Materials Chemistry and Physics 259 (2021) 124066

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Structural, spectral, dielectric and magnetic properties of

Sr2CuxNi2-xFe28-xCrxO46 (0 ≤ x ≥ 0.5) ferrites synthesized via
micro-emulsion route
Muhammad Azhar Khan a, *, Muhammad Qamar uz Zaman a, Abdul Majeed b, c, **,
Majid Niaz Akhtar d, Waseem Abbas e
a
Department of Physics, The Islamia University of Bahawalpur, Bahawalpur-63100, Pakistan
b
Department of Physics, University of Malakand, Chakdara, Dir (Lower), 18800, Pakistan
c
Center for Computational Materials Science, Department of Physics, University of Malakand, Chakdara, Dir (Lower), 18800, Pakistan
d
Department of Physics, Muhammad Nawaz Sharief University of Engineering and Technology (MNSUET), 60000, Multan, Pakistan
e
Department of Physics, Bahauddin Zakariya University, Multan, 60800, Pakistan

H I G H L I G H T S

• Sr2CuxNi2-xCrxFe28-xO46 X-type ferrites were prepared micro-emulsion route.

• The crystallite size is found in the range 19–23 nm.
• FTIR spectra unveiled strong influence of Cr3+-Cu2+ substitution.
• Coercivity of these materials reflects their use in longitudinal recording media.

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

Keywords: In the present study, Sr2CuxNi2-xCrxFe28-xO46 where (x = 0.0, 0.1, 0.2, 0.3, 0.4, 0.5) X-type ferrites were fabri­
XRD cated by micro-emulsion procedure. X-ray diffraction technique assured the phase of fabricated ferrites to be that
Spectroscopic studies of pure X-type ferrites. The reduction in lattice constants (a & c) seemed with the incorporation of Cr3+-Cu2+
Dielectric measurements
metals. The crystalline size of the synthesized materials was obtained in 19–23 nm range, using the Scherer’s
Magnetic studies
Longitudinal recording media
formula. The iron-oxygen bands of X-type hexagonal ferrites at tetrahedral and octahedral sites were confirmed
from FTIR spectra. The FTIR spectra also showed the strong influence of Cr3+-Cu2+ substitution, which confirmed
that the dopants have a meaningful role in these ferrites. The dielectric parameters were explored in a large
frequency range (i.e. from 1 MHz to 3 GHz) and these parameters showed significant variations with Cr3+-Cu2+
doping contents. Moderate values of dielectric constant, low tangent loss, high Q values, and significant response
to the high frequency of these X-type ferrites ensured their applicability for the high (GHz) frequency applica­
tions. Vibrating sample magnetometry technique (VSM) was applied to unfold the magnetic parameters. The
Coercivity (Hc), saturation magnetization (Ms) as well as remanence magnetization (Mr) revealed considerable
variations with doping Cr3+-Cu2+cations. The enhancement in magnetic parameter i.e. coercivity Hc with the
doping of Cr3+-Cu2+ reflects the uses of these materials in longitudinal recording media.

1. Introduction attention of researchers owing to their innovative applications in the

magneto-electronic industry and engineering. Among magnetic nano-
The field of magnetism is considered as limelight of the nanotech­ materials, ferrites are the most focused materials due to their various
nology revolution. Nano-magnetic materials continue to attract the technological applications, easy preparations, low cost, low eddy

* Corresponding author.
** Corresponding author. Department of Physics, University of Malakand, Chakdara, Dir (Lower), 18800, Pakistan.
E-mail addresses: azhar.khan@iub.edu.pk (M.A. Khan), abdulmajeed2276@gmail.com (A. Majeed).

https://doi.org/10.1016/j.matchemphys.2020.124066
Received 26 March 2020; Received in revised form 13 October 2020; Accepted 15 November 2020
Available online 23 November 2020
0254-0584/© 2020 Elsevier B.V. All rights reserved.
 M.A. Khan et al. Materials Chemistry and Physics 259 (2021) 124066

