Journal of Alloys and Compounds 816 (2020) 152501

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Structural and magnetic properties of NieCueCo ferrites prepared

from sol-gel auto combustion method with different complexing
agents
Wei Zhang a, Aimin Sun a, b, *, Xiqian Zhao a, Xiaoguang Pan a, Yingqiang Han a,
Nanzhaxi Suo a, Lichao Yu a, Zhuo Zuo a
a
College of Physics and Electronic Engineering, Northwest Normal University, Lanzhou, 730070, China
b
Key Laboratory of Atomic and Molecular Physics & Functional Materials of Gansu Province, Lanzhou, 730070, China

a r t i c l e i n f o a b s t r a c t

Article history: Sol-gel auto combustion method (EDTA, egg white, oxalic acid, tartaric acid and citric acid as a com-
Received 31 May 2019 plexing agent) was used to prepare NieCueCo ferrite nanoparticles with the chemical composition of
Received in revised form Ni0.2Cu0.1Co0.7Fe2O4. The phase formation has been confirmed by XRD patterns, which is a characteristic
27 September 2019
of spinel ferrite with most intense (311) peak. The crystallization of the material in the cubic spinel
Accepted 28 September 2019
Available online 30 September 2019
structure, the lattice parameter is approximately 8.38 Å. The average crystallite size of the samples
prepared with different complexing agents ranged from 30 to 40 nm. The formation of spinel structure
was also confirmed by Fourier transform infrared (FTIR) measurements. Scanning electron microscopy
Keywords:
Nickel-copper-cobalt ferrites
(SEM) and transmission electron microscopy (TEM) images indicate the existence of spherically cubic
Different complexing agents shaped particles. The synthesized samples were demonstrated by energy dispersive X-ray (EDX) to have
Sol-gel auto-combustion pure phase and structure, Ni, Cu, Co, Fe, and O were the main elements in Ni0.2Cu0.1Co0.7Fe2O4. Confirmed
Structural by X-ray photoelectron spectroscopy (XPS) cation redistribution of spinel ferrite nanoparticles. The
Magnetic properties magnetic parameters were measured by Vibrating sample magnetometer (VSM). Their ferromagnetic
behavior was confirmed by observing the hysteresis loops of the samples. Compared with the samples
prepared with other complexing agents (EDTA, egg white, tartaric acid and citric acid as complexing
agents), the maximum of saturation magnetization and remanent magnetization were obtained for the
sample prepared with oxalic acid as complexing agent. These ferrites have high coercivity. The sample
prepared with oxalic acid has better magnetic properties than those samples prepared with other
complexing agents. This indicates that oxalic acid as a complexing agent has stronger complexing ability
for samples and less hydrolysis of metal ions in precursor solution than other complexing agents.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction [4], or microwave radiation [5,6], such as cobalt ferrite [7], nickel
spinel ferrite [8], and other garnet, spinel, hexagonal ferrite [6].
In the current research, spinel ferrite nanomaterials are widely Spinel is the most commonly used microwave ferrite. Cobalt ferrite
used in the field of magnetic materials science. Its importance is is a mixture of metal oxide ceramic magnetic spinel crystal struc-
self-evident. This is attributed to their special optical, electronic ture [9]. In fact, cobalt, iron oxide nanoparticles with unique
and magnetic properties, which are usually different from volume. chemical properties, magnetic and optical properties. The appli-
Cobalt ferrite nano materials are well known as hard magnetic cation of cobalt ferrite is a kind of drug delivery system, cobalt
materials. Nowadays, magnetic field has been extensively studied modified for recording materials, magnetic materials, light spin
in the fields of high density magneto-optical recording [1e3], SOFC filter [10]. These properties and suitability have made the cobalt
ferrite one of the most highly studied magnetic materials. The
general nature of the spinel ferrite nanoparticles is that their
properties can be changed to meet the requirements by varying the
* Corresponding author. College of Physics and Electronic Engineering, Northwest synthesis process, precursor pH, catalyst ion substitution, anneal-
Normal University, Lanzhou, 730070, China.
E-mail address: AiminSun_1138@163.com (A. Sun).
ing conditions, agglomeration, and the like [11e14]. In spinel

https://doi.org/10.1016/j.jallcom.2019.152501
0925-8388/© 2019 Elsevier B.V. All rights reserved.
2 W. Zhang et al. / Journal of Alloys and Compounds 816 (2020) 152501

