Rare Metal Materials and Engineering

Volume 44, Issue 9, September 2015

Online English edition of the Chinese language journal

Cite this article as: Rare Metal Materials and Engineering, 2015, 44(9): 2126-2131. ARTICLE

Preparation and Characterization of Nickel-Zinc Ferrites by

a Solvothermal Method
Deng Ni, Zhou Lin, Peng Xiaoling, Wang Xinqing, Ge Hongliang

China Jiliang University, Hangzhou 310018, China

Abstract: Nickel-zinc ferrites (Ni-Zn ferrites) nanocomposites were prepared by a solvothermal method and characterized by X-ray
diffraction (XRD), scanning electronic microscope (SEM) and vibrating sample magnetometer (VSM). The effects of solvothermal
parameters such as ratio of Ni2+ to Zn2+, the temperature and the time of solvothermal reaction on the magnetic properties and the
microstructures of Ni-Zn ferrites were investigated. Results demonstrate that with raising of reaction time, the particles become
bigger and more homogeneous, and the saturation magnetization of the Ni-Zn ferrites nanocomposites get higher; and the formation
temperature of Ni-Zn ferrites spherical particles is 180 °C; raising Ni2+ concentration in the Ni-Zn ferrites could not change their
morphologies. The saturation magnetization of the Ni-Zn ferrites increases with the increase of Ni2+ in the product; it will reach the
highest when Ni2+ concentration is up to x=0.30 while it will be the lowest when Ni2+ concentration is down to x=0.20.

Key words: Ni-Zn ferrites; solvothermal method; magnetic properties; microstructures; morphology

Since produced by Snock in 1935[1], ferrite magnetic material
has become a promising non-metallic magnetic material in
high-frequency weak current areas due to its larger resistivity
and higher dielectric properties than that of the metal, and its
high-frequency magnetic permeability[2-5]. Moreover，ferrite has
a higher machining performance, feasibility to be compressed
and molded, better chemical stability and lower cost. Therefore,
it plays a very significant role in research and development of
magnetic materials[6-10]. It is widely applied in wired or wireless
communications, radio, television, aerospace technology, and
used as the inductor components and transformers in other
electronic technologies[11-15].
Ni-Zn ferrite with spinel structure is an important member
of ferrites magnetic materials. Due to its high resistance rate,
low temperature coefficient, high Curie temperature, good
high-frequency performance, the ferrite exhibits interesting
magnetic and magneto-optical properties that are potentially
useful for a broad range of applications[16-18] such as high
frequency inductor cores, transformers, magnetic recording
materials, and microwave absorbing materials.
Many methods have been developed to prepare the
NixZn1-xFe2O4 nanoparticles, such as co-precipitation method[19],
hydrothermal method[20], citrate precursor method[21,22], sol-gel
method[23,24], self-propagating high-temperature method[25,26],
reverse micelle technique [27] and solvothermal method[28].
Sangeeta Thakur and his co-workers prepared nanocry-
stalline nickel-zinc ferrites (Ni0.58Zn0.42Fe2O4) using reverse
micelle technique[27] and all the samples showed superpara-
magnetic behavior at room temperature (300 K) and negligible
hysteresis at low temperature (5 K); Wei Yan synthesized
monodisperse Ni-Zn ferrites (NixZn1-xFe2O4) microspheres via
solvothermal method and the maximum magnetic saturation
value of the Ni0.2Zn0.8Fe2O4 microspheres could reach 60.6
A·m2/kg[28]; Yanling Zhang used solvothermal method to
prepare Ni0.5Zn0.5Fe2O4 coated with multi-wall carbon
nanotubes and the saturation magnetization value of the

Received date: September 17, 2014

Foundation item: National Natural Science Foundation of China (51002132); Public Technology Applied Research Projects of Science and Technology Department
of Zhejiang Province (2012C31022)
Corresponding author: Peng Xiaoling, Ph. D., Professor, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, P. R. China, Tel:
0086-571-86875600, E-mail: pxlqingliu@cjlu.edu.cn
Copyright © 2015, Northwest Institute for Nonferrous Metal Research. Published by Elsevier BV. All rights reserved.

