Materials Science in Semiconductor Processing 40 (2015) 152–157

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Materials Science in Semiconductor Processing

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

Influence of MWCNTs on the formation, structure and magnetic

properties of magnetite
Mahdi Ghazanfari n, Ahmad Yazdani
Department of Basic Sciences, Tarbiat Modares University (TMU), P.O. Box 14115-175, Tehran, Iran

art ic l e i nf o a b s t r a c t

Article history: Solvothermal method was utilized to prepare iron oxide powders and iron oxide–MWCNT nano-
Received 3 April 2015 composites using iron chloride III, ethylene glycol and sodium acetate. The influence of MWCNTs on the
Received in revised form formation, structure and magnetic properties of magnetite was investigated. The contraction of lattice
30 May 2015
parameter was occurred in the magnetite–MWCNT nanocomposite, which indicated that there is a
Accepted 24 June 2015
Available online 10 July 2015
competition between the reduction of Fe3 þ to Fe2 þ by the decomposition of ethylene glycol assisted by
sodium acetate, and the oxidation of Fe2 þ to Fe3 þ by MWCNTs leading to the vacancies. The amount of
Keywords: these vacancies represents the degree of phase transition from near magnetite to near maghemite.
Carbon nanotubes Magnetic properties of the product were investigated by vibrating sample magnetometer. Saturation
Magnetite
magnetization of magnetite was 91 emu/g that is about the bulk magnetization. The observed magnetic
Maghemite
moments per formula unit, estimated by saturation magnetization are in good agreement with magnetic
Magnetic properties
Solvothermal method moments per formula unit calculated from iron ion distribution among the two interstitial (tetrahedral
and octahedral) sites. The results were confirmed by FESEM, TEM and UV–vis analyzes.
& 2015 Published by Elsevier Ltd.

1. Introduction In this paper, iron oxide nanoparticles were synthesized in a

polyol medium with the aim of preparing magnetite. Then iron
The study of iron oxide nanoparticles has been of great interest oxide–MWCNTs nanocomposite was synthesized by using the
in technology and fundamental science due to their unique elec- preceding method by adding MWCNT and Polyvinylpyrrolidone
trical and magnetic properties. The finite size and surface effects in (PVP) as an in situ polymer wrapping agent in a polyol medium.
nano-dimensions of iron oxides, vigorously impact on the mag- The influence of MWCNTs on the structure and magnetic proper-
netic, electrical and optical properties relative to the bulk, which ties of iron oxide was described using X-ray diffractometer, Fourier
cause to be aroused remarkable phenomena such as super- Transform Infrared and vibrating sample magnetometer and in-
paramagnetism [1]. These unique properties are potentially useful dicated that there is a competition between the formation of
for a broad range of applications such as catalysts [2], microwave magnetite or maghemite, due to the competition between reduc-
absorbers [3], chemical sensors [4] and biomedical applications tion of ferric to ferrous iron by the decomposition of ethylene
[5]. glycol (EG) assisted by sodium acetate and the oxidation of ferrous
To improve the novel potential in a variety of iron oxides ap- to ferric by MWCNTs. Our samples displayed good ferromagnetic
plications, multi-walled carbon nanotubes (MWCNTs) are con- properties at room temperature.
sidered a suitable candidate for nanocomposite synthesis due to
their exhibition of excellent thermal conductivity, fascinating
2. Experimental
electronic properties and high mechanical strength.
Although many groups have focused on the decorating
2.1. Materials
MWCNTs with iron oxides and other soft ferrites [6–8], the influ-
ence of MWCNTs on the formation, structure and magnetic
The chemical reagents used in this study were FeCl3  6H2O,
properties of spinel ferrite have not been extensively studied, ex-
Polyvinylpyrrolidone (PVP, average MW ∼ 40000), sodium acetate,
cept for several few examples [6,9], and there is no report on
ethylene glycol and polyethylene glycol (MW ∼3000). All reagents
calculation of lattice parameter of ferrites. were of analytical grade purchased from Merck and used without
further purification. Multi-walled carbon nanotubes (length 10–
n
Corresponding author. Tel.: þ 98 91 27795977; fax: þ98 21 82884406. 30 μm; O.D. 10–20 nm; MWCNTs content 495%) were provided
E-mail address: [email protected] (M. Ghazanfari). by Iran Neutrino Corporation.

