Colloids and Surfaces A: Physicochemical and Engineering Aspects 676 (2023) 132074

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Sol-Gel synthesis of Ni-doped Zn-based spinel nanoferrites with structural

and dielectric characterizations along with magnetic analysis
Ahsan Quddus a, Syed Zia Hussain Hashmi a, Ghulam Mustafa b, Muhammad Khalid a, *,
M.G.B. Ashiq c, d, Ghazanfar Nazir e, *, Thamraa Alshahrani f, *, Mohammed S. Alqahtani g,
Kiran Naz h
a
Department of Physics, University of Karachi, 75270 Karachi, Pakistan
b
Department of Physics, NED University of Engineering and Technology, 75270 Karachi, Pakistan
c
Department of Physics, College of Science, Imam Abdulrahman Bin Faisal University, P.O. Box 1982, Dammam 31441, Saudi Arabia
d
Basic and Applied Scientific Research Center, Imam Abdulrahman Bin Faisal University, P.O. Box 1982, Dammam 31441, Saudi Arabia
e
Department of Nanotechnology and Advanced Materials Engineering, Sejong University, Seoul 05006, Republic of Korea
f
Department of Physics, College of Sciences, Princess Nourah bint Abdulrahman University (PNU), P.O. Box 84428, Riyadh 11671, Saudi Arabia
g
Department of Radiological Sciences, College of Applied Medical Sciences, King Khalid University, Abha 61421, Saudi Arabia
h
Institute of Space Science and Technology, University of Karachi, 75270 Karachi, Pakistan

G R A P H I C A L A B S T R A C T

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

Keywords: Ni-doped zinc ferrites (NixZn1− xFe2O4, 0.00 ≤ x ≤ 0.20 in steps of 0.05) were successfully synthesized using a sol-
Zinc ferrite gel self-combustion method. The addition of nickel was aimed at modifying the high-frequency dielectric and
Sol-gel magnetic properties of zinc ferrites. Various characterizations, including XRD, FTIR, LCR, and VSM analyses,
XRD
were conducted to examine the crystal structure, absorption bands, dielectric properties, and magnetic properties
FTIR
Electric modulus
of the compounds. XRD patterns revealed a monophasic cubic spinel structure with a preferred (311) plane
VSM orientation. The incorporation of Ni resulted in an increased crystallite size as determined by the Scherrer
Remanence equation and Williamson-Hall method. The lattice parameters and unit cell volume decreased, while X-ray

* Corresponding authors.
E-mail addresses: mkhalid@uok.edu.pk (M. Khalid), gnazir@sejong.ac.kr (G. Nazir), thmalshahrani@pnu.edu.sa (T. Alshahrani).

https://doi.org/10.1016/j.colsurfa.2023.132074
Received 27 May 2023; Received in revised form 8 July 2023; Accepted 15 July 2023
Available online 17 July 2023
0927-7757/© 2023 Elsevier B.V. All rights reserved.
A. Quddus et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 676 (2023) 132074

density increased. FTIR transmittance spectra confirmed absorption bands associated with tetrahedral and
octahedral bonding. Dielectric parameters were studied across a frequency range of 1 MHz to 3 GHz, with the
Maxwell-Wagner model used to explain the observations. Both components of the complex dielectric constant
decreased with increasing frequency, indicating normal dispersion behavior of spinel ferrites. The electric
modulus revealed relaxation mechanisms, while AC conductivity demonstrated conduction mechanisms. Mag­
netic properties were characterized using M-H loops measured via VSM. Increasing the Ni concentration led to
higher saturation magnetization (Ms), magnetic remanence (Mr), and coercivity (Hc). Magnetic moments and
anisotropy constants were calculated based on observed values of Ms and Hc. In summary, the nickel-doped zinc
ferrites exhibited notable structural, magnetic, and dielectric properties, suggesting their potential utility in
microwave and high-storage magnetic devices.