ferrite, nickel-copper-cobalt ferrite has mixed spinel structure and acid and citric acid) were dissolved in distilled water. These com-
belongs to the cubic system. It is a magnetic recording material plexing agents are also used as spontaneous combustion fuels. In
with good performance. In the field of material science, magnetic this experiment, the optimum molar ratio of metal cations to citric
materials have become a subject of considerable interest in the field acid, EDTA, tartaric acid and oxalic acid in precursor solution was
of power storage devices. Especially in magnetic data storage, 1:1.3. At the same time, the optimum ratio of using egg white as
magnetic fluid technology, magnetic targeting drug delivery, complexing agent to prepare ferrite sample was 50 mL fresh egg
magnetic resonance imaging has important applications [15,16]. white mixed with 100 mL distilled water to prepare the precursor
Nickel-copper-cobalt ferrite also has high magnetic anisotropy, solution. The mixed precursor solution was stirred evenly with a
high coercivity, high resistivity and good magnetic spectrum glass rod. In the mixing process, ammonium hydroxide solution
properties. Meanwhile, this ferrite is not easy to wear and corro- was added drop by drop to obtain a neutral solution with pH of 7.
sion, and it has good performance in high frequency and ultra-high Then, the mixed uniform precursor solution was stirred and heated
frequency applications. More and more researchers are improving for 3 he4 h at 80  C in a constant temperature magnetic heating
the magnetic properties of spinel ferrite by doping and substitution agitator to form a uniform and stable wet gel. The uniform and
[17,18]. The crystalline structure of spinel ferrites with the general stable wet gel was dried in a blast oven at 120  C for 2 h, the dried
chemical formula MFe2O4 (M ¼ Ni, Cu, Co, Zn, Mg etc.) shows a sample was ignited to obtain a black coloured powder. The final gel
cubic symmetry and its space group is Fd3m. These nanoferrite so obtained was fired at 600  C for 3 h in a tube furnace and then
magnetic materials have been prepared using a range of techniques grind the sintered powder for half an hour. The prepared samples
including coprecipitation, sol-gel, hydrothermal, glass crystalliza- were used for characterization and research. Flow charts of nano-
tion, microemulsion, and ultrasonic spray pyrolysis [19e21]. In the ferrite particles with chemical formula Ni0.2Cu0.1Co0.7Fe2O4 pre-
traditional preparation methods of nanoparticles, the grain size is pared by different complexing agents are shown in Fig. 1.
mainly controlled by changing the sintering temperature. However,
with the increase of sintering temperature, it is usually difficult for 3. Results and discussion
the grains to grow uniformly at the same time, which results in the
non-uniformity of the grains. Due to the limitation of material 3.1. Structural characterization
synthesis temperature, it is impossible to obtain smaller size
nanoparticles by reducing sintering temperature. Therefore, the In Fig. 2, the ferrite crystallizes as a cubic structure. Ferrite
sol-gel auto combustion method adopted in this experiment can crystal cell of each corner is comprised of ferrite molecules. (a)
achieve the purpose of regulating the particle size of the sample to tetrahedral; (b) octahedral. In the spinel ferrite lattice, the inter-
a certain extent by selecting different complexing agents. This is a action of three cations of octahedron and tetrahedron determines
simple process, in contrast to the traditional approach, this is a way the magnetic properties of the samples. The A-A, BeB and A-B are
to save time and energy and require a lower sintering temperature. three types of superexchange interactions, respectively. Compared
The mechanism of the effect of complexing agents on the particle with the other two kinds of superexchange interactions, the ex-
size of samples is complex, which is related not only to complex- change interaction between A-B is the strongest.
ation and other complex chemical reactions in solution, but also to Different complexing agent (EDTA, oxalic acid, egg white, tar-
the specific synthesized oxide system. taric acid and citric acid) synthesis of Ni0.2Cu0.1Co0.7Fe2O4 ferrite
In the present work, we have systematically studied the effects materials of XRD pattern are shown in Fig. 3. The data of XRD show
of different complexing agents (EDTA, oxalic acid, egg white, tar- that all diffraction peaks correspond to the cubic spinel structure.
taric acid and citric acid) on the structure and magnetic properties At the same time, all the main diffraction peak match the standard
of ferrite samples. X-ray diffraction (XRD type D8DISCOVER25) and on the surface of the crystal, and obtain the spinel phase of the
Fourier transform infrared spectroscopy (FTIR type NEXUS 870) samples. And the samples prepared by using citric acid, tartaric
were used to characterize the structural properties of the samples. acid, egg white and oxalic acid as complexing agents show pure
Scanning electron microscopy (SEM type HITACHI, JP S-4800) and single-phase cubic spinel structure. Whilst when the sample pre-
Transmission electron microscopy (TEM type TECHAI, G2 TF20) pared by using EDTA as complexing agents, additional peaks cor-
were used to observe the microstructure of the samples. Energy responding to Fe2O3 are observed to be evolved. It is difficult to
dispersive x-ray (EDX type THERMO, USA S-4800) and X-ray prepare single phase Ni0.2Cu0.1Co0.7Fe2O4 samples at lower sinter-
photoelectron spectroscopy (XPS type ESCALAB 250XI) were used ing temperature with EDTA as complexing agent. This may be
to measure the chemical elements in the samples and their valence attributed to the weaker complexation ability of EDTA to metal
states. Vibrating sample magnetometer (VSM type MICROSENSE cations. It is difficult for the metal ions to be fully complexed to
EV11) was used to measure magnetic properties of ferrite samples. form uniform and stable gel precursors, resulting in the new peaks
appear and form new external phases. Metal ions usually have
2. Experimental different degrees of hydrolysis in water. The higher the pH value of
the solution, the more obvious the hydrolysis. Hydrolysis of metal
Nickel-copper-cobalt ferrite nanoparticles having the basic ions will affect their uniform dispersion in the precursor solution,
chemical formula Ni0.2Cu0.1Co0.7Fe2O4 were prepared by using so some new foreign phase is easily produced at higher pH value. In
different complexing agents and sol-gel auto-combustion method. a solution of pH at 7, compared with these samples prepared with
For these different complexing agents, EDTA, oxalic acid, egg white, other complexing agents (citric acid, tartaric acid, egg white and
tartaric acid and citric acid, they are used as both complexing oxalic acid as complexing agents), the samples prepared with EDTA
agents and combustion aids. The chemical raw materials used were as complexing agent have obvious hydrolysis effect. This may also
cobalt nitrate (Co(NO3)2$6H2O), copper nitrate (Cu(NO3)2$3H2O), explain the weak complexation ability of EDTA as a complexing
nickel nitrate (Ni(NO3)2$6H2O), ferric nitrate (Fe(NO3)3$9H2O), agent and the formation of some new foreign phase. When the
EDTA (Ethylenediaminetetraacetic acid, C10H16N2O8), citric acid sintering temperature rises, the solid phase reaction between the
(C6H8O7$H2O), tartaric acid (C4H6O6), Oxalic acid (C2H2O4) and egg foreign phases will further take place to form nickel-copper-cobalt
white. The mass of various nitrates calculated by stoichiometric ferrite cubic spinel phase. By consulting relevant references, the
ratio is weighed by a laboratory balance. Metal nitrates and single-phase samples can still be prepared by increasing sintering
different complexing agents (egg white, tartaric acid, EDTA, oxalic temperature with EDTA as complexing agent [22]. Detected in the
 W. Zhang et al. / Journal of Alloys and Compounds 816 (2020) 152501 3

Fig. 1. Flow chart for the synthesis of Ni0.2Cu0.1Co0.7Fe2O4 nanoferrite particles by sol gel auto combustion process.