http://dx.doi.org/10.1016/j.mssp.2015.06.055
1369-8001/& 2015 Published by Elsevier Ltd.
 M. Ghazanfari, A. Yazdani / Materials Science in Semiconductor Processing 40 (2015) 152–157 153

Fig. 1. Rietveld refined X-ray diffraction pattern of (a) Fe3O4 and (b) Fe3O4/MWCNT. (c) Comparison of X-ray diffraction line intensity of iron oxides in the absence and
presence of MWCNT.

2.2. Synthesis of magnetite treated MWCNTs in 40 ml of EG and dispersed by ultrasonication

at room temperature for half an hour to form a clear solution. Then
The Spherical shaped magnetite nanoparticles have been pre- 5 mmol FeCl3  6H2O was dissolved in the resulting MWCNTs. Then
pared by using Deng et al. [10] and Kim et al. [11] method. sodium acetate (3.7 g, 45 mmol), polyethylene glycol (1 g,
FeCl3  6H2O (1.35 g, 5 mmol) was dissolved in ethylene glycol 0.05 mmol) and polyvinyl pyrrolidone (10 mg, 4 mmol) were ad-
(40 mL) in an ultrasonic bath to form a clear solution. The pH of ded to the resulting mixture solution under vigorous stirring for
ethylene glycol was 5.9, and was reached to 0.44 after adding Iron 1 h. The obtained dispersion was refluxed at 190 °C for 16 h. After
(III) chloride hexahydrate. Then sodium acetate (3.7 g, 45 mmol) being cooled to ambient temperature, the black products were
and polyethylene glycol (1.0 g, 0.05 mmol) were added to the so- collected by a magnet and rinsed several times with deionized
lution with stirring for 30 min. After adding sodium acetate, the water and ethanol and subsequently dried at 80 °C for 8 h.
pH value was reached to  6.2. The acquired brown precursor was
then refluxed at 190 °C for 16 h. After being cooled to room tem-
2.5. Characterization
perature, the pH value was reached to  6.8. The black products
were washed several times with ethanol and then dried at 80 °C
Water bath sonication was performed with WUC-D06H ultra-
for 8 h.
sonic cleaner (40 kHz/172 W). X-ray diffraction measurements
were carried for phase confirmation and crystallite size estimation
2.3. Purification and carboxylation of MWCNTs
using a Philips X-ray diffractometer Model-Expert with Ni filtered
Co-Kα radiation. Quantitative Rietveld analysis was performed
The as-purchased MWCNTs were first oxidized in air at 350 °C
using diffraction (MAUD) program version 2.33. The initial data-
for 2 h and then the acid treatment was performed by ultra-
base and atomic coordinates are taken from Haavik Crystal-
sonication in 7 mol/L nitric acid for 10 min. Then, the resulting
lographic Information Framework (cif) [12]. Fourier Transform
black solution was refluxed at 140 °C with constant magnetic
stirring for 8 h. Next, the solution was diluted with deionized Infrared (FTIR) spectroscopy was employed in the mid region from
water and filtered with a PTFE membrane (0.45 μm pore size) with 400 to 4000 cm  1, using a Nicolet Nexus 670 FTIR spectrometer in
the aid of a vacuum pump. The resulting carboxylated MWCNTs the transmission mode using the KBr pellet method. The ultra-
were rinsed several times to reach neutral pH and dried under violet–visible (UV–vis) absorption spectra were obtained with a
vacuum at 80 °C for 12 h, for further use. Unico 4802 spectrophotometer. The morphology of clusters was
investigated by scanning electron microscope (SEM, Philips model
2.4. Synthesis of magnetic carbon nanotubes XL30). The magnetization versus field loops were measured using
a vibrating sample magnetometer (VSM, MDK-VSM) at room
Synthesis of iron oxide–MWCNTs was done by adding 20 mg of temperature with the maximum applied field of 10 kOe.
154 M. Ghazanfari, A. Yazdani / Materials Science in Semiconductor Processing 40 (2015) 152–157