1. Introduction nanoparticles as reported in the literature, such as the ball-milling

In the modern world, Nanoscience is considered a leading technol­
ogy. Our primary focus is on spinel ferrite nanoparticles. Spinel ferrites
possessing a crucial role in modern electronic devices due to their
excellent structural and electrical properties. Mainly spinel ferrites used
in technology, have the composition of MFe2O4 (where M denotes the
divalent metal ion), which are immediate in spinel coordination and
exhibit one or more structures. In this research, we have two types of
spinel structures: normal spinel (like zinc ferrite), in which an M2+
metallic ion is symmetrically enveloped by four ions of oxygen and
substituted at tetrahedral sites. Subsequently, the second one is inverse
spinel (like nickel ferrites) has equally distributed Ni2+ and Fe3+ ions.
Half of the Fe3+ ions positioned at tetrahedral sites, while the other half
of Ni2+ ions are occupied at octahedral sites. Spinel ferrites have pre­
dominant growth in many applications. Their use is rapidly increasing in
biomedical science, material science, and engineering as optoelec­
tronics, gas sensors, drug-delivery, magnetic data storage, semi­
conducting, magnetic resonance, gas sensors, and ferrofluid in the 21st
century [1–5]. Mainly, ZnFe2O4 is widely used due to its remarkable
properties. This material demonstrates qualitative physical properties in
various regions characterized as low resistivity and thin-film adsorption
compared to other ferrites [6–8]. On the other side, nickel ferrite is
found as novel material, and its remarkable nanocrystalline properties
have tremendous commercial importance in different ways of telecom­
munication, including radio frequency coil, bar antenna, transformer
cores, high-quality filters, operating systems, and more due to intrinsic
magnetic properties [9,10].
The main motive of this research was to prepare a notable material
having unique properties which play a vital role in scientific society.
There are several chemical techniques in material science to synthesize
method, hydrothermal and solvothermal technique, sol-gel auto com­
bustion method, co-precipitation technique, standard double-sintering
method, microwave sintering technique, reverse micelle reaction pro­
cess, and evaporation method [11–16]. Many researchers have created
Ni doped Zn ferrites with varying Ni and Zn concentrations using various
synthesizing techniques [17]. Most of the published data on Ni-Zn fer­
rites shows low-frequency dielectric properties, and there is a need to
explore the high-frequency dielectric properties of Ni-Zn ferrites.
The sol-gel auto combustion technique was used to dope different
concentration of Ni2+ ions in zinc ferrites. This technique is low-cost and
provided high purity Ni doped zinc ferrites and made this research easy
and valuable. The prepared samples were characterized by impedance
spectroscopy in a frequency range of 1 MHz to 3 GHz, and high-
frequency dielectric properties were investigated. The magnetic prop­
erties were determined by VSM, and the structural properties were
investigated by XRD and FTIR.
2. Experimental procedure
2.1. Synthesis of NixZn1-xFe2O4 spinel ferrites with various Ni-
concentration (x = 0.0–0.20; Δx = 0.05 per sample)
The Ni-Zn spinel ferrite (NixZn1-xFe2O4) nanoparticles were fabri­
cated by the sol-gel self-ignition process. The synthesis method pro­
ceeded with analytical grades of zinc nitrate [Zn(NO3)2. 4 H2O], nickel
(II) nitrate hexahydrate [Ni(NO3)2. 6 H2O] and iron nitrate [Fe(NO3)3. 9
H2O], which were homogenized with citric acid [C6H8O7⋅H2O] as
gelatin agent. The ratio of molarity among metal nitrates and citric acid
was 1:1. Also, the pH value was kept at 7, which was maintained by a
gradual percentage increase of NH3. The solution was stirred with

Fig. 1. (a) XRD spectra of NixZn1-xFe2O4 spinel nano-ferrites with varying doping concentrations (x = 0.00–0.20; Δx = 0.05). (b) Variation in (311) peak position on
2θ axis with different Ni content.

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Table 1
XRD spectroscopic parameters: Full width at half maximum, crystallite size, bulk density, lattice constant, X-ray density, unit cell volume and 2θ value of (311) peak
with varying Ni concentrations in NixZn1-xFe2O4 nanoparticles.
XRD Parameters x = 0.00 x = 0.05 x = 0.10 x = 0.15 x = 0.20 Reference

2θ of (311) peak/degree 35.414 35.450

35.512 35.487 35.526
FWHM/(Radians) x 10-3 8.157 6.256
6.946 8.728 6.265
Lattice constant (Å) (This Work) 8.396 8.388
8.373 8.379 8.370
Lattice Constant (Å) (Ni0.5Zn0.5Fe2O4) BR Babu et al. 8.387 [22]
Lattice Constant (Å) (Ni0.4Zn0.6Fe2O4) M Atif et al. 8.370 [23]
Unit cell Volume/(Å)3 591.960 587.215 590.226
588.4127 586.568
Crystallite size /nm (This work) 17.836 20.953 16.673 23.231
23.258
Crystallite size /nm 23 [22]
(Ni0.5Zn0.5Fe2O4) BR Babu et al.
X-ray density /g cm-3 5.409 5.445 5.426 5.428
5.402
Bulk density /g cm-3 1.232 1.237 1.240 1.250
1.245

magnetic stirrer until the water vaporized and the solution transformed
into a viscous gel. The solution was initially kept at 80 degrees Celsius on
a hot plate and then the viscous gel could combust at about 200-degree
Celsius in a self-transmitting manner. Then the combusted powder could
dry in a thermostatic electric bath for 4 h at 100 oC. The dry powder was
then converted into fine powder by means of mortar and pestle and then
further annealed at 600 oC for three hours. After annealing, the fine
powder of samples was mixed with polyvinyl alcohol and 4 tons of
pressure was used to form pellets.

