Proceedings of the 2017 IEEE
Nanotechnology Material and Devices Conference
October 2-4, 2017, Singapore
Effect of Zn Concentration on Crystal Structure and Magnetic Properties of
ZnxNi1-xFe2O4 Nanoparticles Fabricated by Co-precipitation Method
N. Istikhomah1, J. Widakdo1, A. Rifianto1, E. Suharyadi1*, T. Kato2, and S. Iwata3
Abstract— ZnxNi1-xFe2O4 magnetic nanoparticles with
various x from 0.2 to 0.8 have been synthesized by a
chemical co-precipitation method. The X-ray diffraction
(XRD) patterns confirmed that nanoparticles have spinel
cubic structure with some impurity phases. The lattice
parameter of the sample for x = 0.2 was 8.599 % and then
increases with the increase of Zn concentration. This is due
to the replacement of smaller Ni2+ by larger Zn2+ cation.
The crystallite size of the sample for x = 0.2 about 21.5 nm
and then decrease by the increase in Zn content. It is due to
the lower bond energy of Zn2+-O2- (159 kJ/mol) as
compared with Ni2+-O2- (451 kJ/mol). The Fourier
transform-infrared (FT-IR) spectra between 400 and 4000
cm-1 confirmed the intrinsic cation vibrations of the spinel
structure. Transmission electron microscopy (TEM)
pattern showed that the sample seem to be agglomeration
with spherical shape. Vibrating sample magnetometer
(VSM) measurement showed that the values of the
maximum magnetization at 15 kOe increased from 5.9 to
18.5 emu/g by decreasing of Zn content. The coercivity
(Hc) values of of the sample for x = 0.2 was 48.4 Oe and
then decreases with the increasing of Zn content. It is due
to the decrease in the magnetocrystalline anisotropy
attributed to the absence of Ni2+ cation.
BACKGROUND
Magnetic nanoparticles have become more important for
applications in biotechnology and biomedicine, as well as
technical ones like magnetic data storage over the past few
years. One of the most important magnetic nanoparticles is
spinel ferrite [1]. Among spinel ferrites, nickel ferrite
(NiFe2O4) is one of the most important spinel ferrites. It is
particularly attractive for researchers due to its high magneto
crystalline anisotropy, high saturation magnetization and
unique magnetic structure [2]. NiFe2O4 nanoparticles are
suitable for some applications like magnetic storage systems,
magnetic resonance imaging, and spintronics [3]. The
introduction of third metal ion like Zn in NiFe2O4 can easily
alter the distribution of Fe3+ ion. Zinc substituted mixed
ferittes (Zn-Ni Ferrites) are chosen due to their high electrical
resistivity, large permeability at high frequency, low
coercivity, high magnetization, mechanical
1
Department of Physics, Universitas Gadjah Mada, Yogyakarta,
INDONESIA.
2
Department of Electronics, Nagoya University, JAPAN.
3
Institutes of Materials and Systems for Sustainability, Nagoya University,
JAPAN.
*Contacting Author: esuharyadi@ugm.ac.id
978-1-5386-2772-3/17/$31.00 © 2017 IEEE
hardness, chemical stability and reasonable cost [4].
Different techniques to prepare ferrite nano-particles have
been reported such as low temperature solid state reaction,
chemical co-precipitation method, sol–gel auto-combustion,
hydrothermal, sonochemical reaction and ball milling method
[5]. Amongst the different methods, co-precipitation technique
is an appropriate method for the preparation of ferrites due to
its repeatability, reproducibility, uniform particle size
distribution, chemical stability and homogeneity [4].
Shahane et al [6] have synthesized NixZn1-xFe2O4
nanoparticles with compositions (x = 0.1, 0.3, 0.5) prepared by
co-precipitation method. But, Shahane ‘s research did not
present x-ray density, nanoparticles morphology, particle size,
diffraction rings pattern. And also, composition of x chosen
can’t explore about crystal structure and magnetic properties of
ZnNiFe2O4 when Ni-rich condition. So, the aim of the present
work is to investigate crystal structure and magnetic properties
of ZnxNi1-xFe2O4 with composition (x = 0.2. 0.3, 0.4, 0.5, 0.6,
0.7, 0.8) by co-precipitation method.
