Ceramics International 48 (2022) 14473–14480

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Significant impact of spinel ferrites in evolution of magneto-electric

coupling in novel tri-phase composites
Muhammad Umair a, Abdul Quader a, Muhammad Imran a, Muhammad Atif Yaqub a,
Shahid M. Ramay b, Shahid Atiq a, *
a
Centre of Excellence in Solid State Physics, University of the Punjab, Lahore, Pakistan
b
Physics and Astronomy Department, King Saud University (KSU), Riyadh, Saudi Arabia

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

Keywords: Multiferroic materials have played an important role in recent technological breakthroughs because of their
Multiferroics intrinsic magneto-electric coupling characteristics. In this framework, a cost effective and reliable sol–gel auto-
Magneto-electric coupling combustion method was used to synthesize the 0.8[(1-x) BiFeO3 + xFe3O4] + 0.2Cr2O3 (x = 0.0, 0.2, 0.4, 0.6, 0.8
Composites
and 1) nanocomposites. X-ray diffraction was used to identify three phases and their unique crystal parameters.
Spinel ferrites
Elemental composition of the samples was verified using an energy dispersive X-ray spectroscopy. Field emission
Energy storage density
scanning electron microscopy revealed distinct, well-shaped, and spherical grains when the spinel-ferrite con­
tents were introduced to the series. An irregular behavior in the bulk porosity was observed, courtesy to the
ImageJ software. The vibrating sample magnetometer, operated at ±7 kOe, showed an increase in saturation
magnetism. A rigorous analysis of recoverable energy density, energy loss density, and other ferroelectric pa­
rameters had been presented, demonstrating the potential of the proposed recipe for energy storage devices. The
synthesized specimens demonstrated remarkable magneto-electric coupling at optimal content levels.

1. Introduction ME coupling has a prolonged historical background. Recently, most

Amazing phenomena of magneto-electric (ME) coupling, intrinsi­
cally present in multiferroic (MF) materials has captivated the re­
searchers for its notable significance in multifunctional devices. The
basic requirement for practically viable ME coupling in such MFs is that
they must possess significant and simultaneous, more than one ferroic-
orders (magnetic/electric/elastic) to realize the dream of tinier sized
devices in the modern era [1–3]. Hence, the enhanced ME coupling in
MF materials, provide strong justification to make these materials which
are potential candidates for multifunctional devices [4]. Although, the
ME coupling in MF materials plays a vital role in practical applications
but their use is limited at room temperature (RT) due to some micro­
scopic constraints [5]. For instance, low electrical resistivity and large
leakage currents hinder the practical utilizations of single- and bi-phase
MF materials [6–9]. In this context, a sophisticated approach is estab­
lished to overcome the difficulties by the formation of tri-phase com­
posites. These composites are able to surpass the mentioned deficiencies
and especially, to improve the required range for the ME coupling co­
efficients [1,10–13].
of the researchers are working on ME coupling in BiFeO3 (BFO) and
trying their best to make it significant [14]. BFO possesses ABO3 dis­
torted perovskite like structure with R3c space group, in which A-site
occupies the Bi atom at corners for example, then B-site possesses iron
(Fe) as the central atom tilting with oxygen (O) atoms in the arrange­
ment of the unit cell [15]. The Curie temperature (TC) and Néel tem­
perature (TN) for BFO are ~1103 K and ~643 K, respectively [14].
Magnetization in BFO can be improved via different substitutions in
ceramics [16] and thin films [17], and hence the consequent improve­
ments in ME coupling yet render it fit for advanced technological aspects
[18,19]. The researchers have been making various efforts to undertake
reported difficulties since the discovery of BFO. Recently, different ME
composites were prepared through several configurations e.g.,
BFO-NCZFO (Ni, Co, Zn doped BFO) [20] and erbium (Er) doped BFO
[21] that suggest the disparity between the large value of saturation
magnetization (Ms) and smaller value of coercivity (Hc). This charac­
teristic is considered to be fundamental recipe for future research in­
terests about sensors and memory devices. Nanocomposites (1-x)
BiFeO3-xAFe2O4 (A = Mn, Zn, Ni) synthesized by Narayana et al. [22],