Fig. 2. Ferrites crystallize in the form of a cubic structure. Each corner of a ferrite unit cell consists of a ferrite molecule. (a) tetrahedral or A sites; (b) octahedral or B sites.

was observed that all peaks in the pattern belonged to spinel

structure and the spinel phase of the samples was confirmed [23].
Parameters including interplanar spacing (d), lattice constant
(a), average crystallite size (D), volume of unit cell (a3), dislocation
line density (d) prepared samples are obtained from XRD data are
shown in Table 1.
The inter-planar spacing value is calculated from Bragg’s law,
which is as follows [24]:

nl ¼ 2d sin q (1)
By using the relationship between cubic lattice constant is
determined [25]:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
a ¼ d h2 þ k2 þ l2 (2)
The average crystallite size is calculated using the Scherrer for-
mula [26]:

0:9l
D¼ (3)
Fig. 3. (Color online) X-ray powder diffraction for Ni0.2Cu0.1Co0.7Fe2O4 ferrite nano- b cos q
particles prepared using different complexing agents. (For interpretation of the ref-
erences to colour in this figure legend, the reader is referred to the Web version of this Under formula is used to calculate the preparation of the sam-
article.) ples of the dislocation density [27]:

1
XRD diagram small and strong peak, showed that the preparation d¼ (4)
D2
of samples with higher crystallinity. All the intensities of the
The ‘d’ is the distance between the plane, (h k l) is the miller
highest peaks were observed in the main peaks (311) and other
indices. ‘D’ is the average grain size, ‘b’ is the measurement of
peaks (111), (220), (222), (400), (422), (511) and (440). The position
sample diffraction peak (311) half-width (FWHM), ‘q’ is the
of the peaks match to the JCPDS card No. 22e1086 (for CoFe2O4)
diffraction angle of prague, ‘l’ is the X-ray wavelength
which belongs to the spinel symmetry with Fd3m space group. The
(0.15406 nm), the results are also listed in Table 1. The relationship
strongest reflection comes from the (311) plane in all the samples. It
is used to calculate the A (tetrahedral) and B (octohedral) of the
4 W. Zhang et al. / Journal of Alloys and Compounds 816 (2020) 152501

Table 1
Parameters obtained from XRD data for Ni0.2Cu0.1Co0.7Fe2O4 nano ferrite particles.

Complexing agent Inter planar spacing ‘d’ (Å) Lattice constant Average crystallite size ‘D’(nm) Volume of unit cell ‘a3’(Å3) Dislocation line density ‘d’(103 nm2)
‘a’(Å)

EDTA 2.5249 8.3741 35.20 587.24 0.81

Oxalic acid 2.5247 8.3735 36.43 587.11 0.75
Egg white 2.5250 8.3745 39.16 587.32 0.65
Tartaric acid 2.5255 8.3761 30.78 587.66 1.06
Citric acid 2.5255 8.3761 33.50 587.66 0.89

magnetic ion (hopping length) the distance between [28]: Scherrer’s formula show that the dependence of crystallite size on
pffiffiffi complexing agent from strong to weak is tartaric acid, citric acid,
3 EDTA, oxalic acid and egg white, respectively. Meanwhile, the lat-
dA ¼ a (5)
4 tice constants are also different for samples prepared with different
complexing agents. It can be seen from Table 1, the samples pre-
pffiffiffi
2 pared in 8.3735 Å and 8.3761 Å between the lattice constants. The
dB ¼ a (6) order of lattice constants from small to large is oxalic acid, EDTA,
4
egg white and tartaric acid (citric acid). And the lattice constants
The ‘dA’ is tetrahedral hopping length, the position of ‘dB’ hop- are 8.3735, 8.3741, 8.3745, 8.3761 and 8.3761 Å for these samples
ping length is octahedral position, ‘a’ is the lattice constant. The prepared by oxalic acid, EDTA, egg white, tartaric acid and citric
calculated value of different composition of dA and dB listed in acid as a complexing agent. It was observed that the lattice con-
Table 2. stants of the samples prepared with tartaric acid and citric acid as
X-ray density rx, bulk density rb and porosity ‘P’ are calculated complexing agents were the same. According to this relation (4),
using the formula given below. Table 2 shows the calculated values the dislocation density decreases with increasing average crystal-
of different components. By using the following relationship from lite size. The sample prepared by oxalic acid and egg white as
the lattice parameter value calculation of the ferrite of X-ray complexing agent has the smaller dislocation linear density. The
density: sample prepared by EDTA, tartaric acid and citric acid as com-
plexing agent has the larger dislocation linear density. The lower
8M
rx ¼ (7) the dislocation line density, the lower the defect density, which
NA a3 means the higher the crystallinity [29]. As can be seen from Table 2,
these samples prepared by different complexing agents have
Where M is the molecular weight, NA is the Avogadro number and
different hopping length. This may be due to the different com-
‘a’ is lattice constant. The following formula is used to calculate the
plexing abilities of different complexing agents to the samples,
bulk density of the sample:
resulting in different lattice sizes during the formation of the
.  samples. In addition to this, the porosity values in Table 2 show the
rb ¼ Ms pR2 t (8) ferrite with high porosity. The porosity of the prepared samples is
between 29.21 and 38.19%. The high porosity of the prepared par-
All samples were pressed at 16 MPa pressure to form a cylin-
ticles was observed due to the very low sintering temperature and
drical disc with a radius of 0.5 cm using a tablet press. Ms is mass of
the sol-gel spontaneous combustion method, which reduced the
the sample (pellet), ‘R’ is the radius of the pellet and ‘t’ is the
adhesion between the particles.
thickness of the pellet. According to the volume density and the X-
ray density of knowledge, use the following relationships to esti-
mate porosity percentage (P %): 3.2. Fourier transform infrared spectroscopy (FT-IR)
Porosity P ð%Þ ¼ ððrx  rb Þ = rx Þ  100 (9)
Fig. 4 shows the FT-IR spectra of Ni0.2Cu0.1Co0.7Fe2O4 mixed
As can be seen from Table 1, the average grain size of these nanoferrites prepared by different complexing agents (tartaric acid
samples ranges from 30 to 40 nm. The average crystallite size is and citric acid, egg white, EDTA and oxalic acid) after annealing at
different for samples prepared with different complexing agents 600  C. The crystal structure, chemical composition and
(EDTA, oxalic acid, egg white, tartaric acid and citric acid). The order morphology determine the location of the absorption band and the
of average crystallite size from small to large is tartaric acid, citric number of absorption peaks [30]. Because the bond lengths for
acid, EDTA, oxalic acid and egg white. And the average crystallite Fe3þ-O2- ions at tetrahedral and octahedral positions are different,
size are 30.78, 33.50, 35.20, 36.43 and 39.16 nm for these samples the difference of the expected absorption band positions is
prepared by tartaric acid, citric acid, EDTA, oxalic acid and egg observed [31e33]. The positions of the two strong absorption bands
white, respectively. The results of calculation and analysis by y1 and y2 are about 570 cm1 and 400 cm1, which are related to the

Table 2
Various structural parameters of Ni0.2Cu0.1Co0.7Fe2O4 nano ferrite particles.