current losses, and their tunable properties. The electrical characteristics 2. Experimental procedure
of ferrites offer their applications in high-frequency devices and these
are also related to dielectrics. The advantages of ferrites as compared to 2.1. Samples preparation & characterization
other dielectric systems are their elastic properties and their resistance
to environmental modifications even at high temperatures. However, Micro-emulsion route has been applied to synthesize Sr2CuxNi2-
the soft or hard magnetic nature of ferrites determines its specific ap­ xCrxFe28-xO46 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) X-type Hexa-ferrites. The
plications. Researchers have been focused on hard ferrites or those chemicals Fe(NO3)3.9H2O, Ni(NO3)2, (CuNO3)2.3H2O, Cr(NO3)3.9H2O,
possessing high coercive fields for many years owing to their upgrading Sr(NO3)2 were used to synthesize these samples. All these salts were
numerous technological applications [1–3]. The ferrites having hexag­ dissolved in de-ionized water. The stoichiometric calculation was
onal structure are the major worldwide magnetic ceramics by volume. applied to mix all the salts solutions and were stirred and heated at a
Hexagonal ferrites have replaced expensive permanent magnets such as temperature of 60 ◦ C. As a surfactant, the CTAB (Cetyl trimethyl
rare earth alloys due to their very low price and novel properties [4]. ammonium bromide of formula (C16H33)N(CH3)3Br) solution was added
The extensive use of hexagonal ferrites is attributed to their inimitable to all the samples during the stirring. After that, aqueous ammonia
applications i.e. in magnetic refrigeration, high-frequency devices up to (NH3) soln. was poured in all the samples to move the value of pH up to
several GHz [5], ferrofluids, wireless communication, and perpendicular 10. Then all the solutions were stirred for 6 h. After the stirring, de-
recording media [6,7]. Hexagonal ferrites are of seven types; namely ionized water was used to wash all the samples for the sake of mini­
M-type (SrFe12O19), W-type (SrMe2Fe16O27), Y-type (Sr2Me2Fe12O22), mizing the pH of solutions near to 7. The washed solutions were let to
Z-type (Sr3Me2Fe24O41), U-type (Sr4Me12Fe36O60), X-type (Sr2Me2 dry in a microwave oven. The dried materials were then ground and
Fe28O46) where Me is cation of oxidation state of 2+ i.e. Cu2+, Zn2+, afterward sintered at 1250 ◦ C for a time of 7 h by high temperature-
Ni2+ etc, while Ba or La can be used instead of Sr [8]. The X-type controlled muffle furnace Vulcan A-550.
Hexa-ferrites are more efficient among other hexagonal ferrites due to X-ray diffraction of the model (XRD, PW-1840 Philips diffractometer
their high Curie temperature, the high value of anisotropy, and with Co-Kα radiation) was used to investigate the structural properties of
marvelous applications in microwave devices (multilayer chip in­ these materials. The lattice parameters and phase of the prepared ma­
ductors, phase shifters, circulators, etc) [9–11]. terials were investigated from XRD data. FTIR was employed for spectral
The structure of Ba2Me2Fe28O46 (where Me = Cu2+, Zn2+, Ni2+, etc) analysis of all the prepared samples in the wavenumber (k) range of
X Hexa-ferrites is made by the stacking of R and S blocks in the proper 1600–350 cm− 1. The impedance analyzer (RF Impedance analyzer;