* Corresponding author.
E-mail address: satiq.cssp@pu.edu.pk (S. Atiq).

https://doi.org/10.1016/j.ceramint.2022.01.340
Received 14 November 2021; Received in revised form 28 January 2022; Accepted 30 January 2022
Available online 2 February 2022
0272-8842/© 2022 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
M. Umair et al.
were prepared to investigate the effect of spinel ferrite on ME coupling
features of BFO. Oanh et al., studied co-doped BFO (Ni and Gd) which
exposed the enhancement in saturation polarization (Ps), remanent po­
larization (Pr), Ms, remanent magnetization (Mr), and complex
dielectric-based properties. These outcomes showed the supremacy of
BFO for future research interests in ferroelectric and ferromagnetic
studies [23].
However, tri-phase composites come into play to alleviate the issues
encountered by pure, bi-phase BFO-based composites and to improve
ME coupling. For instance, (1-x)[0.7BiFeO3-0.3CoFe2O4] - xPb(Zr, Ti)O3
[24], poly vinylidene fluoride (PVDF)-BFO-Carbon black (CB) [25],
BaTiO3–Ni0.5Zn0.5Fe2O4–BaFe12O19 [26], BaTiO3–BiFeO3-BiYbO3 [27]
have been reported with better ME coupling, enhanced dielectric con­
stants and reduced leakage current. But these innovations are not
enough to fulfill the futuristic technological demands. Besides these
developments, there are still some gaps for researchers to make the
advancements in FE and ME response.
In this regard, here we present an efficient tri-phase composite of the
form 0.8[(1-x) BiFeO3 + xFe3O4] + 0.2Cr2O3, where x = 0.0, 0.2, 0.4,
0.6, 0.8 and 1.0. In this process we have chosen BFO being the only
multiferroic material giving good ferroelectric and antiferromagnetic
response above RT. Meanwhile, Fe3O4 has been chosen as a good
ferrimagnetic material and Cr2O3 as a fine ferroelectric material. The
appropriate combination of these three phases is intended to assist us in
developing a recipe with excellent ME response.
2. Experimental
In this work, tri-phase composites of the form 0.8[(1–x)BiFeO3 +
xFe3O4] + 0.2Cr2O3 with x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0 were pre­
pared via cost-effective sol–gel auto-combustion and ball-milling
method. Metal nitrates i.e., bismuth, iron and chromium nitrates with
purity greater than 99% were used as precursors. Urea and glycine were
utilized as fuel agents. Metal nitrates to fuel ratio was considered as 1:2.
The solution was placed on a hot plate with 110 ◦ C temperature and a
magnetic stirrer was utilized for continuous mixing of distinct solutions
of the precursors and fuel agents. When the gel was formed, the stirring
was stopped and temperature of the hot plate was gradually raised to
Fig. 1. Synthesis schematics of the composite samples.
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Ceramics International 48 (2022) 14473–14480
250 ◦ C in steps of 25 ◦ C. Consequently, an abrupt combustion yielded
the gel into a fluffy ash. An Agate mortar and pestle was used to grind the
fluffy ash into fine powders of BFO, Fe3O4 and Cr2O3, separately. BFO
powder was calcined at 550 ◦ C for 3 h, while the powders of Fe3O4 and
Cr2O3 were individually calcined at 800 ◦ C for 2 h for proper develop­
ment of the crystalline phases.
To prepare the composites solid state technique was utilized. All the
powders in definite proportion were jumbled in ball milling chamber.
These composites were then converted in pellets with 7 mm diameter
and ~1 mm thickness using Apex hydraulic press with the force of 40
kN. The pellets were then sintered in the muffle furnace at 300 ◦ C. Fig. 1
shows the synthesis process of our specimens.
To analyze the crystal structure, an advanced Bruker D8 X-ray
diffractometer (XRD) was used with CuKα radiations at RT. NovaNano
SEM 450, field emission scanning electron microscope (FESEM) was
used for the analysis of microstructures and grain sizes at different
substitutions. Energy dispersive X-ray spectroscopy (EDX) technique
was used for the integrity and affirmation of the elemental compositions
of prepared samples. Vibrating sample magnetometer (VSM) by Lake­
shore was used to elaborate magnetic response. Precision multiferroic
system by Radiant Tech. (USA) was utilized to analyze the FE features
and ME coupling.
3. Results and discussion
Fig. 2 reveals the intensity peaks for the 0.8[(1–x)BiFeO3 + xFe3O4]
+ 0.2Cr2O3 composites in the range of 10◦ –80◦ . The diffraction peaks for
BFO can be seen at 2θ values of 22.4◦ , 31.7◦ , 32.0◦ , 39.0◦ , 39.5◦ , 45.7◦ ,
51.3◦ , 51.76◦ , 67.0◦ , 71.4◦ , 71.72◦ , 75.6◦ and 76.1◦ corresponding to hkl
values (100), (110), (1 1 0), (111), (11 1), (200), (210), (21 0), (22 0),
(300), (22 1), (310) and (31 0), respectively. The peaks are associated to
inorganic crystal structure database (ICSD) reference card number 01-
072-2035 that exposes rhombohedral crystal system belonging to R-
3m space group. For Cr2O3, intensity peaks can be seen at 2θ values of