Complexing agent Molecular weight X-ray density Bulk density Porosity Tetrahedral site ‘dA’(Å) Octahedral site ‘dB’(Å)
‘M’ (g/mol) ‘rx’(Kg/m3) ‘rb’(Kg/m3) ‘P’(%)

EDTA 235.04 5318.79 3488.84 34.41 3.6261 2.9607

Oxalic acid 235.04 5319.97 3765.77 29.21 3.6258 2.9605
Egg white 235.04 5318.07 3301.52 37.92 3.6263 2.9608
Tartaric acid 235.04 5314.99 3285.08 38.19 3.6270 2.9614
Citric acid 235.04 5314.99 3506.44 34.03 3.6270 2.9614
 W. Zhang et al. / Journal of Alloys and Compounds 816 (2020) 152501 5

FeeO bond shifts to high frequency when egg white is used as

complexing agent, which may also lead to the decrease of magnetic
properties of the samples. The change of absorption peaks y1 can
also be interpreted as the bond-strength and the bond-energy are
increased due to the formation of a new chemical bond with O2-.
Therefore, from the FT - IR measurements also confirmed the for-
mation of the spinel structure sample.

3.3. Scanning electron microscopy (SEM)

The surface morphology of nickel-copper-cobalt ferrite samples

were studied by scanning electron microscopy (SEM). Fig. 5 shows
the morphological images of Ni0.2Cu0.1Co0.7Fe2O4 nanoferrite par-
ticles prepared by different complexing agents. It can be seen from
the figure that the particles of the prepared sample are approxi-
mately spherical when EDTA, oxalic acid, egg white, tartaric acid
and citric acid are used as complexing agents. At the same time, it
can also be seen from the observation that the particles prepared by
using oxalic acid as complexing agent are fine and uniform. And the
average particle size of all samples was less than 50 nm. Moreover,
Fig. 4. FT-IR spectra of Ni0.2Cu0.1Co0.7Fe2O4 ferrite nanoparticles prepared using
the particles of the sample prepared with EDTA, egg white, citric
different complexing agents.
acid and tartaric acid as complexing agent showed irregular shape.
There is obvious calcination adhesivity between particles, and there
cubic structure of spinel. This measurement result was reported by are large clusters at the same time. This phenomenon may be
Ahmad Gholizadehn, Elahe Jafari et al. [34]. That is because of the attributed to the relatively strong interaction between ferrite
octahedral and tetrahedral complexes in the spinel structure, magnetic particles and particles, resulting in the existence of
which shows the y2 and y1 absorption bands, respectively. Mean- agglomeration, such as Van der Waals forces and magnetic dipole
while, High wave number (y1 ¼ 580-594 cm1) and low wave interaction [38].
number (y2) are designated as tetrahedral complexes (Mtetra-O) and
octahedral complexes (Mocta-O), respectively [35]. No y2 in the FTIR 3.4. Transmission electron microscopy (TEM)
absorption peak, this is because it is not in the measurement range.
The figure shows absorption peak y1 for Ni0.2Cu0.1Co0.7Fe2O4 mixed Fig. 6(a) and (b) show images of Transmission Electron Micro-
nano ferrites prepared by different complexing agents. In the 3420 scope (TEM) and size distribution histogram of the Ni0.2Cu0.1Co0.7-
cm-1 and 1630 cm-1 near the wide absorption band attributed to Fe2O4 nano ferrite prepared with oxalic acid as complexing agent.
NieCueCoeFeeO vibration lattice in OeH of H2O [36]. This may be The samples of TEM micrograph shows on particle size,
due to the fact that the stretching vibrations of antisymmetric NO1 3 morphology and microstructure of complete view. Particles and the
and ferrite tetrahedral complexes corresponds to the peaks near TEM images show existence, its shape is spherical cubic micro-
1380 cm1. Absorption bands were observed at 1128 cm1, which crystalline. The particle size distribution histogram of the sample
may be due to the vibration of the remaining CeO bonds [37] (see prepared by using oxalic acid as complexing agent is shown in the
Fig. 4). inset in Fig. 6(a). It was found that the average particle size was
The absorption peaks y1 are also different for samples prepared 36 nm, which was well consistent with the XRD results. Fig. 6(c)
with different complexing agents. Reported in Table 3, Ni0.2Cu0.1- and (d) show images of Transmission Electron Microscope (TEM)
Co0.7Fe2O4 (EDTA, oxalic acid, egg white, tartaric acid and citric acid and size distribution histogram of the Ni0.2Cu0.1Co0.7Fe2O4 nano
as a complexing agent) of the absorption band of the samples. It can ferrite prepared with egg white as complexing agent. From Fig. 6,
be seen from the Table 3 that the absorption peaks y1 of the pre- the particles were observed to be in the shape of spherical cubic
pared samples are between 580 cm1 and 594 cm1. The order of microcrystals, forming a loose aggregate. The particle size distri-
absorption peaks y1 from small to large is citric acid, tartaric acid, bution histogram of the sample prepared by using egg white as
EDTA, oxalic acid and egg white. The chemical bond constant be- complexing agent is shown in the inset in Fig. 6(c). The average
tween FeeO bonds decreases when Fe3þ moves towards O2- bond. particle size of the sample was 39 nm, which was very consistent
This is based on the theory of charge balance. From the reflection of with the results calculated by X-ray diffraction. Similarly, it was
absorption peaks, it can be seen that the peak value of FeeO bond observed that ferrite samples prepared with oxalic acid and egg
shifts to high frequency in Ni0.2Cu0.1Co0.7Fe2O4 nanoferrite particles white as complexing agents formed loose aggregates. This phe-
prepared with egg white as complexing agent. Compared with the nomenon is consistent with that observed in SEM images. This is
samples prepared with other complexing agents, the peak value of due to the strong magnetism of the samples. As a result, each
particle is magnetized and aggregation. This leads to particles

Table 3
Frequency bands y1 of the samples.