sequence of R.S.R.S.S.R*S*R*S*S* in which “R = BaFe6O11” with three Model #E4991a) was applied to analyze dielectric characteristics of the
oxygen layer block while “S = Fe6O8” [12,13]. Hexa-ferrites acquire as-synthesized materials. The magnetic properties i.e. coercivity (Hc)
changeable properties depending upon the process of synthesis, distri­ saturation and remanence magnetization (Ms, Mr) of the prepared ma­
bution, and selection of the metal cations among the sub-lattices [14]. X terials were investigated by the VSM technique.
Hexa-ferrites are ferrimagnetic substances [7] and the magnetic prop­
erties of these materials can be varied with the addition of divalent or 3. Results and discussion
trivalent cations [10]. Gu et al. [15] prepared Ba2Cu2xZn2-2xFe28O46 (0
≤ x ≤ 1) X-type hexagonal ferrites and then inquired Curie temperature 3.1. Crystallographic analysis
of these ferrites. The decrease in magnetic moment and rise in Curie
temperature were observed due to the replacement of Zn2+ ion by Cu2+ The X-ray diffraction (XRD) patterns of Cr3+ and Cu2+ substituted Sr
ion. Leccabue et al. [16] studied the morphological and magnetic based X-type ferrites are displayed in Fig. 1. The diffracted peaks ob­
characterization of Sr2Zn2Fe28O46 X hexagonal ferrite. The saturation tained from XRD analysis were compared with the reference card (ICDD
magnetization (σs) of Sr2Zn2Fe28O46 ferrite was found to be 80 emu/g. # 01-073-2034) and matched well. XRD analysis affirmed the formation
The elevated sintering temperature was accountable for a large grain of a pure X-type ferrites phase. Values of lattice constants (a, c) are
growth (e.g. almost 20 μm) with the consequent decrease of the coercive shown in Table 1. These values have been obtained for all samples by
field (about 100 Oe). Dey et al. [17] studied the Curie temperature and cell software. The lattice constants (a and c) showed a decreasing trend
magnetic characteristics of Sr2Me2Fe28O46 (where Me2+ = Zn2+, Fe2+)
X-type Hexa-ferrites. The Curie temperature of these ferrites was found
to be 721 K. Azhar et al. elucidated the structural, dielectric, and mag­
netic behavior of Cu2+ and Cr3+ doped cobalt-based barium X-type
ferrites. Crystallite size is laid in the range 28–32 nm. They found an
enhancement in coercivity with Cu–Cr doping and observed inverse
relation of coercivity with crystallite size, which revealed the
super-paramagnetic nature of these materials. Dielectric constant and
tanloss reduced with co substitution of Cu2+ and Cr3+, which reflected
their possible use in multi-layer chip inductors [18].
In this research work, micro-emulsion route was used to fabricate
Sr2CuxNi2-xCrxFe28-xO46 (x = 0.0, 0.1, 0.2, 0.3, 0.4, 0.5) X-type hex­
aferrites. The micro-emulsion process was chosen to fabricate these X-
type materials as it provides a high degree of dispersion, better control
over the chemical reaction, and particles of extremely small size in the
nanometer scale. The aim was to examine the impact of non-magnetic
ions Cr3+ and Cu2+ on crystallographic, dielectric, and magnetic pa­
rameters of Sr-X Hexa-ferrites. The main focus of the current research
was to lower dielectric losses and enhance quality factor (Q value) at
GHz frequency regime, so that the prepared X-type materials may find
applications in low loss microwave gadgets.