24.5◦ , 33.60◦ , 54.8◦ and 57.1◦ corresponding to hkl values (012), (104),
(116) and (211), respectively. The peaks are well matched with ICSD
reference card no. 01-082-1484 revealing the rhombohedral structure of
Cr2O3 with R-3c space group. Peaks of Fe3O4 reveals cubic crystal system
M. Umair et al.
Fig. 2. X-ray diffraction patterns of 0.8[(1–x)BiFeO3 + xFe3O4] + 0.2Cr2O3
composite sample for x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0.
at 2θ values of 18.2◦ , 30.09◦ , 35.4◦ , 37.05◦ , 43.05◦ , 53.3◦ and 62.51◦
corresponding to hkl planes (111), (220), (311), (222), (400), (422) and
(440), respectively corresponding to ICSD reference card no. 00-019-
0629 exposing that Fe3O4 has Fd-3m space group. The marvelous re­
sults were observed after a detailed study of the prepared composites
about the maintaining the identity of all compositions and successfully
developing the structure. Hence, throughout series for BFO, Fe3O4 and
Cr2O3, no any phase shift noticed.
FESEM images of 0.8[(1–x)BiFeO3 + xFe3O4] + 0.2Cr2O3 composites
at x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0 are obtained due to the emission of
electrons through the filament and striking the sample’s surface.
Consequently, some of them scatter back and are detected by the de­
tectors. FESEM images are taken at particular magnification to study the
particle size distribution, porosity, grain size and surface morphology.
Fig. 3 reveals the images at x200,000 magnification and average grain
size is calculated to be 50, 83, 45, 82, 51, and 46 nm for x = 0.0, 0.2, 0.4,
0.6, 0.8 and 1.0, respectively. These FESEM images show decreasing
trend of the grain size with substitutional values and reveal the spher­
ical, sharp, and distinct shapes of the grains. Mostly, same trend is shown
Fig. 3. SEM images obtained at x200,000 magnification for the 0.8[(1–x)BiFeO3 + xFe3O4] + 0.2Cr2O3 composite samples with x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0.
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Ceramics International 48 (2022) 14473–14480
by the grains which reveal the homogeneous distributions of phases that
make it hard and complex to distinguish. Normally, the variation of the
grains size is in between 13 and 157 nm. In Fig. 4, (a) at x = 0.0, (b) at x
= 0.2 (c) at x = 0.4 (d) at x = 0.6 (e) at x = 0.8 and (f) at x = 1.0 where
red shaded areas are showing estimated bulk porosity percentage (%) of
the specimens, that is calculated to be 21.58%, 29%, 26.9%, 16%,
29.6%, and 19%, respectively. These bulk porosities are disclosed
through a graphical representation in Fig. 4 (g). The non-red shaded
areas are actually pointing out the grains of the prepared specimens.
Estimations of grains size, surface morphology and bulk porosity % for
FESEM images is studied through a Java-based ImageJ software.
The EDX spectroscopy is used to scrutinize the elemental composi­
tion of the prepared specimens via intensity versus energy spectrum
revealed by Fig. 5 which shows that each element holds unique atomic
structure [28]. EDX spectra shown in the figure confirms the presence of
Bi, Fe, Cr and O, in the exact stoichiometric contents as expected from
the empirical formulae of the 0.8[(1–x)BiFeO3 + xFe3O4] + 0.2Cr2O3
composite samples. The peaks related to C and Al appeared as a
contribution from the surroundings and conductive coatings on the
sample surface. This was another evidence of the successful and phase
pure synthesis of the composite samples. With the increasing concen­
tration of spinel ferrite in the composite samples, the intensity peaks
related to Bi were found to decrease and the intensity of peaks related to
Fe increased, as required from the respective compositions in the series.
Fig. 6(a) shows the magnetic hysteresis (M − H) loops which
demonstrate the correlation of magnetization (M) and applied magnetic
field (H). This type of the loop is created by computing the M which
comes out from the anti-ferro or the ferri-magnetic materials during
changing in the external magnetizing field. Principally, the M − H
curves give the evidence of how much our material is magnetized [29].
Fig. 6(b) shows distinctions between the values of Ms, Mr and Hc with
respect to substitution contents. The saturation behavior can be seen for
specimens with x = 0.0, 0.4, 0.6 and 1.0, while applying the ±7 kOe
magnetic field. This magnetic analysis shows an auspicious improve­
ment in Ms, Mr and Hc as Fe3O4 contents were added in series due to its
inverse spinel ferrite nature having negative magneto-crystalline
anisotropy K1. Hence, a tremendously enhancement of magnetic effect
noticed for prepared composites. The pragmatic values for Ms, Mr, and
Hc are given in Table 1. Maximum observed values of Ms, Mr, and Hc are
62.97, 12.06 emu/g and 13.7 Oe, respectively. The disparity between
the large value of Ms and smaller value of Hc shows research interest
about sensors and memory devices.
M. Umair et al. Ceramics International 48 (2022) 14473–14480