2.2. Characterization techniques

The structural properties of NixZn1-xFe2O4 nanoparticles were

investigated by X-ray Diffraction Analysis (XRD) using a Phillips
diffractometer (MPD-XPET model) along with Cu-Kα radiations having
λ = 1.5404 Å. The XRD analysis also confirmed the spinel phase. The
crystallite size was calculated by Scherrer’s technique using the broad­
ening of the highest XRD (311) peak. The lattice parameters were
investigated from the diffraction (311) peak by applying the D-spacing
formula. Fourier Transform Infrared Spectroscopy (FTIR) helped in
investigating the vibrational bands at tetrahedral and octahedral sites in
the prepared samples using Nicolet TM iS50 FTIR Spectrometer. The
(Agilent E4991A) material impedance analyzer was used to evaluate
modulus spectroscopy, impedance spectroscopy and dielectric parame­
ters at the 1 MHz to 3 GHz frequency range. Magnetic parameters were
analyzed by means of VSM LakeShore/7404 Vibrating Sample Magne­
tometer (VSM).
3. Results and discussion
3.1. Structural investigations
The X-ray diffraction spectra of Ni-substituted ZnFe2O4 spinel nano-
ferrites with varying doping concentrations (0.00–0.20; Δx = 0.05) per
sample are reported in Fig. 1. The XRD spectra of all the compositions
have identified the mono-phase of cubic spinel ferrite structure. The
observed X-ray diffraction patterns with nine different oriented planes
were assigned to the (220), (311), (222), (400), (422), (551), (440),
(531), and (622) miller indices. The X-ray diffraction patterns belong to
the Fd3m space group and found in excellent agreement with JCPDS
card # 10–325 [18]. No detectable impurities were perceived in the
synthesized nano-ferrite samples, which confirms that nickel ions Ni2+
can replace the zinc ions Zn2+ at tetrahedral sites in zinc ferrites
accordingly [16,19]. The prominent structural diffraction peak (311)
was observed at about 35.5◦ and illustrated in Fig. 1(a). The lattice
Fig. 2. Variation in lattice constant and crystallite size with different Ni con­
centrations in NixZn1-xFe2O4 nanoparticles.
constant was determined using the (311) peak position, which shows a
decreasing trend when Ni-content increased. The decrease in lattice
constant is due to the smaller ionic radii of Ni2+ as compared to Zn2+.
The peak broadening method estimated the crystallite size using the
Scherrer equation on the (311) peak, which reveals a nonlinear behavior
with the increased content of Ni2+ ions. The peak broadening of the
doped samples is higher than that of the bare sample, showing the
nonuniform strain. The compressive strain is due to the smaller ionic
radius of Ni2+ as compared to Zn2+. The varying values of crystallite size
and lattice constant have been reported in Table 1 and are explicitly
shown in Fig. 2.
Debye-Scherrer’s technique was employed to estimate the size of
crystallite [20],
Kλ
D= (1)
βcoscos θ
Here, K is the Scherrer’s constant and for spherical cubical crystals it
is approximately 0.94, λ shows the wavelength of the incident X-ray
beam, θ expresses the Bragg’s angle and in the last β shows the broad­
ening of 311 peaks as determined by the full width at half maxima
(FWHM).
For the correlation, the technique of Williamson-Hall was used,
having form [21],

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A. Quddus et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 676 (2023) 132074

Table 2 DW-H is the crystallite size determined by the Williamson-Hall plot

Structural variables: dislocation density, stacking fault, lattice strain, macro­ and ε is the lattice strain.
strain of NixZn1-xFe2O4 nanoparticles with varying doping concentrations. The lattice constant determination with the help of Braggs law and
Parameters x x x x x interplanar spacing is given below:
= 0.00 = 0.05 = 0.10 = 0.15 = 0.20 √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
λ
Lattice strain x 10-3 6.3 5.4 6.8 4.8 4.8 a= h2 + k2 + l2 (3)
2sinsin θ
Micro strain x 10-3 (lines- 1.94 1.65 2.07 1.49 1.49
2
/m-4)
Where (hkl) indicates the value of the Miller indices of the diffraction
Stacking fault 0.4483 0.4476 0.4478 0.4480 0.4475
Dislocation density x 3.14 2.27 3.59 1.84 1.85 plane and ’a’ shows the lattice constant. The following equation
1015 (lines/m2) measured the dislocation density Table 2,
1
δ= (4)
D2
Here D represents the crystallite size. The X-ray density ρx of the
synthesized nanoparticles was estimated as,
8M
ρx = (5)
NA a3
Here, ρx shows the X-ray density to be measured, NA is the Avogadro
number, M presents the molecular mass and a indicates lattice constant.
The bulk density of synthesized ferrite nanoparticles is calculated by the
volume and mass of the pellets Figs. 3 and 4.
Mb
ρb = (6)
πr2 t

Where r is the radius of the pellet, Mb presents the pellet’s mass and t
indicates the pellet’s thickness. The average structural variables
including x-ray density, bulk density, crystallite size and lattice constant
have been listed in Table 1.

