Composites Part B 175 (2019) 107179

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

The microstructure and magnetic behavior of spark plasma sintered iron/

nickel zinc ferrite nanocomposite synthesized by the complex
sol-gel method
Ali Ghasemi *, Mohammad Reza Loghman-Estarki, Shahab Torkian, Majid Tavoosi
Department of Materials Engineering, Malek Ashtar University of Technology, Shahin Shahr, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, a 2.7 wt% (Fe)/97.3 wt% (Zn0.3Ni0.7Fe2O4) nanocomposite (45–100 nm) was synthesized uisng the
Chelating agent non-alkoxide complex sol-gel method by controlling the amount of Triethanolamine (TEA) and the annealing
Sacrificial reducing agent temperature. Various instuments including the simultaneous thermal analyzer (STA), Fourier transform infrared
Triethanolamine
spectrometer, X-ray diffraction, scanning electron microscope equipped with X-ray dispersive spectroscopy, and
Fe/Zn0.3Ni0.7Fe2O4
Spark plasma sintering
vibrating sample magnetometer were used to characterize the samples. The STA results showed that the gel was
converted from the amorphous phase to a crystalline one at 750 � C. The XRD pattern at the temperature of 750 � C
also confirmed the presence of a spinel ferrite structure, α- Fe2O3 and Fe phases. By increasing the annealing
temperature to 1100 � C, α- Fe2O3 as an impurity phase was eliminated, but the iron phase (formed through the
reduction of the partial Fe3þ ions by TEA molecules as a sacrificial reducing agent) was still present. According to
the VSM analysis of the SPSed sample, the exchange coupling between the iron phase and nickel zinc ferrite
nanoparticles significantly improved the saturation magnetization of the spinel ferrite from 66.0 emu/g to 82.9
emu/g.

1. Introduction
Spinel ferrites are widely used in the core of transformers, high-
frequency radar absorber materials (8–12 GHz) and catalysts. Nickel-
Zinc ferrite (with the general formula [(ZnxFe1-x)tetra[Ni1-xFe1-x]octaO4,
where tetra and octa mean tetrahedral and octahedral sites in the spinel
ferrite), due to its mechanical hardness, remarkable stability, low
fabrication cost and significant magnetic behavior, including saturated
magnetism close to that of γ-iron oxide, and low coercivity value, has
been studied extensively [1,2].
Several methods have been used to synthesize ferrite nanoparticles,
such as co-precipitation, hydrothermal method, micro-emulsion, com­
bustion (glyoxylate, citrate), and the sol-gel method [3–9]. Among these
methods, the sol-gel method has been considered by researchers due to
exact stoichiometries control capabilities, the high purity of the manu­
factured products and the homogeneous distribution of ions on a mo­
lecular scale [9,10].
The simultaneous growth of ceramic (spinel nanoparticles) and
metal (iron phase) is typically difficult, and this growth type has not
been reported yet. In this study, the ferromagnetic metal (iron) and
ferrite spinel phase were, therefore, in-situ produced by using TEA
molecules as a reducing and complex agent. TEA is a tertiary amine that
could be used as a reducing agent (amine electron donor [11]), a sur­
factant [12], a capping agent [13], and stabilizer agent in the reaction
media [13–16].
Moreover, some studies on the exchange coupling of metal oxides
(CoO and MnO) such as spinel ferrites have been carried out [17,18].
However, in this study, the improvement in the magnetic behavior via
exchange coupling between the ferromagnetic metal (iron) and the
ferrite spinel phase has been reported. This can be explained by the
exchange coupling of “soft” and “hard” magnetic materials. To do this,
the as-synthesized Fe/NiZn ferrite nanocomposite powder was subse­
quently consolidated by the spark plasma sintering technique. This
method was used due to such advantages as high sintering speed, min­
imum porosity and the minimum grain growth for the sintering of the
nanocomposite [17–19]. Then, the microstructure, magnetic behavior,
apparent density and porosity of the formed bulk were evaluated.

* Corresponding author.
E-mail addresses: ali13912001@yahoo.com (A. Ghasemi), mrlestarki@mut-es.ac.ir (M.R. Loghman-Estarki).

https://doi.org/10.1016/j.compositesb.2019.107179
Received 6 April 2019; Received in revised form 3 July 2019; Accepted 5 July 2019
Available online 6 July 2019
1359-8368/© 2019 Elsevier Ltd. All rights reserved.
A. Ghasemi et al. Composites Part B 175 (2019) 107179

Table 1 2. Experimental
Chemical materials used for sysnthesis.
Chemical formula name of the material 2.1. Materials
Fe(NO3)3.9H2O Iron(III) nitrate nonahydrate
Zn(NO3)2.6H2O Zinc nitrate hexahydrate The chemicals used in this project are summarized in Table 1. All of
Ni(NO3)2.6H2O Nickel nitrate hexahydrate these materials were purchased from the Merck Company. They all had
C6H15NO3 Triethanolamine high purity (99.99%).

