ARTICLE IN PRESS

Journal of Magnetism and Magnetic Materials 321 (2009) 32033206

Contents lists available at ScienceDirect

Journal of Magnetism and Magnetic Materials

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

Fabrication and magnetic property analysis of monodisperse

manganesezinc ferrite nanospheres
Qi Zhang a, Meifang Zhu a, Qinghong Zhang b, Yaogang Li a,, Hongzhi Wang b,
a
b

State Key Laboratory for Modication of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620, Peoples Republic of China
College of Materials Science and Engineering, Donghua University, Shanghai 201620, Peoples Republic of China

a r t i c l e in fo

abstract

Article history:
Received 21 January 2009
Received in revised form
12 May 2009
Available online 31 May 2009

Monodisperse MnZn ferrite (Mn1xZnxFe2O4) nanospheres have been prepared via a simple
solvothermal method. The as-synthesized samples were characterized in detail by X-ray diffraction
pattern (XRD), transmission electron microscope (TEM), high-solution transmission electron microscope (HRTEM), select area electron diffraction pattern (SAED), scanning electron microscope (SEM),
and vibrating sample magnetometer (VSM). The results show that a large number of the high-purity
Mn1xZnxFe2O4 nanocrystallites were synthesized and these nanocrystallites oriented aggregated to
nanospheres. The dependence of magnetic properties of Mn1xZnxFe2O4 nanospheres on the
composition content x of Zn was studied. The maximum saturation magnetization value of the asprepared sample (Mn0.6Zn0.4Fe2O4) reached 52.4 emu g1.
& 2009 Elsevier B.V. All rights reserved.

Keywords:
MnZn ferrite nanosphere
Solvothermal method
Magnetic property

1. Introduction
The fabrication of ferrite nanoparticles has been intensively
investigated in recent years due to their unique physical and
chemical properties. In particular, the spinel ferrites of composition MFe2O4 (M Co, Ni, Mn, Zn, Fe, etc.) exhibit interesting
magnetic, magneto-resistive, and magneto-optical properties,
which show widely potential applications in ferrouids [1],
high-density magnetic recording media [2], biomedicine [3], and
radar absorbent materials [4]. Their magnetic properties can be
systematically varied by changing the identity of the divalent M2+
cation or by partial substitution while maintaining the basic
crystal structure. Seshadri and Masala [5] used a non-aqueous
route to fabricate soluble MFe2O4 nanoparticles of different sizes
to investigate the size-dependence of magnetic properties. Ji et al.
[6] prepared CoFe2O4 nanowire arrays in porous anodic aluminum
oxide template by the solgel process. Yan et al. [7] synthesized Zn
ferrite hollow nanospheres and nanosheets via a solvothermal
method. Jia et al. [8] solvothermally prepared monodispersed
CoxNiyFe3xyO4 nanoparticles, and the sizes of the nanoparticles
can be adjusted by changing the reaction time.
As an important member of the ferrite family, MnZn ferrite
(Mn1xZnxFe2O4) has attracted signicant research interest based
on its fascinating magnetic and electromagnetic properties. It has
good chemical stability, magnetic properties, corrosion resistance,

 Corresponding authors. Tel.: +86 21 67792342; fax: +86 21 67792340.

E-mail addresses: yaogang_li@dhu.edu.cn (Y. Li), wanghz@dhu.edu.cn

(H. Wang).
0304-8853/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2009.05.049

and reasonable cost [9,10]. Many methods have been developed to

prepare the Mn1xZnxFe2O4 nanoparticles, such as the coprecipitation method [11], hydrothermal method [12], microemulsion method [1315], solgel method [16], and self-propagating high-temperature method [17]. However, the research on
self-assembly Mn1xZnxFe2O4 nanoparticles into different architectures and their development were comparatively limited.
Herein, we reported a general, efcient, and environmentally
friendly synthetic strategy for obtaining Mn1xZnxFe2O4 nanospheres constructed with tiny nanocrystallites via a simple
solvothermal method. The unique structure of Mn1xZnxFe2O4
will have an important effect on their corresponding properties
and also will be meaningful for both fundamental studies and
practical applications. The dependence of magnetic properties on
the cationic stoichiometry in a series of Mn1xZnxFe2O4 (0oxo1)
nanospheres has been investigated. Due to the high magnetic
sensitivity of the nanospheres, it displays a great potential
application in biomedical elds.