Fig. 1. XRD patterns of Sr2CuxNi2-xCrxFe28-xO46 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5)

X-type hexagonal ferrites.

2
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M.A. Khan et al. Materials Chemistry and Physics 259 (2021) 124066

Table 1
Lattice constant (a, c), cell volume (V) x-ray density and c/a ratio of the Sr2CuxNi2-xCrxFe28-xO46 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) X-type hexagonal ferrites.
Cu, Cr content(x) X = 0.0 X = 0.1 X = 0.2 X = 0.3 X = 0.4 X = 0.5

Lattice constant(a) (Å) 5.93 5.87 5.86 5.84 5.86 5.92

Lattice constant(c) (Å) 83.91 83.74 83.65 83.57 83.42 83.97
Cell volume (Å)3 2555.36 2498.84 2487.66 2468.34 2480.82 2548.57
X-ray density (g/cm3) 5.05 5.16 5.19 5.23 5.20 5.06
c/a 14.15 14.26 14.27 14.30 14.23 14.18
Crystalline size 21.18 19.66 23.33 22.28 21.15 21.17

from 5.93 Å to 5.84 Å because of the incorporation of Cr3+ and Cu2+ ions
up to a concentration of 0.3 and then increased to 5.92 Å up to the
concentration of 0.5. These modifications in values of lattice constants
are expected, because the ionic radii of substituted ions i.e. Cu2+ (0.73
Å), Cr3+ (0.63 Å) are different from ionic radii of host ions i.e. Ni2+
(0.69 Å) and Fe3+ (0.645 Å) [19,20]. The value of both lattice constants
(a and c) showed decreasing behavior with the amount of doping. This
decreasing behavior might be ascribed to localized lattice distortion and
influence of internal stress in X-type lattice due to the doping of different
ionic radii elements [21]. The unit cell volume V of these samples was
measured using the following equation:
V = ​ a2 c⋅ ​ sin120⋅
The cell volume of all prepared samples of Cr3+-Cu2+ doped SrNi-X
hexagonal ferrites is mentioned in Table 1. The (c/a) ratio was calcu­
lated, its values were compatible with other reported nano X-type fer­
rites [22,23]. The crystalline size (D) was also calculated and it was
found in the range 19–23 nm, using renowned relation named as Debye
Scherer’s equation [24]:
D ​ = ​ 0.9⋅λ/⋅βcosθ
Where λ denotes X-ray’s wavelength, β is called full width at half max­
ima of the most intense peak, and θ is the angle. X-ray density is
calculated using equation (3) and it increased with doping of Cr3+ and
Cu2+ ions. X-ray density is directly linked to the molecular weight of
composition while its values vary inversely with volume, given by the
following formula [25]:
Dx ⋅ = ⋅3M/NV
In equation (4), M represents the molecular mass of the sample, N is
Avogadro number and V denotes the volume.
3.2. FTIR analysis
Fig. 2 shows the FTIR spectra of the Sr2CuxNi2-xCrxFe28-xO46 (x = 0.0,
0.3, 0.4, 0.5) X Hexa-ferrites. FTIR analysis shows the structural, phase,
and chemical changes in the prepared samples. In the FTIR spectra,
various absorption bands appeared within a wavenumber of 400 cm− 1 to
600 cm− 1. The lower wavenumber bands within the 400-500 cm− 1
range are due to the existence of an iron-oxygen band at the octahedral
site while the band in the range of 500–600 cm− 1 is due to the formation
of a metal-oxygen band at the tetrahedral site [26]. These bands
confirmed the phase of these Sr based X-type ferrites. The considerable
variations were also observed with the doping of Cr3+ and Cu2+ which
1
shows the significant role of the dopant in these Hexa-ferrites [27]. A
wavenumber 1456 cm− 1 one more band is also visible which corre­
sponds to the stretching vibration mode of NO1− 3 in these synthesized
materials [28].
3.3. Dielectric analysis
2 The dielectric characteristics of X-type materials can be tuned by
varying number of factors such that, the process of fabrication, sintering
time and temperature, the concentration of a ferrous and ferric ion in the
material, and also on nature and amount of substitution [29]. Dielectric
parameters (dielectric constant, dielectric loss, tan loss, ac conductivity,
and Q-factor) of Cu and Cr substituted Sr based X-type ferrites were
explained briefly concerning varying frequency and composition.
3.3.1. Dielectric constant
3
The following relation has been applied to determine the dielectric
constant (εʹ) of the synthesized samples:
ε’ = ​ Cd/Aεo ​ 4

Where ε′ is used for dielectric constant, d is the thickness of the pellet, A

Fig. 2. FTIR spectra of Sr2CuxNi2-xCrxFe28-xO46 (x = 0, 0.3, 0.4, 0.5) X-type
hexagonal ferrites.
is the cross-sectional area of the pellet and C is for capacitance. The
graph of dielectric constant concerning the frequency (from 1 GHz to 3
GHz) of Sr2CuxNi2-xFe28-yCryO46 (x ≥ 0–0.5) X Hexa-ferrites is shown in
Fig. 3. At lower frequency regions, the dielectric constant has a large
value and then it decreases by increasing frequency. Some resonance
peaks in the frequency regime of 2–3 GHz also appeared in the graph.
The decline in values of dielectric constant with increasing frequency
may be due to the conducting layer in the materials which can be
justified by the Maxwell-Wagner model [30]. This model states that
ferrites are mainly formed by a layer of grains that show conductive
nature and these grains are parted apart by an insulating layer or
boundaries which are called grain boundaries. Moreover, the conduc­
tion process in ferrites is associated with localized hopping or jumping of
charge carriers (ions of identical elements existing in various valence
states). Mainly, jumping of electron between two-valence states of iron i.
e. Fe2+ and Fe3+ is responsible for conduction in the system of ferrites.
Now, when AC external field is applied to this type of dielectric structure
then, charge carriers reaching grain boundaries are gathered there
because of their insulating nature and produce polarization. So,
enhancement in polarization results in the enhancement of dielectric
constant at the region of lower frequency [31]. However, as the fre­
quency of the AC field builds up, the hopping of charge carriers cannot