2.2. Experimental procedure

2. Experimental

2.2.1. Synthesis of the Fe/NiZn ferrite nanocomposite

2.1. Materials
The synthesis of Fe/NiZn ferrite nanocomposite consisted of three
stages, as shown below:
The chemicals used in this project are summarized in Table 1. All of
these materials are purchased from Merck Company and have high
D. Sol formation:
purity (99.99%).
In the first stage, specific mole ratios of metal nitrate salts
(Mnþ¼Fe3þ, Ni2þ, Zn2þ) and Triethanolamine (TEA: Mnþmole
2.2. Experimental procedure
ratio ¼ 2: 1 and 4: 1) were dissolved in distilled water. While the
solution was stirred by a magnetic stirrer, it was heated up to 80 � C
2.2.1. Synthesis of Fe/NiZn ferrite nanocomposite
for one hour, until the solution became completely homogeneous.
The synthesis of Fe/NiZn ferrite nanocomposite consists of three
After a few minutes, a black solution was obtained, indicating the
stages as below:
formation of the TEA-metal complex [15,16].
E. Formation of the gel in solution:
A. Sol formation:
At this stage, the solution was heated to 120–150 � C for one hour to
In the first stage, specific mole ratios of metal nitrate salts
slowly evaporate the solution water. During heating, solvent evap­
(Mnþ¼Fe3þ, Ni2þ, Zn2þ) and Triethanolamine (TEA: Mnþmole
oration occurred and the gel was formed by the sequential hydrolysis
ratio ¼ 2: 1 and 4: 1) were dissolved in distilled water. While the
and condensation reactions. Finally, the gel was turned into xerogel.
solution was stirred by a magnetic stirrer, it was heated up to 80 � C
To complete the drying process, xerogel was heated at the temper­
for one hour, until the solution became completely homogeneous.
ature range of 250–300 � C for one hour; as a result, a brownish-black
After a few minutes, a black solution is obtained which indicates the
powder called precursor (burnt gel) was obtained.
formation of the TEA-metal complex [15,16].
F. Calcining step:
B. Formation of the gel in the solution:
The precursor obtained from the previous part was calcined in a
At this stage, the solution was heated to 120–150 � C for one hour to
furnace at a temperature range of 750–1100 � C for 3 h. The resulting
slowly evaporate the solution water. During heating, solvent evap­
black powder was washed by water and ethanol and kept for further
oration occurred and the gel was formed by sequential hydrolysis
analysis.
and condensation reactions. Finally, the gel turned into xerogel. To
complete the drying process, the xerogel was heated at a temperature
2.2.2. Sintering procedure by the SPS technique
between 250 and 300 � C for one hour, in which a brownish-black
The following temperature cycles were used for the SPS (spark
powder was obtained that called precursor (burnt gel).
plasma sintering) step:
C. Calcining step:
The sample was heated up to 1000 � C at a heating rate of 100 � C/min
Precursor from the previous part was calcined in a furnace at a
and a retention time of 400 s. Then, the temperature was reduced to
temperature of 750–1100 � C for 3 h. The resulting black powder was
room temperature at a cooling rate of 100 � C/min.
washed by water and ethanol and kept for further analysis.

- The following pressure cycle was used:

2.2.2. Sintering procedure by SPS technique
The following temperature cycles were used for SPS (spark plasma
When the temperature reached to 1000 � C, the pressure was
sintering) step:
increased to 45 MPa with the pressure rate of 5 MPa/min; then, until the
The sample heated up to 1000 � C at a heating rate of 100 � C/min and
temperature reached the room temperature, the pressure was reduced to
a retention time of 400 s. Then, the temperature was reduced to room
the atmospheric pressure with the rate of 5 MPa/min.
temperature at a cooling rate of 100 � C/min.
Nanopowders (3 g) were poured into cylindrical graphite with a
The following pressure cycle was used:
diameter of 2 cm and a length of 4 cm. Subsequently, the samples were
When the temperature reaches to 1000 � C, the pressure increased to
subjected to the temperature of 1000 � C at a constant pressure of 45 MPa
45 MPa with the pressure rate of 5 MPa/min, then, until the temperature
in the plasma spark sintering equipment (SPS, 380 V-10000 A model).
reached the room temperature, the pressure was reduced to atmospheric
According to the theoretical density of ferrite nanoparticles (5 g/cm3), it
pressure with the rate of 5 MPa/min.
was expected that after the sintering process, a disk with a thickness of
Nanopowders (3 g) were poured into cylindrical graphite with a
0.2 cm would be obtained. In order to remove the graphite from the
diameter of 2 cm and a length of 4 cm. Subsequently, the samples were
SPSed sample, annealing treatment at 800 � C for 2 h was applied.
subjected to the temperature of 1000 � C at a constant pressure of 45 MPa
in plasma spark sintering equipment (SPS, 380 V-10000 A model). Ac­
2.2.3. Characterization equipment
cording to the theoretical density of ferrite nanoparticles (5 g/cm3), it is
In order to identify the phases of nanoparticles and the sintered
expected that after the sintering process, a disk with a thickness of
sample, the X-ray diffraction technique (XRD, AW/XDM 300 model,
0.2 cm will be obtained. In order to remove the graphite from the SPSed
manufactured by Asenware, in China) with a copper anode and the
sample, an annealing treatment at 800 � C for 2 h was performed.
wavelength of 1.54 Å (Cu Kα) was employed. XRD test was performed
with 40 kV voltage, 30 mA current and the step size of 0.05� , and a step
time of 1 s in the 2θ range, from 10 to 80� . Evaluation of the X-ray
diffraction patterns and Rietveld refinement was done by the Xpert

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A. Ghasemi et al. Composites Part B 175 (2019) 107179

Fig. 1. TG/DTA/DDTA of gel for TEA: M mole ratios (a) 2:1 (b) 4:1.