2126
 Deng Ni et al. / Rare Metal Materials and Engineering, 2015, 44(9): 2126-2131

composites was 45.8 A·m2/kg [29]; Tania Jahanbin compared

Fe2O3 (311)
the structures and the electromagnetic properties of Ni-Zn Ni0.25Zn0.75Fe2O4 (400)
(220) (400) (422)(511)
ferrites prepared via co-precipitation and conventional 12 h

Intensity/a.u.
ceramic processing routes and found that the grain size
increased and the porosity decreased with the decrease of 8h

temperature for both methods, while dielectric constants

5h
decreased with the increase of frequency and increased with
the decrease of sintering temperature for both methods[30]. 2h

In general, solvothermal synthesis offers many advantages

over other methods due to its simplicity, and the products can
be obtained at relatively low temperature with high
crystallinity. What’s more, the chemical composition can be
accurately controlled, and homogeneous nanopowders can be
prepared; therefore the particle shape and size can be
controlled and it is capable to control crystal growth and
adequate to prepare samples in a large scale. In the present
paper, a one-pot solvothermal method was used to produce
Ni-Zn ferrites. Meanwhile, the effects of synthesis conditions
on the morphologies and magnetic properties of Ni-Zn ferrites
were systematically studied. Results demonstrate that using
this method the synthesis conditions can be easily controlled
and produced products have uniform particle sizes and good
magnetic properties. It is expected that the present research
results will be applied in large-scale production.
1 Experiment
All materials used in our experiments were analytically
pure and without further purifying.
Preparation of Ni-Zn ferrites was as follows: First,
FeCl3·6H2O, Zn(NO3)2·6H2O and Ni(NO3)2·6H2O were
dispersed into 50 mL of ethylene glycol according to molar
ratio of NixZn1-xFe2O4, while FeCl3·6H2O was fixed at 5 mmol,
and the mixture was stirred until it was fully dissolved.
Afterwards, 1.54 g of NH4COOH and 0.8 mL of polyethylene
glycol were added into the mixture, followed by stirring for
another 30 min, and the color gradually turned to dark brown.
The mixture was then transferred to a stainless steel autoclave
and heated from 160 °C to 220 °C for 2~12 h. The obtained
black product was washed with ethanol for several times and
was dried at 80°C in a drying oven[31]. In the present so-called
polyol process[32], the ethylene glycol served as both a
reducing agent and a solvent, while NaAc and PEG were used
for electrostatic stabilization to prevent particles from
agglomeration and serve as a protective agent, respectively.
The morphologies and structures of the products were
determined by X-ray diffraction (XRD, DX2700，China) with
Cu Kα radiation and scanning electronic microscope (SEM,
TM3000, Japan), and its magnetic properties were studied by
vibrating sample magnetometer (VSM, Lakeshore7407,
20 40 60 80
2θ/(°)
Fig.1 XRD patterns of products at different reaction time under
the conditions of 200 °C and x=0.25
American).
2 Results and Discussion
2.1 Effects of reaction time on products
Fig.1 shows the XRD patterns of products at different
solvothermal time while the reaction temperature is 200 °C
and value of x is 0.25. When the time is 2 h, no peak
corresponding to Ni-Zn ferrites is found. In other words,
Ni-Zn ferrites crystals are not formed due to too short time.
However, a wide characteristic peak of α-Fe2O3 is presented at
about 2θ=25° and 2θ=48°, but the width of the peak is not
narrow which indicates that the crystallinity is not good. As
the time rises up to 5 h, Ni-Zn ferrites peaks are got. However
the Ni-Zn ferrite phase contains extra peaks corresponding to
α-Fe2O3 and the width tends to be narrow. When the time
continues to increase from 5 h to 8 h, a well-crystallized pure
single Ni0.25Zn0.75Fe2O4 phase is formed. The crystallite size of
the produced Ni-Zn ferrite phase for the most intense peak
(311) is determined from the XRD data. It is demonstrated
that at this time, the crystallinity of Ni-Zn ferrites is relatively
higher. At these steps, the possible reactions may be written as
follows:
Fe3++3OH−→Fe(OH)3 (1)
mFe(OH)3→[Fe(OH)3]m (2)
2[Fe(OH)3]m→mFe2O3+3mH2O (3)
2[Fe(OH)3]m+xNi2++(1-x)mZn2++mOH−→
[Fe(OH)3]2m·NixZn1-xOH− (4)
[Fe(OH)3]2m·NixZn1-xOH−→
NixZn1-xFe2O4+3mH2O+mH+ (5)
Continuing to increase the time from 8 h to 12 h, extra peaks
of α-Fe2O3 are found.
Fig.2 shows the SEM images of products at different time.
It is clear that there is an increase in particle number with
raising of solvothermal time. No Ni-Zn ferrites spherical
particles are formed when the time is 2 h indicating that 2 h is
insufficient for the complete formation of the structure. With