3
 M.A. Khan et al.
Fig. 3. The variation of dielectric constant vs frequency of Sr2CuxNi2-xCrxFe28-
xO46 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) X-type hexagonal ferrites.
fluctuate so rapidly with the alternating field. So, the dielectric constant
shows low values in the region of high frequency. Besides, the reason for
resonance peaks in the dielectric constant vs. frequency plots is owing to
the synchronization of the AC field’s frequency with the frequency of
hopping charge carriers [25].
It can also be observed from Fig. 3 that the doping of Cu2+-Cr3+
increases the dielectric constant of these materials. The enhancement in
dielectric constant with Cu2+ and Cr3+ doping may because of the in­
crease in the amount of Fe2+ ions and an increase in the frequency of the
hopping mechanism. The doping of Cu2+ in place of Ni2+ and Cr3+ in
Fe3+ may promote Fe2+ ions formation to adjust charge neutrality [32].
The availability of Fe2+ ions is favorable for the process of hopping at
B-sites, thus polarization increase at B-site, and consequently dielectric
constant increases [33].
3.3.2. Dielectric loss
Dielectric loss concerning external frequency plots of the synthesized
Fig. 4. Variation of dielectric loss factor with frequency of Sr2CuxNi2-xCrxFe28-
xO46 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) X-type hexagonal ferrites.
4
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Materials Chemistry and Physics 259 (2021) 124066
ferrites is shown in Fig. 4. At lower frequency, the large value of permit
loss was observed and decreases with the increasing frequency. The loss
factor was first found to increase by the doping of Cu–Cr, but for a larger
concentration of dopants, it decreased. The certain resonance peaks also
seemed above 2 GHz. The dielectric loss displays a decreasing trend with
frequency because the hopping of charge carriers cannot alternate with
the frequency of the external alternating field. The low permit or
dielectric loss at high frequency indicates that the energy loss decrease
at high frequency [34,35]. Among all fabricated samples, the dielectric
loss for samples Sr2Ni2Cu0.4Cr0.4Fe27.6O46 and Sr2Ni2Cu0.5Cr0.5Fe27.5O46
was very low (i.e. less than 0.01) in the GHz frequency range.
The dielectric loss was found to initially increase with substitution of
Cu2+ and Cr3+ up to 0.2 concentration and then decreases with the in­
crease of Cu2+ and Cr3+ concentration. These variations may be due to
the different site occupancy of cations, which depend on the concen­
tration and size of substituted cations. These variations may be also
caused due to the disturbances of grains and grain boundaries.
3.3.3. Dielectric tan loss
The Tan(δ) (tangent loss) of the prepared X-type materials is shown
in Fig. 5. It has been observed that the dielectric tangent loss of these X-
type materials decreases with frequency, which may be justified by the
Maxwell Wagner model [30]. In the region of lower frequency, there is
the dominance of insulating grain boundaries, so a greater amount of
energy is required for the movement of electron between Fe2+ and Fe3+
ions which increases energy loss and hence, the tan loss. Whereas,
moving to higher frequency regime, conductive grains become domi­
nant which make the movement of electron between Fe2+ and Fe3+
easier, and therefore result in low energy loss. The tan loss first increases
and then decreases with Cu2+ and Cr3+ concentration, and has very low
values for all the samples. These results suggest that with the proper
amount of doping (Cu2+ and Cr3+) concentration low losses can be
achieved at the GHz frequency range. The samples Sr2Ni2
Cu0.4Cr0.4Fe27.6O46 and Sr2Ni2Cu0.5Cr0.5Fe27.5O46 have very low values
of tan loss i.e. 0.009 and 0.001 at 2.3 GHz frequency respectively, which
propose their applicability in low loss high-frequency devices [33].
3.3.4. AC conductivity
Equation (5) was applied to determine the ac conductivity σac of the
prepared samples [36];
σ ac ​ = ​ 2πf εo ⋅ε˝⋅ = 2πf εo αε˝Tan(∂) 5
Fig. 5. Variation of tangent loss with frequency of Sr2CuxNi2-xCrxFe28-xO46 (x
= 0, 0.1, 0.2, 0.3, 0.4, 0.5) X-type hexagonal ferrites.
 M.A. Khan et al. Materials Chemistry and Physics 259 (2021) 124066