Highscore (version 3, 2013) software with the PDF2 database. Crystal­ condition at a maximum voltage of 30 kV.
lite size (Dc) was calculated from the peak broadening of the (311) plane An energy dispersive spectrometer (EDS) was used to determine the
using the Scherer relation, in which K is the constant coefficient (for the elemental composition of the as-synthesized nanoparticles and the
spherical morphology of 0.9), λ is the X-ray wavelength (1.54 Å), β is the SPSed sample. The EDS analysis was carried out by FEI Quanta 200 SEM
peak width at half maximum height of the (311) peak, and θ is the equipped with EDS, with a voltage of 20 KV and a takeoff angle of 35� .
diffraction angle (Eq. (1)). In order to identify the type of the functional groups in the sample,
the fourier transform infrared (FTIR) spectrometry in the KBr cells was
Kλ
Dc ¼ (1) used. This test was conducted by the FTIR machine (Tensor27 model,
βCosθ
Bruker Company, Germany).
The cubic crystal lattice parameter (a) was obtained from formula By using the NETZSCH STA 409 PC/PG machine (made in Germany),
(2). the TG/DTA analysis of the precursor (gel) was performed. The TG/DTA
analysis was performed from 25 to 1200 � C in an air atmosphere. The
�λ� �h2 þ k2 þ l2 �1=2
a¼ (2) increasing temperature rate was 10 � C/min.
2 sin θ Magnetic properties were analyzed by a vibrating sample magne­
The X-ray density of the sample was calculated from equation (3) tometer (Kavirmagnet model, manufactured by Iran) with a maximum
[20]: applied field of 10 kOe and 100 Oe step size at room temperature.
� � The viscosity of the solution was measured by the CGOLDENWALL
8M
¼ ρð311Þ (3) Digital Krebs Stormer Viscometer with the viscosity meter range of
40–141 KU, the resolution of 0.1 Kreb units and the accuracy of �2%.
Na3

where M is the molecular weight (3691.236 g/mol), N is the Avogadro’s

number (6.022 � 1023), and a3 is the unit cell volume obtained from the
XRD analysis [20–23]. The ferrite bulk density was determined through
the Archimedes method. The porosity of the bulk sample (P) was
calculated by the relation 4; [20,21].
ρx
P¼1
ρs
In equation (4), ρx is the X-ray density of and ρs is the Archimedes
density of solid.
To investigate the shape of the samples, a scanning electron micro­
scope (FEI Quanta 200 ESEM model, Thermofisher Scientific Company,
3. Results and discussion
3.1. TG/DTA analysis of the precursor (gel)
Fig. 1 shows the TG/DTA/DDTA curve of the gel for the TEA: Mnþ
mole ratios of 2: 1 (Figs. 1a) and 4:1 (Fig. 1b). As shown, both samples
(4)
represented approximately 5% weight loss from room temperature up to
1200 � C. This weight loss was due to the separation of the organic matter
such as TEA molecules from the gel. In order to better understand the
exothermic or endothermic peaks, the DDTA curve was derived from the
DTA curve, as shown in a curve with a pale blue color in Fig. 1a. The
exothermic peaks at 300 C and 450 C were related to the decomposi­
� �

United States) , a magnification of 20–100,000-times, and a tungsten tip

tion of the TEA ligands. According to this curve, with TEA:Mnþ ¼ 2:1,
was used. The secondary electrons image was taken in a vacuum
the endothermic peaks observed at the temperatures of 622 � C and

3
A. Ghasemi et al. Composites Part B 175 (2019) 107179

Fig. 2. SEM images of nanoparticles for TEA: M mole ratios (a, b) 2:1 (c, d) 4:1 after calcining at 750 � C.

656 � C were related to the decomposition of the amorphous gel and the
TEA-metal complexes into iron oxide, nickel oxide and zinc oxide
compounds [24,25]. According to the DDTA curve (Fig. 1a), the bond
breakdown continued even at temperatures above 700 � C as an endo­
thermic peak. According to the DDTA curve in Fig. 1b, with increasing
the TEA:Mnþ mole ratio from 2:1 to 4:1, the peaks located at the tem­
peratures of 523 � C, 622 � C and 656 C were of the exothermic type. The
�

peak located at 523 C was related to the burning of organic molecules

�

and hydroxyls (such as CH2OH radicals [24]). The peaks located at

622 � C and 656 � C could be related to the transformation of the amor­
phous phase to the crystalline phase [24]. Contrary to the DDTA curve of
Fig. 1a, according to the DDTA curve in Fig. 1b, the bond breakdown
above 700 � C was less in the case of TEA:Mnþ ¼ 4:1. This indicated that
the TEA:Mnþ mole ratio of 4:1 was suitable for the formation of the
crystalline spinel ferrite phase. As a result, according to Fig. 1b, the
precursor (gel) was calcined at 750 � C to remove the organic molecules
and to form the ferrite nanoparticles.
In the burning state of the TEA gel, the Fe/NiZn ferrite powder was
formed according to the equation number 5 [8,26]. Scheme 1. Schematic of NiZn ferrite nanoparticles stabilization with TEA
3C6H15NO3 þ1Ni(NO3)2þ0.7Zn(NO3)2þ2Fe molecules26.
(NO3)3 → 4N2þ18CO2þ12H2O þ Fe/Ni0.7Zn0.3Fe2O4 (5)
ions. The metal is bubble-shaped, providing a non-saturated common
Of course, it should be noted that the combustion reaction is not surface with the unsaturated bonds of metal oxide; with the sudden
performed according to the above equation at one stage; instead, metal combustion of the organic matter, the penetration reaction is carried out
nitrates (Mnþ) are decomposed into metal oxide (equation (9), reactions 9 in the solid state and the ferrite nanopowder is produced [27].
to 17 are listed in the FTIR analysis section). Then, these nickel zinc
ferrites are produced by the intrusive reaction of the final product. In the
combustion step of the precursor, the gel starts to boil; due to the surface 3.2. SEM images
tension of the organic matter, the gel resembles a soap bubble, releasing a
lot of gas. The heat generated by this process weakens and breaks the Fig. 2 shows the scanning electron microscopic image of the Fe/NiZn
bond between the metal compounds, leading to the formation of metallic ferrite nanocomposite prepared by different TEA:Mnþ mole ratios after

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A. Ghasemi et al. Composites Part B 175 (2019) 107179

Fig. 3. SEM images of nanoparticles for TEA: M mole ratios of 4:1 and calcined at (a, b) 1000 � C (c, d) 1100 � C.

Fig. 4. XRD patterns of Fe/NiZn ferrite at different TEA:M mole ratios and annealing temperatures.

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A. Ghasemi et al. Composites Part B 175 (2019) 107179

Fig. 5. XRD patterns of Fe/NiZn ferrite at 4TEA:1 M mole ratio and different annealing temperatures (a) 900 � C (b) 1000 � C and (c) 1100 � C (d) Rietveld refinement
of “a” pattern.