3. Results and discussion Table 1

Lattice constant (a), crystallite size (D) and strain (η) were taken from Williamson-
Hall plot.
The structures of iron oxides in the absence and presence of
MWCNTs were studied by using X-ray diffraction (XRD) and Williamson–Hall Plot data
Rietveld refined X-ray diffraction pattern, and normalized pattern
of them are shown in Fig. 1a–c. All the XRD peaks of samples a (Å) D (nm) η (%)
Iron oxide 8.390 63 0.23
synthesized in this work correspond to the spinel cubic structure
Iron oxide–MWCNT 8.370 43 0.06
and could be indexed to the magnetite structure of Fe3O4 (Re-
ference code:01-088-0315). The very weak and broad diffraction
peak observed at 2θ ¼31° in the nanocomposite could be attrib-
uted to the (002) reflection plane of the MWCNTs and low in-
tensity of it implies the low weight concentration of MWCNTs.
A Williamson–Hall Plot was used to determine both crystallite
size and microstrain by applying the follow equation
kλ
β cos θ = + 4η sin θ
D
where k is a shape factor normally ranges 0.89–1.0 (in our case,
k ¼1); λ is the Co Kα1 radiation wavelength (λ ¼1.78901 Å); θ is the
Bragg angle and β is the difference of the full-width-at-half-
maximum (FWHM) of XRD peaks and natural width of XRD
spectrometer, generally replaced by full width at half-height of
standard sample, in radians: β ¼ βsample  βstandard. To make a
Williamson–Hall Plot, we first Plot βcosθ on the y-axis (in radians
2θ) and Plot 4sinθ on the x-axis. By getting a linear fit to the data,
the crystallite size (D) and the strain (η) can be extract from the y-
intercept and the slope of the fit, respectively. The Williamson–
Hall Plot of samples is depicted in Fig. 2.
The lattice constant of the ferrites was computed using the
d-spacing values and the respective (hkl) parameters, or equiva-
lently by:

sin2θ λ2
2 2 2
=
h +k +l 4 a2
The values of average lattice parameter, crystallite size and
strain were listed in Table 1.
The main influence of entity MWCNT was a relative contraction
of the lattice parameter compared to the pure magnetite, as well
as an increase in the crystallity and a decrease in strain. Also the
comparison of X-ray diffraction line intensity demonstrates that
the experimental intensity lines of iron oxide–MWCNT have been
decreased at large angles 2θ. The contraction in the lattice con-
stant values could be related to the phase transition from mag-
netite (Fe3O4) to maghemite (γ-Fe2O3) [13]. To investigate the
latter the FTIR analysis was performed. Characteristic absorption
Fig. 3. (a) FTIR spectra of Fe3O4 and Fe3O4/MWCNT. (b) Fourier self-deconvolution
bands of maghemite are about 634 and 582 cm  1 corresponding of infrared in 450–750 cm  1 range.

to the Fe–O frequency deformations in the tetrahedral and the

octahedral sites, while for magnetite there is an absorption line in
the range of 572–582 cm  1 due to the stretching of Fe–O in the
tetrahedral sites [14].
Fig. 3a shows the FTIR spectra of Fe3O4 and Fe3O4/MWCNTs. At
the first glance there is no characteristic absorption band
(634 cm  1) of maghemite, but the spectra modification induced
by Fourier self-deconvolution of infrared (FSD-IR), using Omnic
software, in 450–750 cm  1 range (Fig. 3b) demonstrates that there
is some amount of maghemite in the Fe3O4/MWCNTs composite.
The absorption bands at 636 and 717 cm  1 are characteristics of
vacancy ordering in maghemite, so it can be concluded that
MWCNT increases the oxidation of Fe2 þ to Fe3 þ .
It can be seen from the overview of Fig. 1 that the oxidation of
Fe2 þ to Fe3 þ increases cation vacancies, which results in the de-
creased crystal symmetry and the reduction of experimental in-
tensity lines of iron oxide–MWCNT at large angles 2θ. So we can
Fig. 2. The Williamson–Hall Plot of samples. roughly estimate the lattice parameter (a), oxygen parameter (u)
 M. Ghazanfari, A. Yazdani / Materials Science in Semiconductor Processing 40 (2015) 152–157 155