2127
 Deng Ni et al. / Rare Metal Materials and Engineering, 2015, 44(9): 2126-2131

patterns in Fig.1, and α-Fe2O3 is non-magnetic, so the

saturation magnetization is not very high at this time. When
a b
time is increased up to 8 h, well crystallined Ni-Zn ferrites are
formed and no extra α-Fe2O3 is found at this time, so the
saturation magnetization is relatively high, at about 75.766
A·m2/kg. With further increasing the time from 8 h to 12 h,
saturation magnetization of the product decreases due to the
10 μm 1 μm appearance of α-Fe2O3.
c d
2.2 Effects of reaction temperature on products
Fig.4 shows the XRD patterns of products at different
solvothermal temperatures while the reaction time is 8 h and
the value of x is 0.25. When the temperature is below 180 °C,
no peaks reflecting to Ni-Zn ferrites are found. It indicates that
1 μm 1 μm the temperature is not high enough for Ni-Zn ferrites to be
crystallized. So the crystalline temperature for Ni-Zn ferrites
Fig.2 SEM images of products at different solvothermal time: is 180 °C. However, with raising of temperature, from 180 °C
(a) 2 h, (b) 5 h, (c) 8 h, and (d) 12 h to 220 °C, the intensity and the width of all peaks remain
stable which indicates the stability of the Ni-Zn ferrites
80
crystals.
8h
12 h Fig.5 shows the SEM images of the products at different
Magnetization/A·m2·kg-1

60
40 solvothermal temperatures. When the temperature is below
20 5h 180 °C, the particles are amorphous, which illustrates that the
2h
0 Ni-Zn ferrites are not formed. With increasing of temperature
–20 up to 180 °C, the particles turn from amorphous to spherical,
–40
corresponding to the conformation of Ni-Zn ferrites. Further
–60
increasing of the temperature from 180 °C to 220 °C, particle
–80
–2 –1 0 1 2 size becomes bigger and its distribution becomes more
Field/T homogeneous.
Fig.6 shows the hysteresis loops of products at different
Fig.3 Hysteresis loops of products at different time solvothermal temperatures. The figure is drawn into two
sections because when the temperature is 160 °C, Ni-Zn
the time increasing, until 5 h, a clear crystalline structure can
ferrites are not formed. So the saturation magnetization of the
be observed, but the particle size is not homogeneous. When
products is rather low (Fig.6a). It can be seen from Fig.6a that
the time continues to arise, more and more particles grow, and
the product is almost paramagnetic, and its ferromagnetic
the particle size becomes larger when the time is up to 8 h.
Continuing to raise the time from 8 h to 12 h, more and more
(311)
spherical particles are formed and the particle distribution Ni0.25Zn0.75Fe2O4
(511) (440)
becomes homogeneous, but the particle size intends to be (220) (400)
(422)
220 °C
smaller compared to the products got at 8 h, which may result
Intensity/a.u.

from the presence of extra α-Fe2O3 according to Fig.1. 200 °C

Fig.3 shows the hysteresis loops of products at different time.

180 °C
The results show that the values of saturation magnetization
increase with arising of the solvothermal time from 2 h to 8 h 160 °C

and this may be attributed to an increase in phase formation

and sample grain. When the time is 2 h, no Ni-Zn ferrites 10 20 30 40 50 60 70 80

particles are formed, the product is amorphous, so the 2θ/(°)

saturation magnetization is nearly at zero. When the time

Fig.4 XRD patterns of products at different solvothermal
continues to rise up to 5 h, Ni-Zn ferrites particles are formed,
temperatures in the cases of 8 h and x=0.25
but α-Fe2O3 was detected at this time according to the XRD