Fig. 4. Estimated porosity in the 0.8[(1–x)BiFeO3 + xFe3O4] + 0.2Cr2O3 composite samples obtained using SEM images for x = (a) 0.0, (b) 0.2, (c) 0.4, (d) 0.6, (e)
0.8 and (f) 1.0 respectively, and (g) a graphical representation of bulk porosity percentage versus substitution contents.

A phenomenon in which spontaneous polarization (P) can be density (WR), total energy density (WT), energy loss density (WL) and
reversed by applying the electric field (E) is called ferro-electricity. Di­ percentage efficiency (%η) are calculated via following formulae [31]:
rection of the P can be altered with the applied E. Material’s domains
∫Pm
expansion can be considered for these types of activities. Therefore, PE-
WR = EdP (1)
loops and other curves are drawn to obtain the results and information
to understand the FE behavior in better way [30]. Moreover, remaining Pr

P which was left in the material at zero value of external applied E, is

1
known as Pr. Maximum polarization (Pm) or Ps can also be observed WT = Pm E (2)
2
through the hysteresis loop. Coercive field (Ec), recoverable energy

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Fig. 6. (a) The M − H loops and (b) variations of saturation magnetization

Fig. 5. EDX spectra of the 0.8[(1–x)BiFeO3 + xFe3O4] + 0.2Cr2O3 composite (Ms), remanent magnetization (Mr) and coercive field (Hc) for the 0.8[(1–x)
samples for x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0. BiFeO3 + xFe3O4] + 0.2Cr2O3 composite samples with x = 0.0, 0.4, 0.6 and 1.0.