Table 2
Lattice constant (a), crystallite size (D) and strain (η) oxygen parameter (u) and cation distribution estimated by Rietveld refinement using diffraction program MAUD.

a (Å) D (nm) η (%) u (Å) Fe3tetþ Fe2tetþ þ

Fe3oct þ
Fe2oct Rw (%) Rexp (%) Sigma

Iron oxide 8.395 46 0.06 0.2536 0.91 0 0.49 0.43 28.21 24.07 1.17
Iron oxide–MWCNT 8.373 30 0.01 0.2544 0.84 0 0.47 0.32 16.97 15.28 1.10

Fig. 4. FESEM and statistical histogram images (a,c) of as-prepared Fe3O4 nanoparticles, (b,d) of Fe3O4/MWCNT composite.

and cation distribution by Rietveld refinement method using dif- particles clinging together and the aggregates are spherical-
fraction program MAUD, listed in Table 2. It was seen from the shaped. Statistical histogram shows that the mean diameter of
cation distribution that the site occupancies of the iron oxide– Fe3O4 particles is about 76 nm, as shown in the Fig. 4(a and c). The
MWCNT cations are reduced in the two interstitial sites, especially agglomerated clusters of particles are due to the magnetostatic
in octahedral sites, corresponding to maghemite's vacancies. coupling between the particles. Statistical histogram of the fine
The typical FESEM micrographs of Fe3O4 and Fe3O4/MWCNTs particles on the surface of the powders shows that spherical ag-
are shown in Fig. 4. Fe3O4 micrograph shows clusters of fine gregates of Fe3O4 are composed of a small primary particle size of

Fig. 5. TEM images (a) of as-prepared iron oxide nanoparticles, (b) at the present of MWCNTs.
156 M. Ghazanfari, A. Yazdani / Materials Science in Semiconductor Processing 40 (2015) 152–157

