nanoparticles.
The magnetic properties of the ZnFe2O4 nanoparticles
and decorated MWCNTs were measured in magnetic
fields of 10 kOe at room temperature. The hysteresis
loop of the decorated MWCNTs is presented in (Fig. 7).
The values of the saturation magnetization (MS),
retentivity
(MR)
and
coercivity
(HC)
of
ZnFe2O4/MWCNTs, obtained from the VSM data, were
obtained as 48/35, 12/37 emu/g, and 132/49Oe,
respectively. In Fig. 8, the Hysteresis loops were
compared for the ZnFe2O4nanoparticles and decorated
MWCNTs. Also, the values of MS, HC and MR of
specimens obtained from the VSM data were compared in
(Table 1). The increment in all values of magnetic
parameters is due to the method and the existence of
MWCNTs which it is coused to be synthesized the grand
size of ZnFe2O4nanoparticles. Due to the large sized
nanoparticles. As, shown in the inset of (Fig. 7), the
coercive force (HC) of the magnetic nanocomposites is
only 132/49 Oe, which can reflect a typical characteristic
of superparamagnetic materials. With this unique
property, it can be used as a promising vehicle for
magnetic field-directed drug delivery systems.

Figure 7. Hysteresis loop of the ZnFe2O4/MWCNTs

nanocomposites calcined in Ar at calcined in Ar at 700
C/2h.

Figure 8. Hysteresis loops of (a ZnFe2O4nanoparticeles

and (b) the ZnFe2O4/MWCNTs nanocomposites calcined
in Ar at
700 C/2h

Table 1. Comparison of the Magnetic properties of

ZnFe2O4nanoparticeles
and
ZnFe2O4/MWCNTs
nanocomposites calcined in Ar at 700 C/2h.
Specimen

MS(mueg-1)

HC(Oe)

MR(mueg-1)

ZnFe2O4

50/34

11/41

1/4

ZnFe2O4/MWCNTs

132/49

48/35

12/37

Conclusions
The synthesised superparamagnetic ZnFe2O4/MWCNTs
/MWCNTs nanocomposites can be used in the fabrication
of magnetic, heterogeneous catalysis, magnetic
technologies, and in biotechnology as promising vehicle
for magnetic field-directed drug delivery systems.

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