2. Experimental
2.1. Synthesis of Mn1xZnxFe2O4 nanospheres
All reagents were of analytical grade and used as obtained
without further purication. Mn1xZnxFe2O4 nanospheres were
obtained via a facile solvothermal synthetic route. A series of
Mn1xZnxFe2O4 nanospheres can be synthesized with composition
0oxo1.
The
typical
preparation
procedure
of

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Q. Zhang et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 32033206

Mn0.6Zn0.4Fe2O4 nanospheres is as follows: FeCl3  6H2O (5 mmol),

Zn(NO3)2  6H2O (1 mmol), and MnSO4  H2O (1.5 mmol) were
dissolved in ethylene glycol (50 ml). Then, NH4Ac (0.02 mol) and
polyethylene glycol (0.8 ml) were added into the mixed solution
under vigorous stirring at room temperature for 30 min. Subsequently, the mixture was sealed in a Teon-lined stainless
steel autoclave (70 ml capacity) and maintained at 200 1C for
12 h. Then, the mixture was cooled to ambient temperature. The
product was collected by magnet and rinsed with deionized water
and ethanol until there were no chloride and nitrate ions in the
solution. The nal product was dried in vacuum at 60 1C for 12 h.
2.2. Characterization
Powder X-ray diffraction pattern (XRD) was carried out on a
Japan Rigaku D/max 2550 V X-ray diffractometer using Cu Ka
irradiation (l 1.54056 nm). The operation voltage and current
were kept at 40 kV and 300 mA, respectively. The size and
morphology of the as-synthesized products were determined at
20 kV by a JSM-5600LY scanning electron microscope (SEM).
Transmission electron microscope (TEM), high-solution transmission electron microscope (HRTEM) images, and select area
electron diffraction pattern (SAED) were collected using a JEOL2100F electron microscope to determine further details of the asprepared samples. The Mn2+/Zn2+/Fe3+ atomic ratio of the nanospheres was conrmed via energy-dispersive X-ray (EDX) spectrum, which recorded on an OXFORD ISIS spectroscope attached to
the JEOL-2100F electron microscope. Magnetic characterization
was conducted on a vibrating sample magnetometer (VSM, PPMS
Model 6000) in the eld of 4 kOe at room temperature.

average grain size of ve samples was about 510 nm. Although

no signicant change in the crystal symmetry was observed, we
found a slight shift of (3 11) diffraction peak. Fig. 2 showed it in
detail, as is shown that the XRD peak of (3 11) plane shift towards
the smaller angle (2y) with increase in Zn2+ concentration
indicating a small increase in the lattice parameters of the
Mn1xZnxFe2O4 nanocrystallites.
The size and morphology of the as-produced sample were
investigated by TEM. Fig. 3 shows the representative images of the
sample (Mn0.6Zn0.4Fe2O4) obtained after solvothermal treatment
for 12 h. In Fig. 3a and b, it can be clearly seen that 100200 nm
nanospheres were fabricated. From the higher magnication TEM
image in Fig. 3c, it is visible that the Mn0.6Zn0.4Fe2O4 nanospheres
are constructed with tiny nanocrystallites in an average diameter
of 510 nm, which is closed to the value calculated by Scherrers

3. Results and discussion

The crystallinity and structure of the as-synthesized samples
were conrmed by XRD patterns. As is shown in Fig. 1, the peak
position and relative intensity of all diffraction peaks for ve
samples (ae) match well with standard powder diffraction dates
(JCPDS les no. 74-2402, 74-2401, 74-2400, 74-2399, and 74-2398,
respectively), indicating high purity of the samples. Well-resolved
diffraction peaks reveal good crystallinity of the specimens. The
average particle size of as-prepared ferrite powder was estimated
from the Scherrer formula [18]. The (3 11) peak was chosen for
calculating the average particle size. The results showed that the

2+

Fig. 1. The XRD patterns of MnxZn1xFe2O4 nanospheres with variable Zn

doping.

Fig. 2. The XRD peaks of (3 11) shift with the concentration of Zn2+.

Fig. 3. Morphologies of the Mn0.6Zn0.4Fe2O4 nanospheres: (a) and (b) typical TEM
images; (c) higher magnication TEM image; (d) HRTEM image and the inset
shows the corresponding SAED pattern.