WL = WT − WR (3) Table 1
Evaluated values of Ms, Mr and Hc of 0.8[(1–x)BiFeO3 + xFe3O4] + 0.2Cr2O3
WR composite samples for x = 0,0, 0.4, 0.6 and 1.0
% η= ​ * ​ 100 (4)
WL + WR
Contents (x) Ms (emu/g) Mr (emu/g) Hc (Oe)
A tester named precision multiferroic analyzer is utilized to analyze
0 0.85 0.15 1.78
the P response, which is induced through applied E, at RT. A direct way 0.4 15.34 3.54 4.24
to inspect the ferroelectricity is hysteresis loop P versus E (PE) loop [30, 0.6 26.09 3.76 5.51
32]. 1 62.97 12.06 13.17
At the various concentrations of 0.8[(1–x)BiFeO3 + xFe3O4] +
0.2Cr2O3 composites, the PE-loops at RT are shown in Fig. 7(a). The
discharge curves for the series and Fig. 7(f) is the depiction of %η of the
clear indication for the uniformly distribution of the electric dipoles
prepared samples. So, for pure specimen the %η which is noticed about
inside the specimens is the symmetry of PE-loops at the origin. The
49.02%, which is suitable for energy storage applications. In Table 2, the
continuously enhancement of polarization via applying the external, is
values of the Pm, Pr, WR, WL, Ec and %η are enlisted, respectively.
the confirmation of the linear ferroelectricity of the samples [33]. Fig. 7
The Electric polarization may be generated by applying an external
(b) shows the extent of Pm and Pr values for various substitution con­
magnetic field, or magnetic moments can be induced by applying an
tents. For x = 0.0, the observed value of Pm and Pr are almost 4.14 × 10-4
external electric field, these lexes divulge superlative effect of ME
μC/cm2 and 3.12 × 10-4 μC/cm2, respectively. Moreover, at x = 1.0 the
coupling. Elastic contact via strain is primarily responsible for the
value of Pm enhanced to 5.80 × 10-4 μC/cm2 which is perceived as op­
mutual interphase coupling between the electric and magnetic phases
timum value and long-range ordering of the composites. The constant
[34]. The magnetic phase or electric phase of this strain is converted into
ratio of Pm and Pr implies the phase stability of the ferroelectric mate­
magnetic or electric charges via magneto-strictive or piezoelectric ef­
rials. The variation of different field strength exhibited in Fig. 7(c) and
fects. Moreover, these electric charges or magnetic charges with respect
discrepancy between the WR and WL is displayed in Fig. 7(d). The
to magnetic field or electric field, respectively, may also be used to
enhancement of the Pm means the greater number of diploes are aligned
modify electric/magnetic behavior by altering domain orientation and
due to application of external voltages assuring the more amount of the
orientational features. The coupling coefficient can be used to measure
energy stored. The maximum value for WR is 1.01 × 10-2 mJ/cm3. Fig. 7
the strength of the ME coupling effect [35]. Microstructures
(e) demonstrates the graphical representation for the charge and

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Fig. 7. (a) P-E loops, (b) maximum and remanent polarization (Pm & Pr) versus x, (c) P-E loops for different field strength, (d) variation in WR and WL as a function of
x, (e) graphical representation for the charge and discharge, and (f) % η versus substitutional contents for pure 0.8[(1–x)BiFeO3 + xFe3O4] + 0.2Cr2O3 composites.