about 16 nm. Fe3O4/MWCNTs micrograph shows fine particles

clinging to the surface of MWCNT as well as free magnetite clus-
ters that are formed due to the lack of MWCNT, where the nu-
cleation and growth of magnetite occurs. Statistical histogram of
these free magnetite clusters of composite shows that their mean
size is less than that of pure magnetite. This could be attributed to
the consumption of ions in coating magnetite or formation of
maghemite with a smaller lattice parameter.
Fig. 5 displays the TEM images of iron oxides in the absence and
presence of MWCNTs. According to the TEM image (Fig. 5a),
magnetite nanoparticles are spherical with a mean diameter of
42 nm, which is very close to the value calculated from the XRD
data. The formation of nanospherical cluster could be attributed to
the great viscosity of EG and the capping agent PEG, which could
prevent the fast growth of magnetite and provide enough time to
rotate Fe3O4 nanocrystals to a lower energy configuration, as well Fig. 7. Hysteresis loops of Fe3O4 and Fe3O4/MWCNT.
as dipolar interactions between the magnetite nanocrystals that
contribute to this aggregation. according to Table 2.
In the present of MWCNTs, we also see that the iron oxide Magnetic properties of the obtained nanocomposite were
nanocrystallites were aggregated around the MWCNTs templates characterized using VSM with a maximal applied field of 10 kOe.
and formed spherical aggregation. This aggregation growth will Fig. 7 shows the M–H loop of the specimen at room temperature.
initiate by the self-adsorption of Fe3 þ ions on the high density of The magnetic properties of products are given in Table 3.
carboxylic groups that refined on the MWCNTs. At the same time, The saturation magnetization of this 42 nm magnetite nano-
a competition is initiated between the reduction of Fe3 þ to Fe2 þ particles is 91 emu/g at 10 kOe, which is close to that of bulk Fe3O4.
by the decomposition of ethylene glycol assisted by sodium acet- The high saturation magnetization may be attributed to the very
ate and the oxidation of Fe2 þ to Fe3 þ by MWCNTs. The dominant thin dead layers observed in TEM histogram. The saturation
reaction determines the formation of magnetite or maghemite. In magnetization of Fe3O4/MWCNTs is 64 emu/g. The decrease of
addition to carboxylic groups, PVP molecules with pyrrolidone magnetic saturation value in composite could be related to the
functional groups could easily arrest the crystals of ferrite nano- MWCNTs weight contribution or phase transition from magnetite
particles, which in turn could help to form fine magnetic particles (Fe3O4) to maghemite (γ-Fe2O3) or, as it is seen in FESEM and TEM
as well as to stop the aggregation of nanoparticles. histogram images, magnetic nanoparticles' size in composite case
The analysis of optical absorption spectra is one of the most is slightly less than pure magnetite, so spin canting at the surface
constructive tools for understanding the energy gap of materials. of ferrite nanoparticles in composite is more, and as a result,
The optical absorption spectra of the samples are shown in Fig. 6. magnetic saturation value in composite is less than pure one.
The optical band gap Eg can be determined by the well-known The observed magnetic moment per formula unit at room
Tauc's relation for the absorption coefficient of amorphous semi- temperature in Bohr magneton (nB(obs. )) can be calculated as [15]
conductors, i.e., (αhν )1/ n = A(hν − Eg ), where α is the absorption
MMSM MMSM
coefficient, hν is the photon energy, A is a constant that depends nB(obs. ) = =
NA·μ B 5585
on the transition probability, and n depends on the nature of the
transition and is theoretically equal to 2 and 1/2 for allowed in- where M ¼231.6 g is the molecular weight of the substance cor-
direct and direct electronic transition, respectively. The intersec- responding to one molecule of Fe304, NA ¼6.20  1023 mol  l re-
tion of the linear fits of (αhν )2 versus hν plots determines the direct presents Avogadro's number, μB, the Bohr magneton and MSM is
band gaps. The Tauc plot is presented in the inset of Fig. 6. The the saturation magnetization of Fe304 (emu/g) after subtracting
direct band gap of composite is 1.89 eV, which is less than the near MWCNTs weight contribution that can be calculated using the
magnetite band gap, 1.96 eV. This observation could be attributed following formula:
to the presence of more vacancies in composite structure
MST
MSM = MMWNT
1− MFerrite

On the other hand, according to Neel's molecular-field model,

the calculation of the magneton number nB(cal. ) is given by the
difference in the magnetic moment of tetrahedral (A) and octa-
hedral [B] sites, i.e.

Table 3
Total saturation magnetization (MST), saturation magnetization of ferrites after
subtracting MWCNTs weight contribution (MSM), remanent magnetization (Mr),
reduced remanent magnetization (Mr/MST) and coercive field (Hc), observed mag-
netic moment (nB (obs.)), calculated magneton number (nB (cal.)).

Sample MST MSM Mr Mr/Ms Hc (Oe) nB (obs.) nB (cal.)

(emu/ (emu/ (emu/
g) g) g)

Iron oxide 91 91 11 0.12 53 3.77 3.79

Iron oxide– 64 66 5 0.078 40 2.74 2.71
MWCNT
Fig. 6. UV–visible spectra of Fe3O4 and Fe3O4/MWCNT. Inset: Tauc plot.
 M. Ghazanfari, A. Yazdani / Materials Science in Semiconductor Processing 40 (2015) 152–157 157

nB(cal. ) = MB − MA Council for financial support of the work.

nB(cal. ) values are calculated by using the cation distribution of

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Acknowledgment

The authors would like to thank Iran Nanotechnology Initiative