2128
 Deng Ni et al. / Rare Metal Materials and Engineering, 2015, 44(9): 2126-2131

ratios of Ni2+ to Zn2+. The XRD patterns of all systems show

a b sharp and intensive peak characteristics of the pure single
phase of cubic structure of NixZn1-xFe2O4. The diffraction
peaks corresponding to (111), (220), (311), (222), (400), (422),
(511) and (440) planes of Ni-Zn ferrites can be observed. With
the increase of Ni2+ in the products as seen in Fig.7, no
obvious change takes place.
10 μm 1 μm
d
Fig.8 shows the SEM images of products at different ratios
c
of Ni2+ to Zn2+. Spherical particles are all formed no matter
what the ratio of Ni2+ to Zn2+ is. This research was done when
the solvothermal time was set at 8 h and temperature was set
at 200 °C, and under this condition the materials have
experienced sufficiently reaction and reached stable state, so
1 μm 1 μm no obvious differences on the morphology and the structure of
particles obtained are seen. But when x value is 0.20, the
Fig.5 SEM images of products at different solvothermal particle size of the product is the most homogeneous among
temperatures: (a) 160 °C, (b) 180 °C, (c) 200 °C, the three products, but it is apparently smaller; when x value is
and (d) 220 °C
0.25 or 0.30, the particles are obviously larger, but particle
160 °C a size is not so homogeneous. So by controlling the synthesis
0.4
conditions, products with different particle performances can
Magnetization/A·m2·kg-1

0.2 be got.
Fig.9 shows the hysteresis loops of products at different
0.0
ratios of Ni2+ to Zn2+. The saturation magnetization increases
–0.2 with the increase of Ni2+ in the product. Magnetic properties of
–0.4 Ni-Zn ferrites are strongly dependent on the Ni2+ concentration.
Magnetization of ferrites, due to the difference between B and A
–0.6
–2 –1 0 1 2 sublattices, is primarily determined by the contributions of
100 magnetic ions residing in those sublattices. Compared to the
220 °C b
bulk ferrites, the magnetization of nanoparticles was reported to
Magnetization/A·m2·kg-1

200 °C
60 180 °C
be different in many instances [31,32]. This could be due to the
20 speculated differences in inversion degree of distribution of
0 the cations between A and B sites, to the spin canting and to
–20
the spin disorder in the shell around the core [33]. Thus, it may
–60 be argued from the above that the observed magnetization

–100
–2 –1 0 1 2 (311)
Field/T
(220) (400) (511) (440)
(111) (222) (422)
Intensity/a.u.

x=0.30
Fig.6 Hysteresis loops of products at different solvothermal
temperatures: (a) 160 °C and (b) 180~220 °C
x=0.25

performance is negligible. When the temperature reaches

180 °C that is the formation temperature of Ni-Zn ferrites x=0.20

(Fig.6b), the saturation magnetizations of products get 20 40 60 80

relatively higher. The saturation magnetizations of products 2θ/(°)
increase with the raising of solvothermal temperature.
2.3 Effects of x value on products Fig.7 XRD patterns of products at different ratios of Ni2+ to Zn2+
Fig.7 shows the XRD patterns of products with different

2129
 Deng Ni et al. / Rare Metal Materials and Engineering, 2015, 44(9): 2126-2131

a b c

1 μm 1 μm 1 μm

Fig.8 SEM images of products at different ratios of Ni2+ to Zn2+: (a) x=0.20, (b) x=0.25, and (c) x=0.30
109
80 x=0.30
x=0.25 3 Hyeon T. Chem Commun[J], 2003, 8: 927
Magnetization/A·m2·kg-1