(connectivity mode, shape, volume fraction, etc.) of composites are

Table 2
major factors in determining the value of this parameter. Consequently,
Ec, η%, WL, WR, Pr and Pm of 0.8[(1–x)BiFeO3 + xFe3O4] + 0.2Cr2O3 samples at
ME-coupling is a successive extrinsic in nature. Fig. 8 shows satisfactory
multiple substitution contents.
ME coupling of the prepared samples of the 0.8[(1–x)BiFeO3 + xFe3O4]
x Pm (μC/ Pr (μC/ WR (mJ/ WL (mJ/ η% Ec (V/
+ 0.2Cr2O3 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) composites. As after
cm2) cm2) cm3) cm3) cm)
applying the external magnetic field, a linear increasing trend about the
0.0 4.14 × 10- 3.12 × 1.01 × 10-2 1.06 × 10- 49.02 57.49 P can be seen in Fig. 8. These results variations can be ascribed to
4
10-4 2
- -3 - specimen’s porosity and grain size. Hence, by means of such linear
0.2 3.90 × 10 3.19 × 7.08 × 10 1.24 × 10 36.39 63.60
4
10-4 2 behavior between P and H, the existence of remarkable signal of
0.4 4.08 × 10- 3.34 × 7.33 × 10-3 1.31 × 10- 35.93 63.90 ME-coupling coefficient is revealed by the prepared composites.
4
10-4 2

0.6 3.40 × 10- 2.60 × 7.94 × 10-3 9.03 × 10- 46.80 58.60
4 4. Conclusion
10-4 3
- -3 -
0.8 3.85 × 10 3.21 × 6.40 × 10 1.28 × 10 33.30 65.19
4
10-4 2 The meticulously preparation of samples of BiFeO3, Fe3O4 and
1.0 5.80 × 10- 5.04 × 7.57 × 10-3 2.14 × 10- 26.11 69.31 Cr2O3, were individually synthesized via sol gel route due to need of
4
10-4 2
phase quality development. These samples were mixed via ball-milling
process to get tri-phase BiFeO3/Fe3O4/Cr2O3 composites with configu­
ration of 0.8[(1–x) BiFeO3 + xFe3O4] + 0.2Cr2O3 (x = 0.0, 0.2, 0.4, 0.6,

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M. Umair et al.
Fig. 8. ME response of polarization vs applied field for 0.8[(1–x)BiFeO3 + xFe3O4] + 0.2Cr2O3 composites for various values of substitution contents.
0.8 and 1.0). In this summary, multiple characterizations unveiled
attractive astonishing results. For the prepared samples, crystal param­
eters and phase purity identified by XRD. Spherically, sharp and distinct
shaped grains and the size of the grains, was realized through FESEM
images. Additionally, these FESEM images were also used for the esti­
mation of the bulk porosity percentage. Due to Fe3O4 substitutions in
prepared specimens, peaks intensity variations and compositions of el­
ements discovered via EDX. The maximum values of Ms, Mr and Hc are
obtained i.e., 62.97, 12.06 emu/g and 13.7 Oe, respectively. FE and ME-
coupling results were precisely surveyed by FE-tester. In addition, the
ferroelectric analysis reveals the trend of charging and discharging for
the PE curves at different substitution contents. For x = 0.0, the value of
Pm, Pr and WR are observed to be 4.14 × 10-4 μC/cm2 and 3.12 × 10-4
μC/cm2, 1.01 × 10-2 mJ/cm3 respectively, perceived. However, when
Fe3O4 concentration substituted in the sample at x = 1.0, then Pm is
enhanced to the 5.80 × 10-4 μC/cm2 and WR is remarked as 7.57 × 10-3
mJ/cm3. In the prepared specimens the electric polarizability is suc­
cessfully divulged by applying the external magnetic field of 45 G. These
results are efficient for energy storage devices and other technological
aspects in the field of engineering and technology.
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.
Acknowledgement
The authors would like to acknowledge the Researcher’s Supporting
Project Number (RSP-2021/71), King Saud University, Riyadh, Saudi
Arabia for their support in this work.
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