Where f is applied frequency, σac symbolizes ac conductivity, ε′′ is the

dielectric loss factor, ε′ represents dielectric constant, while Tan(δ) de­
notes the permit tan. The ac conductivity (σac) concerning frequency
graphs of the entire samples of Sr2CuxNi2-xFe28-yCryO46 where (x ≥
0–0.5) X Hexa-ferrites is shown in Fig. 6. The ac conductivity of these X-
type samples revealed increasing behavior with frequency. The ac con­
ductivity was increased with an increment of doping contents (Cu2+ and
Cr3+) up to 0.2 while decrease with the further increase of doping
concentration. The cause of the rise in ac conductivity with frequency
has been briefly explicated by Koop’s and Maxwell-Wagner theory [35].
When external AC frequency is low, the grains as well as grain bound­
aries are randomly oriented. However, with increasing frequency they
become more organized, thus exhibiting capacitive nature. So, ac con­
ductivity enhances with a rise in alternating frequency. The highest
value of dielectric constant and ac conductivity of Sr2Cu0.1Ni2Fe27.9
Cr0.1O46 sample is ascribed to the existence of a large concentration of
Fe2+ ions in this sample [37]. Fig. 7 shows that the value of logac in­
creases with the increase of log(ɷ). The increase in logac can be justified
by the Maxwell-Wagner model, hopping mechanism, and Koop’s theory
[35].
Fig. 7. Log (ω) versus log (ac) of Sr2CuxNi2-xCrxFe28-xO46 (x = 0, 0.1, 0.2, 0.3,
The slope was obtained for all samples from the graph of logac vs. log
0.4, 0.5) X-type hexagonal ferrites.
(ω). The slope was plotted concerning the doping concentration of
Sr2CuxNi2-xFe28-yCryO46 where (x ≥ 0.5) X-type Hexa-ferrites, and is
depicted in Fig. 8. The slope of the prepared materials was found to
increase from 0.40 to 0.56 with an increase of Cr3+-Cu2+ concentration.
This assures that all the prepared X-type samples reveal frequency-
dependent behavior [30].

3.3.5. Q value
The Q value of Cu–Cr doped SrNi-X hexagonal ferrites is shown in
Fig. 9. The Q value enhances with frequency and with Cu–Cr contents.
The high-quality factor corresponds to high dielectric constant and low
values of dielectric losses. Some negative peaks in the Q value graph
were also observed, which were due to the existence of pores in these
materials. The Q value of Sr2Ni2Cu0.5Cr0.5Fe27.5O46 sample is found to
be highest among all samples, and at 2 GHz it showed a maximum Q
value of 2560. Therefore, the sample can be considered the best material
for resonant circuits and multilayer chip inductors [38]. However, all
the currently explored samples revealed optimized dielectric properties
(low dielectric losses and high Q-values) which endorse their applica­
tions in devices operating at microwave frequency.

Fig. 8. Slope vs. concentration of Sr2CuxNi2-xCrxFe28-xO46 (x = 0, 0.1, 0.2, 0.3,

0.4, 0.5) X-type hexagonal ferrites.

3.4. Electric modulus analysis

Electric modulus analysis provides an understanding of the mate­

rial’s electrical behavior, which is based on polarization studies. Using
the following equation electric modulus (M*) can be calculated;

6
′
M∗ ​ = ​ M +M"

7
′ ′ ′
M ​ = ​ ε /(ε )2 ​ + ​ (ε")2 ​

8
′
M" ​ = ​ ε"/(ε )2 ​ + ​ (ε")2
In equation (6), Mʹ represents the real part of the electric modulus,
while the complex part of the electric modulus is denoted by Mʺ. Plots of
Mʹ vs. frequency for all samples of Cr–Cu substituted X-type hexaferrites
is displayed in Fig. 10. It is noticed that at the region of low-frequency Mʹ
has a low value of nearly 0.1 which indicates the negligible value of
electronic polarization [39], but as frequency gradually builds up Mʹ
also increases, thus depicting increased dispersion while moving to the
Fig. 6. AC conductivity (σac) vs frequency (Hz) of Sr2CuxNi2-xCrxFe28-xO46 (x =
region of high frequency. Increased dispersion of Mʹ at the region of high
0, 0.1, 0.2, 0.3, 0.4, 0.5) X-type hexagonal ferrites.