40
0 3768
40
80
–2 –1 0 1
Field/T
Fig.9 Hysteresis loops of products at different ratios of Ni to Zn
value in our study could be influenced by a combined effect of
chemical composition, the degree of inversion in the cation
distribution, spin canting, surface spin disorder and particle
size. The results show that among the three products, the
values of saturation magnetization are the highest when the
ratios of Ni2+ to Zn2+ is 0.3:0.7 for 71.515 A·m2/kg, and the
lowest is 0.2:0.8 for 61.988 A·m2/kg.
3 Conclusions
1) Ni-Zn ferrites nanocomposites can be prepared via a
solvothermal method.
2) Phases of NixZn1-xFe2O4 can be obtained by increasing
the solvothermal time up to 5~12 h.
3) Temperature for Ni-Zn ferrites to be crystallized is
180 °C, while further increasing the temperature will make
particle size bigger and more homogeneous and the saturation
magnetization higher.
4) Saturation magnetization of the Ni-Zn ferrites increases
with the increase of Ni2+ in the product and reaches the highest
when Ni2+ concentration is up to x=0.30 for 71.515 A·m2/kg
and the lowest when Ni2+ concentration is down to x=0.2 for
61.988 A·m2/kg.
References
1 Li M Y, Li G D. Ferrite Physics[M]. Beijing: Science Press,
1978: 2 (in Chinese)
2 Caruso F, Spasova M, Susha A et al. Chem Mater[J], 2001, 13:
x=0.20
4 Xiong Y J, Xie Y, Chen S W et al. Chem Eur J[J], 2003, 9: 4991
5 Yu A, Mizuno M, Sasaki Y et al. Appl Phys Lett[J], 2002, 81:
6 Schaefer M, Dietzmann G, Writh H. J Magn Magn Mater
[J], 1991, 101: 95
7 Yu S, Yoshimura M. Chem Mater[J], 2000, 12: 3805
8 Vestal C R, Zhang Z J. J Am Chem Soc[J], 2003, 125: 9828
2
9 Sun S, Zeng H, Robinson D B et al. J Am Chem Soc[J], 2004,
126: 273
2+ 2+ 10 Jia X, Chen D, Jiao X et al. J Phys Chem C[J], 2008, 112: 911
11 Tartaj P. Curr Nanosci[J], 2006, 2: 43
12 Daos T J, Pourroy G, Bejin-Colin S et al. Chem Mater[J],
2006, 18: 4399
13 Lu H M, Zheng W T, Jiang Q. J Phys D: Appl Phys[J], 2007,
40: 320
14 Na H B, Song I C, Hyeon T. Adv Mater[J], 2009, 21: 1
15 Grancharov S G, Zeng H, Sun S et al. J Phys Chem B[J], 2005,
109: 13 030
16 Bao N Z, Shen L M, Padhan P et al. J Am Chem Soc[J], 2007,
129: 12 374
17 Wang Z L, Liu X J, Lü M F et al. J Phys Chem B[J], 2008,
112: 11292.
18 Kislov N, Srinivasan S S, Emirov Y et al. Mater Sci Eng B[J],
2008, 153: 70
19 Gul I H, Ahmed W, Maqsood A. J Magn Magn Mater[J], 2008,
320: 270
20 Wang H W, Kung S C. J Magn Magn Mater[J], 2004, 270: 230
21 Verma A, Goel T C, Mendiratta R G et al. J Magn Magn
Mater[J], 2000, 208: 13
22 Verma A, Thakur O P, Prakash C et al. Mater Sci Eng B[J], 2005,
116: 1
23 Zahi S, Hashim M, Daud A R. J Magn Magn Mater[J], 2007,
308: 177
24 Albuquerque A S., Ardisson J D, Macedo W A. J Magn Magn
Mater[J], 1999, 192: 277
25 Choi Y, Cho N I, Kim H C et al. J Mater Sci-Mater El[J], 2000,
11: 25

2130
 Deng Ni et al. / Rare Metal Materials and Engineering, 2015, 44(9): 2126-2131

26 Choi Y, Shim H S, Lee J S. J Alloy Compnd[J], 2001, 326: 56
27 Thakur S, Katyal S C, Singh M. J Magn Magn Mater[J], 2009,
321: 1
28 Yan W, Jiang W, Zhang Q H et al. Mater Sci Eng B[J], 2010,
171: 144
29 Zhang Y L, Zhu M F, Zhang Q H et al. J Magn Magn Mater[J],
2010, 322: 2006
30 Jahanbin T, Hashim M, Mantori K A. J Magn Magn Mater[J],
2010, 322: 2684
31 Calvin S, Carpenter E E, Harris V G et al. Phys Rev B[J], 2002,
66: 224 405
32 Liu J H, Wang L, Li F S. J Mater Sci[J], 2005, 40: 2573
33 Nathani H, Gubbala S, Misra R D K. Mater Sci Eng B[J], 2005,
111: 95

2131