Complexing agent Sample Sintering temperature ( C) y1 (cm1)

EDTA Ni0.2Cu0.1Co0.7Fe2O4 600 584
Oxalic acid Ni0.2Cu0.1Co0.7Fe2O4 600 586
Egg white Ni0.2Cu0.1Co0.7Fe2O4 600 594
Tartaric acid Ni0.2Cu0.1Co0.7Fe2O4 600 582
Citric acid Ni0.2Cu0.1Co0.7Fe2O4 600 580
6 W. Zhang et al. / Journal of Alloys and Compounds 816 (2020) 152501

Fig. 5. Scanning electron microscopy micrographs of Ni0.2Cu0.1Co0.7Fe2O4 ferrite nanoparticles prepared using different complexing agents: (a) EDTA, (b) Oxalic acid, (c) Egg white,
(d) Tartaric acid, (e) Citric acid.

together to form a loose conglomeration. The corresponding se- egg white as complexing agent. A small amount of S, Cl and K el-
lective area electron diffraction (SAED) analysis of the sample is ements were also detected in the samples. This is attributed to the
shown in Fig. 7 (a) and (b). Through the SAED pattern confirmed the use of egg white as a complexing agent in the preparation of
preparation of the crystallization properties of the sample. From samples. Elements S, Cl and K are chemical constituents of egg
the SAED pattern can see clearly the diffraction rings. white. The pure phase and structure of the synthesized ferrite were
proved by EDX (Fig. 8 (a)). And it has also been successfully proved
that Ni, Cu, Co, Fe and O are the main elements in Ni0.2Cu0.1Co0.7-
3.5. Elemental analysis (EDX)
Fe2O4 (Fig. 8).

Representative EDX spectra of ferrite samples prepared with

oxalic acid and egg white as complexing agents are shown in Fig. 8. 3.6. X-ray photoelectron spectroscopy study (XPS)
Fig. 8(a) shows the EDX spectra of Ni0.2Cu0.1Co0.7Fe2O4 nanoferrites
prepared with oxalic acid as a complexing agent. Ni, Cu, Co, Fe and In the prepared spinel nickel-copper-cobalt ferrite, the oxidized
O are the main elements detected in Ni0.2Cu0.1Co0.7Fe2O4 prepared states of Ni, Cu, Co and Fe can be detected by X-ray photoelectron
with oxalic acid as complexing agent. Fig. 8(b) shows the EDX spectroscopy (XPS). At the same time, the tetrahedral and octahe-
spectra of Ni0.2Cu0.1Co0.7Fe2O4 nanoferrites prepared with egg dral positions in spinel ferrite lattices can also be measured by this
white as a complexing agent. Meanwhile, Ni, Cu, Co, Fe and O are method. The X-ray photoelectron spectroscopy (XPS) of Ni0.2Cu0.1-
the main elements detected in Ni0.2Cu0.1Co0.7Fe2O4 prepared with Co0.7Fe2O4 nanoferrite particles prepared with oxalic acid was
 W. Zhang et al. / Journal of Alloys and Compounds 816 (2020) 152501 7

Fig. 6. TEM images and size distribution histograms of Ni0.2Cu0.1Co0.7Fe2O4 ferrite nanoparticles prepared using different complexing agents: (a)e(b) Oxalic acid and (c)e(d) Egg
white.

Fig. 7. (a) and (b) shows SAED images of Ni0.2Cu0.1Co0.7Fe2O4 nano ferrite particles: (a) Oxalic acid, (b) Egg white.

Fig. 8. EDX spectra of Ni0.2Cu0.1Co0.7Fe2O4 ferrite nanoparticles prepared using different complexing agents (Oxalic acid and Egg white).
8 W. Zhang et al. / Journal of Alloys and Compounds 816 (2020) 152501

Fig. 9. X-ray photoelectron spectra (XPS) of Ni0.2Cu0.1Co0.7Fe2O4 nano ferrite particles prepared using complexing agents of oxalic acid, (a) survey spectrum and high-resolution
spectra for (b) Ni 2p, (c) Cu 2p (d) Co 2p, (e) Fe 2p, and (f) O 1 s.

shown in Fig. 9. The peaks of Ni, Cu, Co, Fe, O and C were observed respectively (Fig. 9(d)). The presence of Co2þ in the oxidation state
by XPS spectra from Fig. 9(a). The Fig. 9(b)e(f) represents the XPS of Ni0.2Cu0.1Co0.7Fe2O4 nanoparticles, this is because the Co 2p3/2
core level spectra of Ni 2p, Cu 2p, Co 2p, Fe 2p and O 1s of shakeup satellite peak be detected by XPS spectroscopy [40]. The
Ni0.2Cu0.1Co0.7Fe2O4 sample prepared with oxalic acid. The binding relative contributions of tetrahedral and octahedral positions to the
energy of Ni 2p, Cu 2p, Co 2p and Fe 2p confirmed the existence of total strength of Co2þ ions are 16% and 84%, respectively. Fig. 9(e)
nickel, copper, cobalt and iron ions in the synthesized ferrite shows that the binding energy of Fe 2p3/2 and Fe 2p1/2 at 710.9 and
nanoparticles. As can be seen from Fig. 9(b), the peaks of 855.3 eV 724.6 eV, with a typical satellite peak of Fe3þ at 719.3 eV. These
and 872.5 eV can be attributed to Ni 2p3/2 and Ni 2p1/2, while the binding energies indicate the presence of Fe3þ in Ni0.2Cu0.1Co0.7-
same peaks in NiFe2O4 occur at 855.1 eV [39]. Fig. 9(c) shows that Fe2O4 nanoparticles [41]. Meanwhile, The relative contributions of
the binding energy 933.4 and 953.2 eV correspond to Cu 2p3/2 and tetrahedral and octahedral positions to the total strength of Fe3þ
Cu 2p1/2, and the typical satellite peak Cu2þ is 941.6 eV [41]. For Co ions are 23% and 77%, respectively. The O 1s peak can be fitted by
2p3/2 and its shake-up satellite peak, they correspond to the bind- two peaks as shown in Fig. 9(f). The peaks of 529.74 eV and
ing energy peaks at 780.2 and 786.3 eV, respectively. At the same 531.57 eV can be attributed to lattice oxygen (O2-) ions [42] and
time, for Co 2p1/2 and its shake-up satellite peak, they correspond other oxygen components [43]. Therefore, in the process of syn-
to another two binding energy peaks at 795.6 and 803.6 eV, thesizing Ni0.2Cu0.1Co0.7Fe2O4 ferrite. It can be concluded that metal
 W. Zhang et al. / Journal of Alloys and Compounds 816 (2020) 152501 9

ions exist in the crystal structure of ferrite in a suitable valence defined as (11)
state.
SFD ¼ DH=Hc (11)