5
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M.A. Khan et al.
Fig. 9. Quality factor vs. frequency of Sr2CuxNi2-xCrxFe28-xO46 (x = 0, 0.1, 0.2,
0.3, 0.4, 0.5) X-type hexagonal ferrites.
Fig. 10. Mʹ vs frequency of Sr2CuxNi2-xCrxFe28-xO46 (x = 0, 0.1, 0.2, 0.3, 0.4,
0.5) X-type hexagonal ferrites.
frequency is due to the phenomenon of relaxation, thus Mʹ saturates
reaching the highest value which depicts that the process of conduction
in as prepared X-type ferrites are owing to the movement of short-range
charge carriers i.e. hole transfer among Cr4+↔Cr3+ and electron transfer
among Fe2+↔Fe3+ [40].
The behavior of the complex component of electric modulus Mʺ
against frequency can be seen in Fig. 11. The value of Mʺ decrease with a
rise in frequency, and beyond the frequency of 2 GHz some resonance
peaks appear for all currently investigated materials. The plot of Mʺ vs.
frequency gives more information regarding charge transfer mecha­
nisms like; conductivity relaxation, electric transport, and ion dynamics
with frequency. The area on the left side of a resonance peak in Mʺ vs.
frequency plot represents the region of frequencies where charge car­
riers are mobile over a large distance i.e. in this region successful hop­
ping of charge carriers can occur between neighboring sites. Whereas,
the high frequency or right side region of Mʺ resonance peak shows the
area of frequency where charge carriers are locally bound to their po­
tential wells and therefore have restricted movement within the well.
However, at the frequency where resonance peak appears to indicate the
6
Materials Chemistry and Physics 259 (2021) 124066
Fig. 11. Mʺ vs. frequency of Sr2CuxNi2-xCrxFe28-xO46 (x = 0, 0.1, 0.2, 0.3, 0.4,
0.5) X-type hexagonal ferrites.
transition or conversion of mobility from long range to the short-range
by increasing frequency. Besides, the appearance of resonance peaks
in the spectra of electric modulus symbolizes conductivity relaxation
[41].
Cole-Cole plots of the prepared ferrites are depicted in Fig. 12. Fig. 12
displays the appearance of one semicircle for all synthesized X-type
materials, which confirms the influential involvement of grain boundary
resistance in the process of conduction. The radius of semi-circles is seen
to be affected by the concentration of Cu2+-Cr3+ substitution. The radius
of the semi-circle in Cole-Cole plots is directly related to resistance and
varies oppositely with AC conductivity. In the present investigation, it is
analyzed that radius of semi-circles increases with Cu2+-Cr3+ contents,
thus suggesting enhancement in resistance with substitution [42].
3.5. Magnetic behavior studies
3.5.1. Saturation, remanence magnetization & coercivity
The graph of hysteresis (M − H) loops of Sr based X-type ferrites
doped with Cu2+ and Cr3+ is depicted in Fig. 13. From M − H loops,
values of magnetic parameters (saturation magnetization Ms, remanence
magnetization Mr, and coercivity Hc were extracted and were plotted
(Fig. 14) against doping (Cr3+ and Cu2+) contents to observe the impact
of substitution. The influence of Cr3+ and Cu2+ doping on magnetic
parameters (Ms, Mr, and Hc) of SrNi based X-type ferrites is displayed in
Fig. 14, and their values are written in Table 2. It is evident from Fig. 14
that, Ms at first increased with Cr3+ and Cu2+ doping contents, while
after x = 0.3 it decreased. The remanence magnetization “Mr” illustrated
an increasing decreasing trend with doping concentration. The distri­
bution of cations in different sites of “S" and “R" blocks of X-type hex­
agonal lattice may be responsible for this variation in magnetic
parameters [43]. Table 3 shows the spin direction of positive ions and
the various sub-lattices of X-type Hexa-ferrites. The slight increase in Ms
with doping concentration might be ascribed to the replacement of
ferromagnetic ions (Fe3+) by ions having a less magnetic moment (Cr3+)
in the spin-down direction of octahedral and tetrahedral sites of X-type
lattice. It has been reported by many researchers that if ferromagnetic
Fe3+ ion is replaced by any other ion in the spin-up state then it is likely
to reduce magnetization, whereas, for spin upstate, the net magnetiza­
tion will always enhance [44]. However, the reduction in saturation
magnetization may be because of the weakening of super-exchange
interaction due to the incorporation of cations of diverse magnetic
moments in different lattice sites of X-type hexagonal lattice [45]. The
M.A. Khan et al.
Fig. 12. Cole-Cole plots of Sr2CuxNi2-xCrxFe28-xO46 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) X-type hexagonal ferrites.
Fig. 13. Plot between variation of Magnetization (emu/g) and applied Mag­
netic Field (Oe) of Sr2CuxNi2-xCrxFe28-xO46 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) X-type
hexagonal ferrites.
substitution of Fe3+ (5μB) by chromium Cr3+ (3 μB) and Ni2+ (2 μB) by
Cu2+ (1μB) may reduce the magnetic interactions in the sample [46].
The coercivity of these ferrites raised from 408 to 687 Oe with Cu2+ and
Cr3+ substitution. The increase in coercivity “Hc” might be the result of
change in the magneto-crystalline anisotropy (MCA) direction from
c-plane to c-axis with the doping of Cr3+ [46]. Another reason for the
increase in coercivity might be the increment in c/a ratio with substi­
tution [30].
7
Materials Chemistry and Physics 259 (2021) 124066
Fig. 14. Plots of Ms, Mr and Hc versus doping concentrations for Sr2CuxNi2-
xCrxFe28-xO46 (x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5) X-type hexagonal ferrites.
3.5.2. Mr/Ms ratio
The squareness ratio of these materials was also calculated from the
values of Mr and Ms and its fall in range 0.25–0.38. As the values of
squareness ratio are less than 1 for all the prepared X-type materials; so
it indicates that all these X Hexa-ferrites are single domain isolated
ferrimagnetic particles. So, it can be concluded from the magnetic pa­
rameters that magnetic properties were strongly influenced by the doing
of Cu2+ and Cr3+ in these X Hexa-ferrites. The obtained values of
coercivity, which are greater than Mr/2 confirm that the prepared ma­
terials are hard and may be applicable for high-frequency devices [7].
M.A. Khan et al. Materials Chemistry and Physics 259 (2021) 124066