Fig. 3. X-ray and bulk density of Ni-substituted ZnFe2O4 spinel nano-ferrites

with varying doping concentrations in NixZn1-xFe2O4 nanoparticles. 3.2. FTIR spectroscopy

The magnetic and electrical attributes of ferrites are based on their

chemical stability and composition, the distribution of cations, and in
general, their preparations of methodology. The non-destructive tech­
niques are helpful for the identification of the accurate ordering of ions
and atoms in ferromagnetic materials. The Fourier Transform Infrared
Spectroscopy (FTIR) is the best way to investigate ordering phenomena
in various bands. The FTIR technique provides the precise location of
ions in crystals and further briefly describes phonons. As shown in Fig. 5
FTIR behavior analysis of Ni-doped zinc spinel ferrite nanoparticles, two
absorption bands in the range 400–415 cm-1 and 519–538 cm-1 are
visible [24]. Both the absorption peaks of high-frequency and
low-frequency bands are generated due to Fe3+-O2- ions stretching vi­
bration at tetrahedral site and M2+-O2- ions stretching at octahedral site,
respectively. Fig. 5 shows that two frequency bands were observed and
provide a confirmation of Ni substitution in Zn ferrites. A significant
shifting of absorption bands perceived with different concentrations of
nickel may be due to octahedral and tetrahedral locations. The position
of the absorption band is changed, which depends on octahedral and
tetrahedral and is correlated to the metal and oxygen’s bond lengths,
which relates with the is the force constants [25]. The force constants
(Ko and Kt) for both (octahedral and tetrahedral sites) were determined
by the expressions given below:
/
Ko = 0.942128M(v1 )2 (M + 32) (7)

√̅̅̅ /
Kt = 2Ko v1 v2 (8)
Fig. 4. Williamson-Hall’s plots of Ni-substituted ZnFe2O4 spinel nano-ferrites
with varying doping concentrations at Δx = 0.05 per sample and The ν1 and ν2 denote frequency bands and M stands for mass. The
x = (0.00–0.20). following expression is used for the tetrahedral and octahedral radii
calculation.
√̅̅̅
β⋅coscos θ=
k⋅λ
+ 4ε⋅sinsin θ (2) Rtetra = a 3(μ − 0.25) − R◦ (9)
DW− H

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A. Quddus et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 676 (2023) 132074

Fig. 5. FTIR transmittance spectra of Ni-substituted ZnFe2O4 spinel nano-ferrites with varying doping concentrations at Δx = 0.05 per sample and x = (0.00–0.20).

( )
5
Table 3 Rocta = a − μ − R◦ (10)
8
Comparison of size of nano crystallites measurement through Williamson-Hall’s
and Scherrer’s methods. Where a is the lattice constant, Rtetra shows the radius at tetrahedral and
Ni-doped concentration Crystallite size Rocta is the radius at octahedral sites and μ is the position parameter of
Scherrer’s method Williamson-Hall’s method oxygen.
0.00 17.83 23.43
0.05 20.95 27.81 3.3. Dielectric investigations
0.10 16.67 21.98
0.15 23.25 33.64 Spinel ferrites exhibit dielectric properties that are exceptionally
0.20 23.23 32.70
significant and are suitable for high-frequency devices. These spinel

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A. Quddus et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 676 (2023) 132074

Fig. 6. The variations in the frequency dependent dielectric constant for all the
five compositions of NixZn1-xFe2O4 nanoparticles.
Fig. 7. The variations in the frequency dependent dielectric loss for all the five
compositions of NixZn1-xFe2O4 nanoparticles.
ferrites have properties based on the synthesis method, materials
composition, sintering temperature, and annealing time, which are
essential parameters that can enhance material’s dielectric properties. In
the present work, the dielectric properties such as complex impedance,
ac-conductivity, dielectric loss, electric modulus, dielectric constant and
loss tangent of NixZn1-xFe2O4 nanoparticles, having Ni-concentrations
varied from x = 0.00 to x = 0.20, were investigated at room tempera­
ture in the applied frequency varied from 1 MHz to 3 GHz. The calcu­
lated values from various formulae have been listed in Table 3.