6
A. Ghasemi et al.
Fig. 6. SEM image and EDS of Fex/NiZn ferrite nanoparticles annealed at 1100 � C.
calcining at 750 � C. According to Fig. 2a and b, the sample prepared by
the TEA: Mnþ mole ratio of 2:1 was a mixture of pyramid-like and
polyhedral shapes. Also, this sample clearly had a twin size distribution
from 40 to 60 nm and 100–200 nm. In accordance with Fig. 2, when the
concentration of the TEA: Mnþ mole ratio was increased from 2:1 to 4:1,
the particle size distribution had a single-peak distribution with an
average particle size of 45 nm. By raising the mole ratio of TEA mole­
cules as both chelating and stabilizing agents, the viscosity of the solu­
tion was increased from 400 cP (cP) to 900 cP. Further increase in the
TEA polymer chains decreased the mobility of cations and prevented the
agglomeration of nanoparticles [25–28]. Therefore, the size of nano­
particles was decreased due to the spatial repulsion or steric hindrance
(Scheme 1). Furthermore, by enhancing the viscosity of the solution and
decreasing the mobility of the cations, the growth mechanism of the
nanoparticles became a diffusion-controlled type. In general, the
diffusion-controlled type reaction could produce ferrite nanoparticles
with a finer particle size distribution [28,29].
Fig. 3 shows the scanning electron micrographs of the NiZn ferrite
nanocomposite prepared with the TEA: M mole ratios of 4:1 after
annealing at 1000 � C and 1100 � C. According to Fig. 3a and b, the
sample annealed at 1000 � C had a quasi-spherical shape. According to
this figure, the average size of the ferrite nanoparticles was in the range
of 50 nm–70 nm. As shown in Fig. 3c and d, with increasing the
annealing temperature up to 1100 � C, a noticeable particle size growth
over 100 nm was observed.
3.3. XRD patterns
The effect of the annealing temperature and the amount of the TEA
agent on the phase formation of the NiZn ferrite nanocomposite is shown
in Fig. 4. According to Fig. 4a and b, for both TEA: Mnþ ¼ 4:1 and 2:1 and
the constant annealing temperature of 750 � C, a mixture of hematite
(a ¼ b ¼ 0.5083 nm, c ¼ 0.13772 α-Fe2O3) and nickel - zinc ferrite phase
was obtained. By increasing the annealing temperature from 750 � C to
7
Composites Part B 175 (2019) 107179
900 � C in TEA: Mnþ ¼ 4:1, the diffraction patterns in Fig. 4c could be
matched with (NiZn) Fe2O4 (JCPDS No. 08–0234). The type of the
crystal system was cubic with a lattice parameter of 0.83990 nm. The
absence of NiO and ZnO phases in the diffraction pattern of samples
indicated the formation of a solid solution and the successful formation
of the nickel zinc ferrite phase. Of course, according to the XRD detec­
tion limit, in the determination of the low amount of the impurity phase,
which is usually less than 5 vol % [29], it could be said that the mini­
mum impurity phases were present in the sample. However, at 900 � C,
the hematite phase was not completely eliminated, and only the dif­
fractions of this impurity were reduced, as compared to the sample
annealed at 750 � C.
A careful look at the specimen’s diffraction peaks, as compared to the
reference pattern (JCPDS No. 08–0234) shown in Fig. 4, showed that
there was a small amount of displacement, relative to the referenced
pattern. This was due to dopping nickel and zinc cations in the iron oxide
network, which caused the shift peaks relative to the reference pattern.
According to the Bragg law (nλ ¼ 2dsinθ), to keep the value of nλ con­
stant, by increasing the distance between the crystalline plane (d) with
dopping nickel oxide and zinc oxide in the iron oxide network, the sinθ
must be reduced [8,24]. Thus, Ni0.7Zn0. 3Fe2O4 reflections show a small
shift to the lower 2θ, as compared to the iron oxide reflections.
Also, the comparison of the crystallite size (calculated from the
Scherer relationship on the (311) reflections) in different samples
showed that by changing the TEA: Mnþ mole ratio from 2:1 to 4:1, the
crystallite size (not the particle size) was kept constant (34.3 nm).
However, by varying the annealing temperature from 750 � C to 900 � C,
the crystallite size was increased from 34.3 nm to 42.4 nm, due to an
increase in the penetration rate of cations by raising the annealing
temperature during the conversion of the amorphous gel phase into the
crystalline NiZn spinel ferrite one.
The effect of the annealing temperature on the NiZn ferrite phase
formation is shown in Fig. 5. To this goal, the TEA: Mnþ mole ratio of 4:1
was kept constant and different annealing temperatures at 900 � C,
 A. Ghasemi et al.
Fig. 7. FTIR of (a) gel prepared with 4TEA:1 M mole ratio (b) NiZn ferrite nanoparticles annealed at 750 � C.
1000 � C, and 1100 � C were applied. In accordance with Fig. 5, at both
temperatures of 900 � C and 1000 � C, the samples were composed of
hematite (α-Fe2O3) and NiZn ferrite phases. By increasing the annealing
temperature from 1000 � C to 1100 � C, the diffraction patterns in Fig. 5
corresponded entirely to the (NiZn)Fe2O4 phase with the JCPDS No.
08–0234. The as-formed spinel phase had the lattice parameter of
0.83990 nm. In this pattern, there was not any impurity such as NiO and
ZnO phases, indicating the successful formation of the nickel zinc ferrite
phase. Interestingly, the sample of nickel ferrite nanoparticles annealed
at 1100 � C had two additional reflections at 2θ of 44� and 66� . These
reflections were related to the presence of the iron phase (Fe). These
extra diffractions were also observed in the samples annealed at 750 � C
(Fig. 4a and b). The reason for the presence of this phase could be the
reduction potential of the Triethanolamine agent (approximately
1.05 V versus SCE on a mercury drop or Pt electrode [30]). The
oxidation behavior of the pure iron and iron alloys and iron composite
could be affected by the sample-preparation methods and the oxidation
temperature [22,23]. Chen and Yuen [22] showed that oxidation of the
iron alloy was slower than that of the pure iron. In the current research,
the Fe/Zn0.3Ni0.7Fe2O4 composite was expected to have more oxidation
8
­
Composites Part B 175 (2019) 107179
resistance than a pure iron phase. Zn0.3Ni0.7Fe2O4 particles presumably
covered iron particles and protected them against iron oxidation. On the
other hand, the remained TEA (as confirmed by FTIR analysis, Fig. 7b)
stabilized the sample and prevented it from being oxidized.
Chengliang et al. [15] investigated the iron–TEA complex as a
mediator for the reduction of the organic compounds due to its low
redox potential. In this research, for the first time, the Triethanolamine
(TEA) agent was used as a chelating and sacrificial reducing agent in the
synthesis of iron/nickel zinc ferrite nanoparticles. According to our
knowledge, the development of the Fe/NiZn ferrite nanocomposite has
not yet been reported by another research group. Furthermore, ac­
cording to the Rietveld refinement, the amount of iron and Ni0.7Zn0.3
Fe2O4 was 2.7 wt% and 97.3 wt%, respectively (with the goodness of fit
2.79, Rexpected or Robserved ¼ 23.46, Rweight profile or Rcalcu­
lated ¼ 31.19, the microstrain percent was 0.34238%).
Also, the comparison of the crystallite size in different samples
showed that by changing the TEA:Metal ion ratio from 2 to 4, the
crystallite size (not the particle size) was constant (34 nm). However,
with changing the annealing temperature ranging from 900 � C to
1100 � C, the crystallite sizes were increased from 42.4 nm to 62.4 nm.
A. Ghasemi et al. Composites Part B 175 (2019) 107179

The reason for this increase could be related to the increase in the rate of
the penetration of cations by raising the annealing temperature during
the conversion of the amorphous gel to the spinel NiZn ferrite phase.
Fig. 6 shows the EDX analysis and the scanning electron microscopic
image from the NiZn ferrite nanocomposite prepared by 4TEA:1Mnþ at
1100 � C. The region taken by the EDX analysis is shown by the red box.
According to the EDS table, there were iron, nickel, zinc, oxygen and
carbon elements in the sample annealed at 1100 � C. As shown, the iron
element with a value of 49.29 mol.% could be observed in the left-hand
side of the SEM image (semi-sintered particles). This value was about
17% higher than that of the particles in the right-hand side of the SEM
image (spherical particles). The reason for this could be the presence of
the elemental iron phase in the semi-sintered particles. This was because
the iron melting point was less than that of NiZn ferrite, causing the
incomplete fusion of this region. These results were in a good agreement
with the presence of the iron phase in the X-ray diffraction pattern in
Figs. 4 and 5.