3.7. Magnetic measurements Where, DH is dM/dH curve of half peak width, the largest and
distinguish the hysteresis loop for dM/dH. In the second quadrant,
The magnetic property of synthesized Ni0.2Cu0.1Co0.7Fe2O4 the steepness of the hysteresis loop of the magnetic recording
(EDTA, egg white, tartaric acid, oxalic acid and citric acid as a material can be described by SFD. Meanwhile, SFD is also used as a
complexing agent) nanoparticles were investigated by using method to characterize the rectangularity of hysteresis loops. For
Vibrating sample magnetometer (VSM). At the same time, these ferrite samples, the smaller SFD and the larger squareness (Mr/Ms),
samples were measured by applying a magnetic field of 1 T at room the better the properties of hard magnetic materials.
temperature. In the spinel ferrite lattice, crystallite size, cation Table 4 shows that the samples prepared with different com-
distribution, chemical composition and preparation technology plexing agents have different magnetic properties. Moreover,
determine the magnetic properties of spinel ferrite magnetic different complexing agents have great influence on the magnetic
nanoparticles. With the change of the applied magnetic field, the properties of the samples. It can be seen from Table 4 that the
magnetization of Ni0.2Cu0.1Co0.7Fe2O4 samples prepared by remanent magnetization are 22.30, 27.37, 27.74, 28.18 and 29.05
different complexing agents also changed correspondingly, as emu/g for these samples prepared by egg white, tartaric acid, citric
shown in Fig. 10. It can be noticed from magnetic hysteresis loops of acid, EDTA and oxalic acid, respectively. The value of remanent
synthesized Ni0.2Cu0.1Co0.7Fe2O4 (tartaric acid, egg white, EDTA, magnetization is the largest for the sample prepared with oxalic
oxalic acid and citric acid as a complexing agent) nano particles that acid as complexing agent. And the value of remanent magnetiza-
these Ni0.2Cu0.1Co0.7Fe2O4 nano particles exhibit ferromagnetic tion is the smallest for the sample prepared with egg white as
behaviour with remanent magnetization, saturation magnetization complexing agent. It can be also seen from the table that the
and coercivity. This is attributed to the fact that bivalent and saturation magnetization are 46.48, 50.67, 53.81, 54.48 and 56.98
trivalent metal cations occupy octahedral (B) sites and tetrahedral emu/g for these samples prepared by egg white, EDTA, citric acid,
(A) of the spinel structure in the formation of spinel ferrites in tartaric acid and oxalic acid, respectively. Similarly, the value of
synthetic samples. When the octahedral position is occupied by saturation magnetization is the largest for the sample prepared
trivalent metal ions and the tetrahedral position is occupied by with oxalic acid as complexing agent. And the value of saturation
bivalent metal ions, it belongs to the positive type magnetic spinel magnetization is the smallest for the sample prepared with egg
structure. However, when the tetrahedral site is occupied by white as complexing agent. Compared with the samples prepared
trivalent metal ions and the octahedral site is occupied equally by with EDTA, tartaric acid, citric acid and egg white as complexing
trivalent and divalent metal ions, it belongs to the inverse type agents, it can be clearly observed from Table 4 and Fig. 10 that the
magnetic spinel structure. The magnetic parameters of the pre- saturation magnetization and remanent magnetization of the
pared samples were measured by VSM in Table 4. The coercivity sample prepared with oxalic acid as complexing agent reaches the
rectangular ratio and switching field distribution are expressed by maximum. This may be attributed to the strong complexation
S* and SFD in Table 4, respectively. ability of oxalic acid to metal cations. Simultaneously, oxalic acid
The coercive rectangle (S*) and switching field distribution can completely complexe the metal ions to form a uniform and
(SFD) are also important magnetic parameters for characterizing stable gel precursor. Meanwhile, this change in magnetic properties
magnetic recording media materials. The definition of S* is (10) was observed in ferrite samples prepared with different complex-
  ing agents. This is also attributed to the fact that different com-
dM dHjHc ¼ Mr ½Hc ð1  S Þ (10) plexing agents will lead to different cation distribution in ferrite
The formula of the distribution of switching field (SFD) is
el’s
lattices during the formation of ferrite lattices. According to Ne
theory of super-exchange interaction between A-B, this sufficient
complexation reaction is also between citric acid and tartaric acid
and metal ions. For oxalic acid as complexing agents, this strong
complexation ability enhances the super-exchange interaction be-
tween A-B during the formation of ferrite, which leads to the in-
crease of saturation magnetization and remanent magnetization.
Table 4 also shows that the coercivity values are 880.11, 1260.14,
1309.14, 1419.87 and 1591.59 Oe for egg white, citric acid, tartaric
acid, oxalic acid and EDTA as complexing agents, respectively. The
coercivity values in Table 4 show that ferrite samples prepared with
egg white, citric acid, tartaric acid, oxalic acid and EDTA as com-
plexing agents have high coercivity. The high coercivity may be due
to the high porosity of the samples (column 5 of Table 2) and other
reasons, such as smaller grain size and magnetic anisotropy. This is
due to the smaller the particles, the surface effect dominates, and
the magnetic domain wall of the nanoparticle decrease, resulting in
high coercivity of the samples. Squareness (Mr/Ms) needs to be
large, so that it helps reduce their own demagnetization effect to
improve the information recording effect. Meanwhile, the square-
ness ratio are 0.480, 0.503, 0.509, 0.516 and 0.557 for these samples
prepared by egg white, tartaric acid, oxalic acid, citric acid and
EDTA, respectively. Moreover, the Mr/Ms of the prepared ferrite
Fig. 10. M-H hysteresis loops of Ni0.2Cu0.1Co0.7Fe2O4 ferrite nanoparticles prepared samples are less than 0.6, which indicates the existence of cubic
using different complexing agents at room temperature. anisotropic single domain particles in the composite [44]. Table 4
10 W. Zhang et al. / Journal of Alloys and Compounds 816 (2020) 152501

Table 4
Magnetic parameters of the prepared ferrite samples.