3.3.1. Dielectric constant

The dielectric constant, also known as relative permittivity, mea­
sures a material’s capacity to become polarized when exposed to an
electric field. Dielectric constant ε’ of Ni-substituted ZnFe2O4 spinel
nano ferrites with varied doping concentration at Δx = 0.05 per sample
and x = (0.00–0.20) in the flat disc-form pellet were calculated by the
following relation [26].

t Z″
ε′ = × (11)
ωAε◦ Z′2 + Z″2
In the above equation, Z’ and Z″ refer to impedance’s real and
imaginary components, A is the area of surface of pellets, t presents the
thickness of the pellet and permittivity of free space is symbolized by εo.
The explanation of graphical behavior from Fig. 6 shows that the
dielectric constant of all compositions decreasing with respect to fre­
quency from (1 MHz to 3 GHz) range. At low frequencies, all Ni2+ doped
samples show enhanced dielectric constant compared to the undoped
sample. At x = 0.10, the dielectric constant was found to have the most
enhanced impact on the host material. Whereas, at x = 0.15, the
dielectric constant obtained, showing a much steeper decrease with
increasing frequency than the base sample due to a significant decrease
in interfacial polarization. Further, the dielectric constant of all com­
positions has a nearly stable behavior between 10 MHz and 1.5 GHz
frequency region, making these materials suitable for microwave de­
vices [27].
3.3.2. Dielectric loss
Dielectric loss ε’’ of Ni-substituted ZnFe2O4 spinel nano-ferrites with
varying doping concentrations at Δx = 0.05 per sample and x =
(0.00–0.20) in flat disc-form pellet was calculated as [28],
t Z′
ε′ = × (12)
ωAε◦ Z′2 + Z′2
As many terms are mentioned in the formulae, the applied electric
field’s frequency was represented by ω, Z’ and Z’’ referred to real and
imaginary components of impedance, A is the cross-sectional area of
Fig. 8. Dielectric loss tangent versus frequency plot of Ni substituted ZnFe2O4
spinel nano-ferrites with varying doping concentrations at Δx = 0.05 per
sample and x = (0.00–0.20).
pellets, t be the pellet’s thickness and permittivity of free space sym­
bolized by εo.
Fig. 7 illustrating the composition and frequency-dependent
behavior of dielectric loss in NixZn1-xFe2O4. It can be observed that ε’’
decreases with increasing Ni content other than x = 0.10 compositions,
for which the maximum dielectric constant value was obtained. In low
frequency domain, a clear fall of dielectric loss can be analyzed, whereas
a stable response in the mid-frequencies and relaxation peaks in the
high-frequency domain have been observed. These relaxation peaks at
high frequencies might be due to the to the space charge and orientation
polarizations [27]. The nearly stable response of low dielectric loss in
the frequency range of 10 MHz to 1.5 GHz signifies the importance of
these ferrites as low-loss materials in high-frequency devices.
3.3.3. Dielectric tangent loss (tan δ)
The tangent loss of dielectric materials quantifies the dissipation of
energy (i.e., energy loss) in it over a complete cycle of applied electric
field frequency. The dielectric loss tangent in relation with ε’ and ε’’ is
given by:
ε′
tantan δ = (13)
ε′

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A. Quddus et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 676 (2023) 132074

Fig. 9. Variations in AC conductivity of NixZn1-xFe2O4 nanoparticles with
varying frequency and with varying doping concentrations at Δx = 0.05 per
sample and x = (0.00–0.20).
Fig. 8 depicting a relatively high loss tangent at 1 MHz, which sud­
denly drops with increased applied field frequency. Noticeably, all
synthesized samples have a low loss tangent value (≈ 0.001) in the
applied frequency range of 10 MHz to 1 GHz. At high frequencies, the
relaxation peaks might be because of the space charge and orientational
polarizations. The prepared samples show smaller loss tangent values.
The low value of loss tangent from 10 MHz to 1 GHz, shows that these
materials have a small energy loss rate and can be used efficiently in
capacitors and microwave devices.
3.3.4. AC conductivity
The AC conductivity σ ac of NixZn1-xFe2O4 ferrites annealed at 600 ℃
has been investigated by varying frequency from 1 MHz to 3 GHz. The
following equation determined the AC conductivity.
Fig. 10. Plot of real component of impedance with frequency for all the five
samples of NixZn1− xFe2O4 spinel nano-ferrites.
t Z′
σ ac = × (14)
A Z′2 × Z′2
Here σac indicates AC conductivity, Z’ and Z’’ are respectively real
and imaginary components of complex impedance, A be the cross-
section area, t be the thickness of the pellet.
The characteristics of AC-conductivity of NixZn1-xFe2O4 were studied
for increasing frequency and different nickel compositions. A graphical
representation of AC conductivity against frequency has been plotted in
Fig. 9. It is appeared that the ac conductivity for all compositions is small
at low frequencies, which pointing towards the resistive behavior of
grain boundaries due to low hopping frequency of electrons across the
grains. At higher frequencies, the σac has greater values because at
higher frequencies, the hopping frequency of electrons across the grain
boundaries becomes high [29]. This property of spinel ferrite materials
regarding maximal conducting behavior at higher frequencies explained
by electrons hopping across the grain boundaries is agreed with the