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high-frequency devices applications. The significant variations in Ms, substitution on structural, magnetic and dielectric properties of Sr2-xZnxNi2Fe28-
yCryO46 X-type hexagonal ferrite, Solid State Sci. 100 (2020) 106090.
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the doping of Cr3+-Cu2+. Among all fabricated X-type ferrites samples,
Influence of Nd-Co substitution on structural, electrical, and dielectric properties of
Sr2Ni2Cu0.5Cr0.5Fe27.5O46 X-type material revealed exceptional proper­ X-type hexagonal nanoferrites, JMEPEG 23 (2014) 622–627.
ties such as low tangent loss of 0.001, high Q value i.e. 2560 at 2.3 GHz, [23] I.K. Imran Sadiq, Evgeny V. Rebrov, M. Naeem Ashiq, Shahzad Naseem,
and high coercivity of 687 Oe. So, Sr2Ni2Cu0.5Cr0.5Fe27.5O46 X-type Imran Shakir, Mazhar U. Rana, Influence of Sm-Mn substitution on Structural,
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Author credit statement [25] J. Rehman, M.A. Khan, A. Hussain, F. Iqbal, I. Shakir, G. Murtaza, M.N. Akhtar,
G. Nasar, M.F. Warsi, Structural, magnetic and dielectric properties of terbium
Muhammad Azhar Khan: Stoichiometric calculations, draft prepa­ doped NiCoX strontium hexagonal nano-ferrites synthesized via micro-emulsion
route, Ceram. Int. 42 (2016) 9079–9085.
ration, Supervision. Muhammad Qamar uz Zaman: Methodology. [26] M. Ahmad, R. Grössinger, M. Kriegisch, F. Kubel, M. Rana, Magnetic and
Abdul Majeed: editing, software. Majid Niaz Akhtar: Conceptualiza­ microwave attenuation behavior of Al-substituted Co 2 W hexaferrites synthesized
tion, validation. Waseem Abbas: re-writing, data analysis. by sol-gel autocombustion process, Curr. Appl. Phys. 12 (2012) 1413–1420.
[27] G. Murtaza, R. Ahmad, T. Hussain, R. Ayub, I. Ali, M.A. Khan, M.N. Akhtar,
Structural and magnetic properties of Nd–Mn substituted Y-type hexaferrites
Declaration of competing interest synthesized by microemulsion method, J. Alloys Compd. 602 (2014) 122–129.
[28] S. Mansour, M. Abdo, S. El-Dek, Improvement of physico-mechanical properties of
Mg–Zn nanoferrites via Cr3+ doping, J. Magn. Magn Mater. 422 (2017) 105–111.
The authors declare that they have no known competing financial
[29] M. Lodhi, M. Khan, M. Akhtar, M. Warsi, D.A. Mahmood, S. Ramay, Role of Nd-Ni
interests or personal relationships that could have appeared to influence on structural, spectral and dielectric properties of strontium-barium based nano-
the work reported in this paper. sized X-type ferrites, Ceram. Int. 44 (2017).
[30] A. Majeed, M.A. Khan, F.u. Raheem, A. Hussain, F. Iqbal, G. Murtaza, M.N. Akhtar,
I. Shakir, M.F. Warsi, Structural elucidation and magnetic behavior evaluation of
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