3.4. FTIR analysis

To determine the functional groups of the precursors and nano­

particles, the FTIR spectra of them was taken. Several bands were
observed in the precursor or the polymeric gel in the FTIR spectrum
(Fig. 7a). The bands in the gel spectrum were related to the stretching
vibrations of –OH (3408 cm 1) and aliphatic –CH2 (2924 and
2858 cm 1), and the bending vibrations of the –NH functional group in a
complex with a metal ion (1617 cm 1) [15and27]. Following the
calcination of the gel at 750 � C, the peaks of the carbon-skeleton and the
–NH groups on the gel were not eliminated, as shown in Fig. 7b. The
observed shift for the peak of the –NH group from 1617 cm 1 to
1640 cm 1 was related to the interactions between ferrite nanoparticles
and TEA molecules [27].
Of course, a very small amount of TEA molecules remained on the
samples, as confirmed by the presence of the –NH bond (1640 cm 1), the
bending vibrations of –OH (1428 cm 1), and the stretching vibration
bands of –CH2 (2847 and 2924 cm 1). These complex agents (TEA
molecules) were used to stabilize the nanoparticles and the presence of a
small amount of them prevented nanoparticles from agglomeration.
Furthermore, the presence of the TEA agent at the high temperature
protected the iron phase against oxidization. It is worth noting that the
peaks located in the regions 395 cm 1and 580 cm 1corresponded to the
vibrational frequencies of the M-O-M bonds in the octahedral and
tetrahedral positions, respectively [32,33]. Since the length of MOM in
the tetrahedral site of the spinel structure was shorter than that of the
octahedral one, the high wave number (580 cm 1) was related to the
Fig. 8. (a) Hysteresis loop (b) Zoom around the coercive field of NiZn ferrite
vibrations of the metal-oxygen bonds in the tetrahedral position. nanoparticles prepared with TEA:M mole ratios equal to 2:1 and 4:1 annealed
In the sol-gel method, first, the metal salts were in the form of hy­ at 750 � C.
drated water ([M(OH)x]Zþ); then, with the addition of Triethanolamine
(C6H15NO3), the hydrated metal ions, due to the bipolar-bipolar in­
ferrite nanoparticles. Also, in some sources, this agent was used as a
teractions, were linked to the TEA molecules, forming C6H15NO3- [M
surfactant and a viscous solvent [8,15,16]. Reactions 6 to 14 show the
(OH)x]Zþ complex molecules (reactions 6 and 7). Therefore, TEA pre­
route of gel formation from TEA-metal [8,15,16].
vented Mnþ ion deposition during hydrolysis. Also, due to the polari­
zation of the complex species C6H15NO3- [M(OH)x]Zþ, the protonation MZþ(NO3)X þ xH2O→[M(OH)x]Z-x þ HNO3 M ¼ Fe3þ, Zn2þ, Ni2þ (6)
of water and the dissolution of the species in water became faster [27]. Z-x Z-x Z-x
The metal-TEA bond ([M(OH)x]Z-x –N(CH2CH2OH)2) was further broken [M(OH)x] þ C6H15NO3→C6H15NO3 –[M(OH)x] or [M(OH)x] –N
down by water molecules, forming M(OH)x molecules (reactions 8 and (CH2CH2OH)2 Complex (7)
9). Furthermore, according to reactions 10 and 11, some of the produced Z-x
[M(OH)x] –N(CH2CH2OH)2 þ H2O→M-N(CH2CH2OH)x-1 þ HNO3 þ
Fe(OH)2 the was reduced to the iron phase; then, over time, the com­ CH2CH2OH (8)
binations of hydrolysis and condensation process led to the formation of
M-O-M or M-OH-M bonds (Oxolation bridge or Olation bridge, equa­ M-N(CH2CH2OH)2 þ H2O→M(OH)Xþ1 (colloidal gel) þ NH(CH2CH2OH)
tions (12 )and (13) and created a regular three-dimensional net named
For M ¼ Fe: Fe–N(CH2CH2OH)2 þ H2O→Fe(OH)3 (colloidal gel) þ NH
the gel. Then, at a temperature range of 250 � C–300 � C, a gel burning
(CH2CH2OH) (9)
step occurred [27]. After the crystallization of the polymer network
connected to zinc, nickel and iron metals, Fe/NiZn ferrite nanoparticles Fe(OH)3 (colloidal gel) þ NH(CH2CH2OH)→Fe(OH)2 þ [NH
were formed (equation (14). In this project, for the first time, TEA was (CH2CH2OH)]þ (10)
used as a chelating and polymerizing agent for the synthesis of NiZn

9
A. Ghasemi et al. Composites Part B 175 (2019) 107179

Fig. 9. (a) Hysteresis loop (b) Zoom around the coercive field of NiZn ferrite nanoparticles prepared with TEA:M mole ratios equal to 4:1 annealed at different
temperatures.