Table 4
FTIR parameters of the NixZn1-xFe2O4 nano ferrites with varying doping concentrations at x = (0.00–0.20).
Parameters x = 0.00 x = 0.05 x = 0.10 x = 0.15 x = 0.20

Molecular weight (g/mol) 241.070 240.736 240.401 240.067 239.733

ν1 (cm-1) 525.51 535.15 533.22 537.08 519.73
ν2 (cm-1) 404.02 413.66 404.02 404.02 414.62
Kt (N/m) 249731.8 260338.4 253313.1 255105.1 253299.4
Ko (N/m) 135764.1 142296.9 135719.8 135697.6 142888
Rtetra (nm) 1.8177 1.8128 1.8141 1.8160 1.8121
Rocta (nm) 0.7790 0.7732 0.7747 0.7770 0.7725

Table 5
Electrical parameters of Ni-substituted ZnFe2O4 spinel nano-ferrites with varying doping concentrations at Δx = 0.05 per sample and ( x = 0.00–0.20).
Parameters Frequency Ɛ’ Ɛ" tan (δ) Z’ Z" M’ M"

x ¼ 0.00 1 MHz 5.358 0.524 0.097 7351 75085 0.184 0.0180

1 GHz 5.078 0.057 0.011 0.900 79.52 0.196 0.0022
3 GHz 5.480 0.233 0.042 1.050 24.64 0.182 0.0077
x ¼ 0.05 1 MHz 6.318 0.030 0.004 307.0 64285 0.158 0.0007
1 GHz 5.782 0.130 0.022 1.581 69.81 0.172 0.0039
3 GHz 6.190 0.325 0.052 1.145 21.79 0.160 0.0084
x ¼ 0.10 1 MHz 7.531 1.127 0.149 7898 52750 0.129 0.0190
1 GHz 6.389 0.077 0.012 0.768 63.20 0.156 0.0019
3 GHz 6.750 0.217 0.032 0.643 20.01 0.147 0.0047
x ¼ 0.15 1 MHz 5.703 0.324 0.056 4044 70990 0.174 0.0099
1 GHz 5.004 0.043 0.008 0.697 80.69 0.199 0.0017
3 GHz 4.980 0.198 0.039 1.082 27.11 0.200 0.0079
1 MHz 5.699 0.254 0.044 3179 71125 0.175 0.0078
x ¼ 0.20 1 GHz 5.281 0.500 0.009 0.734 76.46 0.189 0.0018
3 GHz 5.340 0.228 0.042 1.078 25.27 0.186 0.0079