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Q. Zhang et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 32033206

formula. In other words, the tiny Mn0.6Zn0.4Fe2O4 nanocrystallites

aggregated to nanospheres. The crystallographic orientation of the
Mn0.6Zn0.4Fe2O4 was investigated by HRTEM, as shown in Fig. 3d,
parallel lattice fringes among almost all the nanospheres and the
grain boundaries clearly indicated the oriented aggregation of
these nanocrystals. The prominence of lattice fringe of
d 0.51 nm among the observed nanocrystallites agrees well
with the separation between the (111) lattice planes. The
corresponding SAED pattern of the selected region indicates that
the product is well-crystallized. The result from EDX spectra
shows that as-prepared Mn0.6Zn0.4Fe2O4 nanospheres contain Mn,
Zn, Fe, O, and no contamination element was detected. The atomic
ratio of Fe:Mn:Zn is about 4.88:2.91:1.89, indicating that the
chemical formula of the as-prepared sample is consistent with the
experimental stoichiometry.
The probable formation mechanism of the nanospheres can be
explained that the aggregation growth will initiate when the
repulsive interactions are not large enough to block their access
due to Brownian motion and van der Waals attraction [19,20].
Currently, the main driving force for oriented aggregation of
nanocrystals is attributed to the tendency to decrease the high
surface energy. In our case, dipolar interactions between the
magnetite nanocrystals are also contributive to their oriented
aggregation. At the same time, the non-aqueous solution of our
system could slower the aggregating rate of Mn1xZnxFe2O4
nanocrystals because of fewer surface hydroxyls and greater
viscosity, comparing with that in aqueous solution, and provides
Mn1xZnxFe2O4 nanocrystals enough time to rotate to the lowenergy conguration interface [21]. Moreover, the capping agent
PEG could prevent fast growth of Mn1xZnxFe2O4 crystallite and
be helpful to the oriented aggregation [22].
Fig. 4 shows the SEM photomicrographs of the sample. It
provides more structural information about the threedimensional morphology of the product. A large quantity of
Mn0.6Zn0.4Fe2O4 nanospheres have been synthesized and have
very narrow diameter distributions.
The magnetic property of the as-prepared Mn1xZnxFe2O4
nanospheres was investigated with a vibrating sample magnetometer at room temperature. Fig. 5 shows the magnetizationhysteresis loop of the samples for different compositions.
It shows that for a given external magnetic eld, the magnetic
saturation value of Mn1xZnxFe2O4 powders is closely related with
the substitution degree of Zn2+. For smaller value of the
composition content x, the magnetic saturation value of the

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Fig. 5. Room-temperature magnetic hysteresis of Mn1xZnxFe2O4 nanospheres

with variable Zn2+ doping.

sample increases with the increase in the substitution degree of

Zn2+, but it decreases in the substitution degree of Zn2+ if x40.4,
which agree with the literatures[23,24]. The magnetic saturation
value of Mn0.6Zn0.4Fe2O4 reached 52.4 emu g1. In addition to the
deviation from normal cation distribution, many other factors
may contribute to the reduction of Ms value in nanoparticles. It
can be attributed to the smaller Ms value in nanoparticles to the
existence of random canting of particle surface spins caused by
competing anti-ferromagnetic exchange interactions due to
asymmetry in the environment of these spins [25]. Hysteresis
loops for the samples at room temperature show nonlinear,
reversible characteristic with no hysteresis (zero coercivity),
exhibiting superparamagnetic behavior.

4. Conclusion
In summary, the solvothermal method has been used to
successfully synthesize Mn1xZnxFe2O4 nanospheres. This approach developed a simple, efcient, and scalable route to
fabricate the tiny magnetic Mn1xZnxFe2O4 nanocrystals oriented
aggregation to form the nanospheres. The maximum saturation
magnetization value of the product (Mn0.6Zn0.4Fe2O4) is 52.4 emu
g1. The ferrite nanospheres display a great potential application
in manipulation and organization of magnetic structures into
integrated systems as well as in biomedical eld.

Acknowledgements
We gratefully acknowledge the nancial supports by the
Ministry of Education of the Peoples Republic of China (No.
NECT-05-0419), Shanghai Municipal Education Commission (No.
07SG37), Natural Science Foundation of China (Nos. 50772022 and
50772127), Shanghai Leading Academic Discipline Project (B603),
the Cultivation Fund of the Key Scientic and Technical Innovation
Project (no. 708039), and the Program of Introducing Talents of
Discipline to Universities (No. 111-2-04).
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Fig. 4. Representative SEM images at low magnications of the Mn0.6Zn0.4Fe2O4

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