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A. Ghasemi et al. Composites Part B 175 (2019) 107179

Fig. 10. SEM (a–c) of fractured cross-section of SPSed Fe/NiZn ferrite nanoparticles and EDX of bright particles in SEM image of (c).

number of TEA chains on the NiZn ferrite nanocomposite [27,31]. The

Fe(OH)2 þ 2NH(CH2CH2OH) → Fe þ [NH(CH2CH2OH)]2þ (11) major method for the stabilization of Ni–Zn ferrite nanoparticles in this
study was the steric hindrance method (Scheme 1).
Fe(OH)2 þ Fe(OH)3→Fe–O–Fe (Oxolation bridge) þ 2H2O (12)

Fe(OH) þ Fe(OH)2→Fe–OH–Fe (Olation bridge) þ H2O (13) 3.5. VSM curve

2 M(OH)2.M(OH)3 Fe/NIZnFe2O4 þ H2O (M ¼ Fe, Zn, Ni ions) (14) Fig. 8 shows the hysteresis loops of the Ni0.7Zn0.3Fe2O4 nano­
composite prepared by different values of TEA: Mnþ mole ratios, as
In general, there are three methods for stabilizing nanoparticles. The
annealed at 750 � C for 3 h. As shown in Fig. 8, both samples showed the
first method is a space repellent technique in which bulky groups such as
behavior of the ferrimagnetic curves. According to this curve (Fig. 8a),
surfactants or long-chain polymeric molecules prevent nanoparticles
the specimen prepared with the 4TEA:1 Mnþ mole ratio had a higher
from sticking together. The second method is the electrostatic repellent.
saturation magnetization (Ms ¼ 54.3 emu/g), as compared to the sample
In this approach, molecules that have negative or positive charge pro­
synthesized with the 2TEA:1 M mole ratio (Ms ¼ 45.9 emu/g). Also,
vide some electrical hindrance to prevent nanoparticles from sticking to
according to Fig. 8b, the coercivity value of the samples synthesized
each other. The third method is to use a combination of the previous two
with 4TEA and 2TEA was in the range of 101.5 Oe and 110.6 Oe,
approaches [27]. The factor that makes the nanoparticles stable and
respectively.
prevents them from agglomeration is, in fact, the maintenance of a small
Fig. 9 shows the VSM curves of the sample Ni0.7Zn0.3Fe2O4

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A. Ghasemi et al. Composites Part B 175 (2019) 107179

Fig. 11. (a) XRD pattern of SPSed Fe/Ni0.7Zn.3Fe2O4 sample (α means α-Fe2O3) (b) Rietveld refinement of “a” pattern.

12
A. Ghasemi et al. Composites Part B 175 (2019) 107179

Fig. 12. X-ray mapping of fractured cross-section of SPSed NiZn ferrite nanoparticles.

nanocomposite prepared with the 4TEA:1 Mnþ mole ratio at different

annealing temperatures of 900 � C, 1000 � C and 1100 � C for 3 h. As
shown in Fig. 9, all samples showed a ferrimagnetic behavior. Com­
parison of Figs. 8 and 9 shows that by increasing the annealing tem­
perature from 750 � C to 900 � C, the saturation magnetization in the
4TEA:1 M sample was raised from 54.3 emu/g to 58.8 emu/g and the
coercivity values were decreased from 110.6 Oe to 58.5 Oe. The
decrease of coercivity with increasing the annealing temperature was
due to the coarsening of particles [34].
According to Fig. 9a, the sample annealed at 900 � C, 1000 � C, and
1100 � C had the saturation magnetization of 57.3 emu/g, 58.6 emu/g
and 66.0 emu/g, respectively. Also, as shown in Fig. 9b, the Hc of the
sample annealed at 900 � C, 1000 � C and 1100 � C was in the range of
60.0 Oe, 49.7 Oe and 49.6 Oe, respectively.
According to Fig. 9, with changing the annealing temperature from
900 � C to 1100 � C, the amount of the saturated magnetization at 1100 � C
was enhanced from 57.3 emu/g to 66.0 emu/g and the coercivity value
was reduced from 60.0 Oe to 49.6 Oe. It was due to the observed particle
growth with increasing the annealing temperature from 900 � C to
1100 � C (see SEM images in Fig. 3) [34,35].
The increase in the saturation of the magnetization value with the Fig. 13. H-M loop curve of SPSed Fex/NiZn ferrite nanoparticles (a) without
annealing temperature could be related to the removal of the hematite degraphitization (b) after removing graphite by calcining the sample at 800 � C
impurity phase and the presence of the iron phase (according to XRD for 2 h.
results, Fig. 5) in this sample.
related to (110), (200) and (211) planes of the cubic phase of iron.
According to Rietveld refinement of SPSed sample (Fig. 11b), the
3.6. SPS treatment
amount of iron, hematite and Ni0.7Zn0.3Fe2O4 was 2.7 wt%, 34.5 wt%,
and 62.8 wt% (the goodness of fit 2.49). Furthermore, the microstrain of
Fig. 10 shows the FESEM image of the fracture cross-section of the
SPSed sample percent was 0.0%.
Fe/nickel ferrite composite condensed at 1000 � C for 400 s. According to
Fig. 12 shows the X-ray map analyses of the fracture cross-section of
this picture, the facets could be observed with an average growth of 2
the sample consolidated at 1000 � C for 400 s. According to this picture,
μm. Also, the porosity in the fracture cross-section of the sample could the elements Ni, Zn, Fe and O from nickel zinc ferrite particles and Fe
be well observed. These porosities could be related to the presence of
from the iron phase elements were well distributed alongside each other.
oxygen due to the transformation of some nickel zinc ferrite into the
Fig. 13 shows the VSM analysis of the SPSed iron/nickel ferrite
alpha-Fe2O3 phase [35]. This transformation could be confirmed by the
composite. According to this curve (Fig. 13a), the Ms value reached to
XRD analysis of the SPSed sample (Fig. 11). The EDS analysis (Fig. 10f)
58.0 emu/g after the SPS process. The observed decrease in the Ms value
of the brighter particles in this image (Fig. 10e) showed that these
from 66 emu/g (Fe/NiZn ferrite nanocomposite), as compared to the
particles were rich in the iron element. However, due to the limitation of
sintered sample (58.0 emu/g), was due to the formation of the hematite
the FESEM probe (up to 500 nm), other elements including oxygen and
phase and the existence of graphite from graphite molding in the SPSed
nickel and zinc could be observed in this analysis.
sample. According to Fig. 13b, after removing the penetrated graphite
Fig. 11a shows the XRD pattern of the SPSed Fe/nickel ferrite com­
from graphite molding by annealing the sample at 800 � C for 2 h, the
posite sample. According to this image, some SPSed NiZn ferrite parti­
saturation magnetization value reached to 82.9 emu/g. The high satu­
cles were transformed to α-Fe2O3 (Hematite) phases. Furthermore, the
ration magnetization could be due to the coupling exchange between the
reflections of the iron phase with JCPDS No. 85–1410 could be clearly
NiZn ferrite and iron phases in the SPSed sample. Also, the comparison
observed in this pattern. The diffractions at 44.2, 65.16 and 81.84� were