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A. Quddus et al.
Fig. 11. Plot of imaginary component of impedance with applied frequency for
all the five samples of NixZn1− xFe2O4 spinel nano-ferrites.
Fig. 12. Plot of real component of modulus with applied frequency for all the
five samples of NixZn1− xFe2O4 spinel nano-ferrites.
Maxwell-Wagner theory and Koop’s phenomenological model [30,31].
3.3.5. Complex impedance
To understand the impedance quality of dielectric materials, the
graphical behavior of the impedance of NixZn1-xFe2O4 nanoparticles has
been investigated for all the five samples by changing frequency from
1 MHz to 3 GHz. The real and imaginary parts (Z’ & Z") of complex
impedance has been estimated by the following relations, Table 4.
Z′ = R = |Z|coscos θz
Z′ = X = |Z|sinsin θz
Table 5 contains the measured values of Z’ and Z". Fig. 10 illustrates
the frequency dependency of the impedance of NixZn1-xFe2O4 nano­
particles. The highest impedance at low frequencies was found for the
x = 0.10 composition. With the increase in frequency, the impedance of
all samples decreased, which shows enhanced conductivity in the GHz
frequency region. The enhanced conductivity is because at higher fre­
quency domain, the electron’s hopping frequency becomes high which
agrees with the σac plot in Fig. 9. The variations in impedance loss (Z") by
changing frequency has been illustrated in Fig. 11, which explores the
contribution of reactance in total impedance. The undoped sample dis­
played the maximum reactance and for all compositions, Z" decreased
with increasing frequency [32]. The low values of Z’ and Z" in the GHz
Colloids and Surfaces A: Physicochemical and Engineering Aspects 676 (2023) 132074
Fig. 13. Plot of imaginary component of impedance with applied frequency for
all the five samples of NixZn1− xFe2O4 spinel nano-ferrites.
Fig. 14. M-H loops of Ni1-xZnxFe2O4 spinel nano-ferrites with varying doping
concentrations at Δx = 0.05 per sample and x = (0.00–0.20).
frequencies depicting that the grain boundaries have conductive nature
at that region, which is due to the hopping of electrons under the in­
fluence of the time-varying applied electric field [33].
3.3.6. Complex electric modulus analysis
To study the conduction mechanism in a medium due to grain
boundaries and grains, another approach of electric modulus is used.
The advantage of this method is that it suppresses the effects of electrode
polarization. Both the real and imaginary components (M′ and M″) of
(15) electric modulus can be computed by means of the components of
dielectric constant [34],
(16)
ε′
M′ = (17)
ε′2 + ε′2
ε′
M′ = (18)
ε′2 + ε′2
Fig. 12 depicting the variations arise in electric modulus with vary­
ing frequency. Initially, at 1 MHz, all samples exhibited a small M’
value, which then rapidly increased with frequency. The 10 MHz to
1.5 GHz region shows a nearly stable value of M’ due to the constant
resistive nature of grains. At higher frequencies, after 1.5 GHz, the
relaxation peaks describing that the grain boundaries possess the
conductive nature because of the hopping of electrons. Fig. 13 shows the
8
A. Quddus et al.
Fig. 15. (a) remnant and saturation magnetization as a function of Ni concentration, (b) squareness and coercivity depending on Ni-concentration and (c) magnetic
moment and anisotropic constant depending on Ni-concentration.
M’’ vs. frequency plots of all compositions. At 1 MHz, the imaginary part
of the modulus has a high value, which sharply decreases with fre­
quency, and then M’’ is nearly set to a stable low value till 1.5 GHz. At
2.5 GHz, the relaxation peaks are also visible in M’’ vs. f plot. The values
of (real and imaginary) electric modulus for all compositions at 1 MHz,
1 GHz, and 3 GHz have been presented in Table 5.
3.4. Magnetic investigations (VSM)
Investigations on the magnetic behavior of NixZn1-xFe2O4 for con­
centrations Δx = 0.05 per sample and x = (0.00–0.20) spinel ferrite
nanomaterial was done by making use of Vibrating Sample Magne­
tometer (VSM). The magnetization of the compound depends on the
applied H field, as shown in Fig. 14, presenting the hysteresis loop from
30 to − 30 kOe. The concentration at (x = 0.00) shows paramagnetic
behavior with a very small saturation magnetization, and the concen­
tration at (x = 0.05) shows weak ferromagnetic behavior. Other con­
centrations from (x = 0.10–0.20) indicate enhancement of magnetic
properties and saturation magnetization having stable ferromagnetic
behavior. The squareness ratio Mr/Ms was found to be 0.01 for the
undoped sample, indicating paramagnetic behavior. In consonance with
the Neel’s model, the sites A-B interact with one another across A-A and
B-B interactions, where A is orientated as a tetrahedron and B is orien­
tated as an octahedron and both are opposing, and their exchange
interaction is the reason for variation in magnetism. The divalent Zn2+
ion and trivalent Fe3+ ion are allocated on the tetrahedral and octahe­
dral sites, respectively. The increasing Ni2+ doping in Zn ferrites im­
proves the impact on magnetic behavior, possibly due to the
ferromagnetic nature of the Ni2+ ion. The following parameters of
magnetic properties as magnetic squareness (Mr/Ms), magnetic anisot­
ropy constant (K) and Bohr magneton (ηB) were estimated by given
9
Colloids and Surfaces A: Physicochemical and Engineering Aspects 676 (2023) 132074
formulae [35,36]:
Mr
Magnetic squareness = (19)
Ms
Ms × Hc
Anisotropy constant = (20)
0.96
M × Ms
Bohr magneton = (21)
5855 ∗ ρXray
Where Mr represents remanent magnetization, Ms represents saturation
magnetization, Hc represents coercive field, M represents molecular
weight, and ρXray represents X-ray density of Ni-substituted ZnFe2O4
spinel nano-ferrites. Fig. 15(a) shows the variations of magnetic rema­
nence Mr and saturation magnetization Ms for different Ni doping con­
centrations. Both Ms and Mr were found increasing with Ni content.
Fig. 15(b) shows the variations in magnetic squareness and coercivity
with varying Ni-content. Coercivity was found increasing with increase
of Ni content. The increase in coercivity can be attributed to the influ­
ence of the dopant on the magnetic interactions and anisotropy of the
material. The exchange interaction between magnetic moments is
altered when Ni ions are substituted for Zn ions. In comparison to Zn
ions, Ni ions have a greater magnetic moment, which results in stronger
exchange interactions. The increased coercivity is a result of this
improved exchange interaction. Fig. 15(c) shows the variations in
magnetic moment and anisotropy constant with varying Ni content. The
calculated magnetic variables were observed to be modified with the
increase of Ni content in Zn ferrites. The calculated values have been
summarized in Table 6.
A. Quddus et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 676 (2023) 132074