Complexing Remanent Saturation magnetization Ms Coercivity Squareness S (Mr/ Coercivity Squareness Switching field distribution SFD (dH/
agent magnetization (emu/g) Hc (Oe) Ms) S* Hc)
Mr (emu/g)

EDTA 28.18 50.67 1591.59 0.557 0.382 0.67

Oxalic acid 29.05 56.98 1419.87 0.509 0.290 0.77
Egg white 22.30 46.48 880.11 0.480 0.222 0.82
Tartaric acid 27.37 54.48 1309.14 0.503 0.358 0.69
Citric acid 27.74 53.81 1260.14 0.516 0.381 0.67

also shows that the distribution of switching field (SFD) and the acid as complexing agents. Moreover, the Ms by Brown relations
coercivity squareness (S*) are related to the samples prepared by associated with Hc. Thus, according to the formula of magnetic
different complexing agents. The grain size distribution is generally anisotropy is given below [50]:
associated with SFD, because the particles with different shapes
and sizes will be reversed under different field strengths. Higher Hc
2K
and smaller SFD are also very important for high density magnetic HC ¼ (14)
recording media materials. The value of SFD is as small as possible, m0  MS
with the distribution of switching field (SFD) are 0.67, 0.67, 0.69,
Where ‘K’ is anisotropy constant, Ms is saturation magnetization
0.77 and 0.82 for these samples prepared by citric acid, EDTA, tar-
and Hc is coercivity taken from the M-H loops as given by
taric acid, oxalic acid and egg white, respectively. By comparison, it
StonereWohlfarth theory. In Gauss unit, the value of vacuum
can be found that the maximum value of SFD is the sample pre-
permeability is 1. All magnetic data calculated from the relationship
pared with egg white as complexing agent. This also shows that egg
are recorded in Table 5. Similarly, SFD is also an important
white as a complexing agent has weak complexing ability to the
parameter. It can characterize the micro and macro integration
sample. The coercivity squareness (S*) are 0.222, 0.290, 0.358, 0.381
uniformity of magnetic recording materials. The values of dM/dH
and 0.382 for these samples prepared by egg white, oxalic acid,
and Hm obtained by differential treatment of hysteresis loops are
tartaric acid, citric acid and EDTA, respectively. The bigger the
recorded in Table 5. Fig. 11 is obtained by differential hysteresis
better for the coercivity squareness (S*), it is found that coercivity
loops of Ni0.2Cu0.1Co0.7Fe2O4 samples prepared with different
squareness (S*) is larger for samples prepared with EDTA, oxalic
complexing agents.
acid, citric acid and tartaric acid as complexing agents. But
In Table 5, the experimental value of Ni0.2Cu0.1Co0.7Fe2O4 mag-
compared with the samples prepared with other complexing
netic moment are 2.13, 2.40, 1.96, 2.29 and 2.26 mB for these samples
agents, the coercivity squareness (S*) of the samples prepared with
prepared by EDTA, oxalic acid, egg white, tartaric acid and citric
egg white as complexing agent was significantly reduced.
acid, respectively. The experimental value of Ni0.2Cu0.1Co0.7Fe2O4
In cubic spinel ferrites, each ion at A-position has 12 B-position
magnetic moment is smaller for samples prepared with egg white
ions as its nearest neighbor. The A-B super exchange interaction
as complexing agents. Meanwhile, it is found that the experimental
dominates the A-A and BeB interaction in the lattice, which is

el’s molecular field model [45]. Magnetic structure of value of Ni0.2Cu0.1Co0.7Fe2O4 magnetic moment is larger for sample
known by Ne
prepared with oxalic acid as complexing agents. This shows that the
ferrite Ni0.2Cu0.1Co0.7Fe2O4 as decribed following [46]:
sample prepared with oxalic acid as complexing agents have a large
magnetic moment. And it also indicates that oxalic acid have strong
complexing ability. The difference of cation net magnetic moment
between octahedral (B) and tetrahedral (A) sites leads to different
magnetization of spinel ferrites. Compared with the intergranular
A-A and BeB interactions, the A-B superexchange interaction is
This is because the two Ne
el’s sublattice model proposed by the
relatively stronger, which is known by Ne
el’s model. The vector
cation distribution between A and B sublattice [47,48]. Because of
sum of the net magnetic moments of a single A and B sublattices
the spinel ferrite usually show the ferrimagnetic, their theoretical
gives the saturation magnetization [51,52]. In spinel nickel-copper-
magnetization by position A and B of the difference of the total
cobalt ferrite, Ni2þ ions, Cu2þ ions and Co2þ ions mainly occupy
magnetic moment of the decision, to calculate the net magnetic
octahedral B-sites, while Fe3þ ions occupy octahedral B-sites and
moment by using the relationship:
tetrahedral A-sites, respectively. For nickel-copper-cobalt ferrites,
mBðCal:Þ ¼ MB  MA (12) Ni2þ (2 mB), Cu2þ(1 mB) and Co2þ (3 mB) mainly occupy the octahedral
B sites. The theoretical value of Ni0.2Cu0.1Co0.7Fe2O4 magnetic
moment is expected to be at least 2.6 mB for a complete inverse
Where, MB and MA are the total magnetic moments at position B
spinel structure. After the magnetic moments of iron ions at A and B
and position A, respectively. By consulting the relevant references
positions of spinel structure cancel each other out, and it must be
of magnetic ferrite materials, the magnetic moment of the ion Ni2þ
used more for mixed spinel structure. The intrinsic internal
is 2mB, the ion Cu2þ is 1mB, the ion Co2þ is 3mB, and the ion Fe3þ is
demagnetization in nanoparticles due to surface effect and
5mB. The experimental values of the magnetic moments (mB) of per
incomplete magnetization of the samples in the applied field lead
formula unit in Bohr magneton are calculated by using the
to the decrease of the experimental values of the magnetic mo-
following relationships [49]:
ments of the prepared samples. The inherent internal demagneti-
MW  MS zation in nanoparticles is explained by the core shell model of
mBðexp:Þ ¼ (13) nanoparticles. Magnetic nanoparticles have spin twisting or tilting
5585
with the core, and can also be considered as a combination of the
Where MW is the molecular weight of Ni0.2Cu0.1Co0.7Fe2O4 samples core and the demagnetizing shell (surface) in this model [53,54].
prepared with EDTA, oxalic acid, egg white, tartaric acid and citric Assuming that magnetic particles are isolated (exchange
 W. Zhang et al. / Journal of Alloys and Compounds 816 (2020) 152501 11

Table 5
The values of magnetic moment, magnetic anisotropy, dM/dH and Hm calculated from M(H) data of Ni0.2Cu0.1Co0.7Fe2O4.