The starting materials used were NiCl2.6H2O,
ZnSO4.7H2O, FeCl3.6H2O were mixed in their stoichiometric
ratio at room temperature under constant stirring. Those
combined solutions were added of 3.37 mL HCl. After that,
the mixture was added dropwise to NaOH solution with
constant stirring and homogenized at 600C for 60 minutes. The
precipitated particles then washed six times with distilled
water to remove the salt residues and other impurities.
Furthermore, it was dried at 900C to obtain the powder. The
obtained powder were characterized for their structural,
morphological, and magnetic properties by XRD, FT-IR,
TEM, and VSM.
CURRENT RESULT
The X-Ray diffraction patterns of ZnxNi1-xFe2O4
nanoparticles (x = 0.2 – 0.8) prepared by co-precipitation
method are shown in Fig.1. XRD patterns confirmed that
nanoparticles have spinel cubic structure with some impurity
phases. Furthermore, it is shown that all the peaks of
nanoparticles undergoes shift in the 2Ʌ with the increase in Zn
content. This indicates the expansion of lattice parameter
value. It was found that the lattice parameter increases from
8.599 % (x = 0.2) to 8.650 % (x = 0.8) by the increase in Zn
content, this is due to the larger ionic radius of Zn2+ (0.74 %) as
compared with Ni2+ (0.69 %). Whereas, the crystallite size
decreases from 21.5 nm (x = 0.2) to 11.2 nm by the increase in
Zn content. This is due to the lower bond energy of Zn2+-O2-
(159 kJ/mol) as compared with Ni2+-O2- (451 kJ/mol) [1].
The formation of functional groups was confirmed by
Fourier transform-infrared (FT-IR) spectroscopy. Fig.2 shows
the FT-IR spectra of ZnxNi1-xFe2O4 (x = 0.2, 0.5, and 0.8)
between 400-4000 cm-1. Two major absorption peaks of metal-
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oxygen bands are seen in the FT-IR spectra of all samples. The
highest band (ɋ1) observed around 590 cm-1, corresponds to
intrinsic stretching vibrations of the tetrahedral M-O group,
whereas the lowest band (ɋ2) observed around 400 cm-1,
corresponds to intrinsic stretching vibrations of the octahedral
M-O group. In addition to these vibrational frequencies, the
absorption peak around 1628 cm-1 is due to the bending of H-
O-H group and around 3408 cm-1 is due to the stretching of O-
H group. Symmetric and asymmetric stretching of C-H group
are observed around 2855 cm-1 and 2921 cm-1. The size and
morphology of the nanoparticle with Zn content of 0.5 was
investigated by transmission electron microscopy (TEM).
Fig.3 shows the mainly of nanoparticles tend to agglomerate
with spherical shape.
Vibrating sample magnetometer (VSM) measurement
confirmed the magnetic properties of nanoparticles. Fig. 4
represents the hysteresis loops for various compositions of Zn.
The narrow loops for all the nanoparticles indicate the soft
nature of the nanomaterials. Various magnetic properties such Fig. 1. XRD patterns for ZnxNi1-xFe2O4 : (a) x=0.2, (b) x=0.3,
as maximum magnetization (Mmax), magnetic remanence (Mr), (c) x=0.4, (d) x=0.5, (e) x=0.6, (f) x=0.7, and (g) x=0.8.
and coercivity (Hc) are calculated from the hysteresis loop.
The maximum magnetization, remanence, and coercivity
decreased by increasing of Zn content from 18.53 to 5.92
emu.gram, 1.71 to 0.02 emu/gram, and 48.37 to 36.80 Oe. The
decrease of maximum magnetization is due to lattice defect,
weak magnetic super-exchange interaction between tetrahedral
and octahedral sites, and random orientation of spin on the
surface of the nanoparticles [7]. Whereas, the decrease of
coercivity values is due to the magnetocrystalline anisotropy
attributed to the absence of Ni2+ cation.

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