Table 6
Magnetic parameters of NixZn1− xFe2O4 spinel nano-ferrites with varying doping concentrations at Δx = 0.05 per sample of and x = (0.00–0.20).
Parameters Symbol x = 0.00 x = 0.05 x = 0.10 x = 0.15 x = 0.20

Coercive Field (This work) Hc (Oe) 60.044 171.224 164.920 175.824 161.694
Coercive Field (Ni0.5Zn0.5Fe2O4) BR Babu et al.[22] Hc (Oe) 103
Saturation Magnetization (This work) Ms (emu/g) 1.86 2.32 13.61 19.68 23.70
Saturation Magnetization (Ni0.5Zn0.5Fe2O4) BR Babu et al.[22] Ms (emu/g) 47
Saturation Magnetization (Ni0.4Zn0.6Fe2O4) M Atif et al.[23] Ms (emu/g) 69
Remanent Magnetization (This work) Mr (emu/g) 0.01 0.32 1.29 2.29 3.81
Remanent Magnetization (Ni0.5Zn0.5Fe2O4) BR Babu et al.[22] Mr (emu/g) 6
Squareness value Mr/Ms 0.01 0.14 0.09 0.12 0.16
Magnetic Moment n (nB) 0.08 0.10 0.59 0.85 1.02
Anisotropy Constant K (erg/cm3) 116.22 414.61 2338.66 3604.53 3991.94

4. Conclusions The authors extend their appreciation to the Deanship of Scientific

The primary motive of this work is to observe the effect of nickel
substitution in zinc ferrite (NixZn1-xFe2O4) nanoparticles with different
concentrations at (x = 0.00, 0.05, 0.10, 0.15 and 0.20). The samples
have been prepared by means of sol-gel auto combustion method. The
spectra obtained through XRD verified the crystal structure of NixZn1-
xFe2O4 nanoparticle and showed that the particles acquired spinel
crystal structure of Fd3m space group. The crystallite size obtained in
the range of 16–23 nm, which was computed through Scherrer equation
and correlated by WH method. The FTIR spectra were recorded by iS50
FT-IR spectrometer, which confirmed the tetrahedral and octahedral
bonding in the prepared spinel ferrites. Dielectric analysis was done to
investigate the ac conductivity and other dielectric parameters for all the
samples in the frequency range of 1 MHz to 3 GHz. In the frequency
range of 1 MHz to 1.5 GHz, the tangent loss appeared low and dielectric
constant was found stable, which depicting that Ni-doped Zn ferrites
might be the suitable material for microwave devices and good-quality
capacitors. Further, doping of Ni in Zn ferrites resulted in enhanced
magnetic properties. The concentration at (x = 0.00) shows para­
magnetic behavior with a fragile saturation magnetization, and the
concentration at (x = 0.05) shows weak ferromagnetic behavior. Other
concentrations from (x = 0.10–0.20) indicate enhancement of magnetic
properties and saturation magnetization having stable ferromagnetic
behavior.
CRediT authorship contribution statement
Ahsan Quddus: Conceptualization, Methodology, Software. Syed
Zia Hussain Hashmi.: Data curation, Writing – original draft prepara­
tion. Ghulam Mustafa: Visualization, Investigation. Muhammad
Khalid: Conceptualization, Supervision. M.G.B.Ashiq: Software, Vali­
dation. Ghazanfar Nazir: Writing – review & editing, Supervision.
Thamraa Alshahrani: Funding acquisition, Supervision. Mohammed S.
Alqahtani: Methodology, Validation, Funding acquisition. Kiran Naz:
Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data Availability
Data will be made available on request.
Acknowledgement
This research was funded by the Princess Nourah bint Abdulrahman
University Researchers Supporting Project number (PNURSP2023R1),
Princess Nourah bint Abdulrahman University, Riyadh, Saudi Arabia.
Research at King Khalid University, Saudi Arabia for funding this work
through Large Groups Project under grant number L.R.G.P2/516/44.
Compliance with ethical standards
None.
Statements & Declarations
None.
Author contributions
All authors contributed to the study conception and design. Material
preparation [Ahsan Quddus], [Syed Zia Hussain Hashmi] and [Dr.
Muhammad Khalid], data collection [Abeer AlObaid], [Ghulam Mus­
tafa], and [Ghazanfar Nazir] and analysis were performed by [Ghulam
Mustafa], [Kiran Naz], [Dr. Muhammad Khalid][M G B Ashiq]. The first
draft of the manuscript was written by [Ahsan Quddus] and all authors
commented on previous versions of the manuscript. All authors read and
approved the final manuscript.
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