Complexing agent Unit cell mag. mom mB(exp.) Anisotropy Hm (Oe) dM/dH (emu/(g Oe))103
Constant K104 (erg/g)
H/0 H/Hm

EDTA 2.13 4.03 1598.5 9.74 28.73

Oxalic acid 2.40 4.05 1548.4 14.13 29.36
Egg white 1.96 2.05 798.8 16.58 32.78
Tartaric acid 2.29 3.57 1498.4 13.46 33.26
Citric acid 2.26 3.39 1348.4 13.17 35.95

Fig. 11. Field dependence of dM/dH of different samples. 2Hm measures the magnetic field that separates two peaks.
12 W. Zhang et al. / Journal of Alloys and Compounds 816 (2020) 152501

interaction spin) single domain, the anisotropic constants are 4. Conclusions

calculated by using coercivity and saturation magnetization. As
shown in Table 5, it can be observed that the anisotropy constant The Ni0.2Cu0.1Co0.7Fe2O4 nano-particles have been prepared
are 4.03  104, 4.05  104, 2.05  104, 3.57  104 and 3.39  104 erg/ successfully by sol-gel auto combustion technology with egg white,
g for these samples prepared by EDTA, oxalic acid, egg white, tar- tartaric acid, EDTA, oxalic acid and citric acid as complexing agents.
taric acid and citric acid, respectively. The magnetic anisotropy is XRD results showed that the spinel structure of Ni0.2Cu0.1Co0.7Fe2O4
proportional to the coercivity, and the changes of coercivity are exhibited cubic spinel structure. The sample was prepared by EDTA
observed with EDTA, oxalic acid, egg white, tartaric acid and citric as complexing agent, new small peaks formed, which was identi-
acid as complexing agents to prepare ferrite nanoparticles. Simi- fied as Fe2O3. For the samples prepared with different complexing
larly, the maximum of magnetic anisotropic constant is obtained agents, the change of average crystallite size is larger. Fourier
for samples prepared using oxalic acid as a complexing agent. transform infrared (FTIR) measurements also confirm the forma-
However, the minimum of magnetic anisotropic constant is ob- tion of the cubic spinel structure of ferrite. SEM and TEM images
tained for samples prepared using egg white as a complexing agent. can be used to observe the particle size and morphology of the
It also shows that oxalic acid as a complexing agent has stronger prepared samples at magnification. It can be observed from SEM
complexing ability to the sample and egg white as a complexing images that the particles prepared by using oxalic acid as com-
agent has weaker complexing ability to the sample. The anisotropy plexing agent are fine and uniform with the average particle size is
constants have very large variation for the samples prepared by less than 50 nm. Meanwhile, the particles with spherical cubic
different complexing agents. This may be attributed to the contri- microcrystals are displayed by TEM images. And the particles pre-
bution of several factors, such as density, grain size, porosity, acidity pared by using oxalic acid as complexing agent are fine and uni-
and alkalinity of precursor solution, sintering temperature and form. The average particle size of the samples are 36 and 39 nm
chemical composition, which influence the shape and width of the with oxalic acid and egg white as complexing agents to prepare
hysteresis loop (M-H). This leads to demagnetization effect, high samples, which are in good agreement with the results calculated
coercivity and magnetic anisotropy. Therefore, the prepared nickel- by X-ray diffraction. Energy dispersive X-ray (EDX) confirmed that
copper-cobalt ferrites with high porosity show high value of coer- the peak of Ni, Cu, Co, Fe and O were detected in the prepared
civity. When the grain size of nano-ferrite magnetocrystalline samples, and they are the main elements in Ni0.2Cu0.1Co0.7Fe2O4. X-
materials becomes larger, the contained internal magnetic domains ray photoelectron spectroscopy showed that cations redistributed
of nano-ferrite magnetocrystalline materials will increase. In some in the synthesized spinel ferrite nanoparticles. Compared with the
cases, the domain wall energy of single domain is higher than that samples prepared with other complexing agents (EDTA, egg white,
of multi-domain. In this case, the material will be divided into tartaric acid and citric acid as complexing agents), the maximum of
several domains, and a certain multi-domain structure will be saturation magnetization and remanent magnetization were ob-
formed at the same time. However, the magnetization and tained for the sample prepared with oxalic acid as complexing
demagnetization of materials are relatively easy due to the domain agent. Similarly, the prepared samples have high coercivity. This is
wall displacement magnetization and domain rotation magneti- due to the high porosity of the prepared ferrite resulting in high
zation of multi-domain particles. Compared with those samples coercivity. Meanwhile, the larger value of the dM/dH peak at Hm
prepared with other complexing agents (EDTA, egg white, tartaric indicates that the samples have a magnetically stable state, and it
acid and citric acid), the magnetic parameters of the sample pre- also has a good crystalline cubic spinel structure. So the sample
pared with oxalic acid as complexing agent are larger. This may be prepared with oxalic acid has better magnetic properties than
attributed to the large grain size of ferrite nanoparticles prepared those prepared with other complexing agents. This indicates that
by oxalic acid. And the increase of the magnetic parameters oxalic acid as a complexing agent has stronger complexing ability
(saturation magnetization, remanent magnetization, magnetic for samples and less hydrolysis of metal ions in precursor solution
moment, etc.) of the sample prepared with oxalic acid as com- than other complexing agents. It also shows that nickel-copper-
plexing agent indicates that the magnetic grains in the ferromag- cobalt ferrite prepared with oxalic acid as complexing agent is
netic material change from single domain (SD)/pseudo-single suitable for magnetic recording and magnetic storage materials.
domain to multi-domain (MD) state [55,56].
This value of dM/dH represents the magnetic susceptibility of
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