13
A. Ghasemi et al.
Table 2
Comparison of magnetic property of the Ni0.7Zn0.3Fe2O4 by other references.
Ms Hc Synthesis method Particle size
(emu/g) (Oe)
65 35 Coprecipitation 34.7
58 21 Sol-gel auto- 40 nm
combustion
26.9 – microemulsion 50–80 nm
12.01 15.55 self-propagation Agglomerated
combustion submicro-size
69 27 Coprecipitation 33 nm
31.64 20 combustion 19.2 nm
82.6 25–26 Complex Sol-gel
method
of the saturation magnetization of the sample before and after annealing
process (Fig. 13) showed that the amount of saturation magnetization
was improved from 66.0 emu/g to 82.9 emu/g (the improvement value
was about 25%). In this case, some exchange coupling behavior between
iron as the soft phase and ferrite as the hard phase could occur. Through
an exchange interaction, the magnetic moments of the two phases were
coupled to each other, simultaneously rotating under an external mag­
netic field. Therefore, the magnetization and demagnetization of the
sample had the single ferrimagnetic phase features. Single hysteresis
loops (Fig. 13) represented the synergistic magnetic switching of the two
interacting phases through good exchange coupling between the ferrite
and iron phase boundaries. The high saturation of the magnetization of
iron led to an increment of the total Ms in the structure.
The magnetic property of the sample in comparison to others has
been summarized in Table 2. According to this table, the saturation
magnetization of the current work was significantly higher, in com­
parison to other studies.
Furthermore, according to Fig. 13b, the coercivity value of the SPSed
samples before and after annealing step was 26 Oe and 25 Oe, respec­
tively. Thus, the Hc value was not affected by removing the graphite
process. With the comparison of Figs. 13b and 9b, it was revealed that
the coercivity value was decreased from 49.6 Oe to 26 Oe. This was due
to the decreased porosity and grain growth after the SPS process.
The apparent and theoretical densities of the SPSed sample were
5.251 g/cm3 and 5.419 g/cm3, respectively. The porosity value obtained
from the relation was 3.1%. Thus, densities reached to 96.9% of the
theoretical density.
4. Conclusion
Iron/Nickel-zinc ferrite nanocomposites with the composition of
2.7 wt%(Fe)/97.3 wt% (Zn0.3Ni0.7Fe2O4) were fabricated by a complex
sol-gel method in a TEA-water medium from the corresponding iron,
nickel and zinc nitrate precursors. Synthesis conditions allowed the
successful formation of the Fe/NiZn ferrite nanocomposite. The iron/
NiZn ferrite nanocomposite synthesized with the 4TEA:1Mnþ mole ratio
and the annealing temperature of 1100 � C for 3 h had a particle size
more than ~100 nm. This nanopowder was subsequently consolidated
by the spark plasma sintering (SPS) technique under a pressure of
40 MPa and the temperatures of 1000 � C for 400 S. Densities reached to
96.9% of the theoretical density. According to the M H loop curve, the
SPSed sample showed a ferrimagnetic behavior with an excellent satu­
ration magnetization (82.9 emu/g) and low coercivity (26 Oe) at room
temperature. The main reason for this high saturation of magnetization
was exchange coupling in the synthesized particles in which iron and
ferrite phases were in-situ grown in the vicinity of each other.
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