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Structural and magnetic characteristics of NiO/NiFe2O4/α-Fe2O3 nanocomposite

B. Sahu, U.K. Panigrahi, C.J. Sheppard, A.R.E. Prinsloo, P. Mohanty, P. Mallick

PII: S0254-0584(23)00467-4
DOI: https://doi.org/10.1016/j.matchemphys.2023.127759
Reference: MAC 127759

To appear in: Materials Chemistry and Physics

Received Date: 28 November 2022

Revised Date: 29 March 2023
Accepted Date: 9 April 2023

Please cite this article as: B. Sahu, U.K. Panigrahi, C.J. Sheppard, A.R.E. Prinsloo, P. Mohanty, P.
Mallick, Structural and magnetic characteristics of NiO/NiFe2O4/α-Fe2O3 nanocomposite, Materials
Chemistry and Physics (2023), doi: https://doi.org/10.1016/j.matchemphys.2023.127759.

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B. Sahu: Formal analysis, Investigation, Methodology, Writing - original draft

U.K. Panigrahi: Formal analysis, Investigation, Methodology, Writing - original draft

C.J. Sheppard: Data curation, Validation, Editing

A.R.E. Prinsloo: Data curation, Validation, Editing

P. Mohanty: Data curation, Validation, Editing

P. Mallick: Conceptualization, Investigation, Supervision, Validation, Editing

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 Structural and Magnetic Characteristics of NiO/NiFe2O4/α-Fe2O3
Nanocomposite
B. Sahu1,#, U.K. Panigrahi1,#, C.J. Sheppard2, A.R.E. Prinsloo2, P. Mohanty2 and P. Mallick1*
1
Department of Physics, Maharaja Sriram Chandra Bhanja Deo University, Baripada 757003, India
2
Cr Research Group, Department of Physics, University of Johannesburg, Johannesburg, PO Box
524, Auckland Park, South Africa.
*e-mail: [email protected]
#
First two co-authors (B. Sahu and U.K. Panigrahi) have contributed equally to this work

Abstract
Effect of Fe concentration in forming NiO/NiFe2O4/α-Fe2O3 nanocomposite (NC) was probed

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through structural and magnetic characterizations. Presence of two-magnon mode in Raman
spectra confirms the existence of NiFe2O4 and α-Fe2O3 phases in the background of

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antiferromagnetic (AFM) NiO matrix. Magnetic study further confirms the occurrence of weak

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ferromagnetism in the AFM background. The behaviour of temperature dependence of saturation
magnetization revealed that the samples exhibit some type of inhomogeneity. The NC samples
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show robust exchange bias characteristics at room temperature. The occurrence of ferromagnetic
like feature in the NC samples could be due to the combine effect of the formation of BMP along
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with the magnetic inhomogeneity. The samples show the persistence of robust exchange bias field
at 300K. The amplification of anisotropic constant with higher Fe concentration in the NC
sample could be ideal for device applications like magnetic recording media.
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Keywords: Nanocomposite; exchange bias; magnetism; BMP model

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1. Introduction
In recent years, spinel ferities nanoparticles are more attractive to scientific community
due to their unique properties like moderate magnetic loss in kHz range and high Curie
temperature which leads to multifunctional application in heat inductors [1], microwave heating
[1], self-combustion [2], magnetic recording [3], gas sensors [1,4] catalysts [5] and magnetic
resonance imaging (MRI) [6]. Among the different application of spinel ferrites one of the most
favorable areas of the practical use of spinels nanoparticles are biomedical application [7,8].
Research activities on the nanocomposite (NC) systems have attracted the attention of the
materials science community due to their synergetic properties encouraged by the interactions
among two or more different phases present in the systems [9]. In the nanoscale regime, the
transition from a single component to composite systems provides abundant possibilities for
modifying the performance of the subsequent composite [10–12]. From literature it is evident
that the addition of secondary phase with in the host matrix can significantly modifiy the
electronic as well as magnetic properties of resulting composite material [13–16]. Dippong et al.
[3] reported that CoFe2O4 embedded in PVA-SiO2 hybrid matrix could be useful for catalyst
and magnetic application. It has also been evident that ceramics nanoparticle embedded in
polymer matric would exhibit increased microwave properties [17,18]. Among the different NC
materials, the bi-magnetic NC materials have the potential applications in the field of Li ion
batteries [19–21], energy storage devices [19], catalyst [22,23], drug delivery [24,25], water
splitting [26,27], permanents magnets [28,29], etc.

Among the different characteristic features that emerged due to the synergetic effects in

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bi-magnetic nanomaterial systems, the exchange bias (EB) effect is one of the significant

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properties which is evolved among the magnetic interaction between the antiferromagnetic

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(AFM) and ferromagnetic (FM) phases [30–32]. In magnetic NC materials, the EB characteristic
has extended much attention due to its use in spintronics devices [33,34], magnetic tunnel
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junction [35], spin valves [36], magnetic storage media [33,37], magnetic sensors [38,39],
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recording-heads [36], magnetoresistive random-access circuits [40], high density magnetic disks
[41] etc. The observation of EB coupling in AFM/FM interface has fascinated considerable
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attention after discovery by Meiklejohn and Bean in 1956 [42]. In addition to FM/AFM systems,
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EB may also be detected in NC samples comprising a ferrimagnet (FiM) (FiM/AFM, FM/FiM)

or a spin-glass (SG) phase (FiM /SG, AFM/SG) [43]. Among these, AFM/FM or AFM/FiM NC
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system would provide surplus degrees of freedom to progress the properties of the material for
industrial application [26–29,44]. Further, the studies of NC systems comprising the triple phases
are of interest to investigate the EB characteristics [45].

In the present work, we synthesized NiO/NiFe2O4/α-Fe2O3 NC following a simple wet

chemical method. Our study indicated (i) the persistence of exchange bias characteristics in the
NC samples, (ii) the temperature dependent saturation magnetization suggests the presence of
some type of defects in the NC samples and (iii) the occurrence of ferromagnetic-like features in
the NC samples which could be due to the combined effect of BMP formation and the magnetic
inhomogeneity.
2. Experimental
There are different synthesis methods available in literature to synthesize the oxide based
composite materials [15,46]. We have adopted a low cost effective wet chemical method to
synthesize 5 and 10% Fe doped NiO nanoparticles using stoichiometric amount of nickel nitrate
[Ni(NO3)2. 6H2O] and iron nitrate [Fe(NO3)2. 9H2O]. These initial precursor salts were added
with distilled water to make a solution. These solutions were subjected separately to
homogenization using magnetic stirrer for 1h. The as-prepared solutions are then dried on a hot
plate. The obtained samples are initially calcined at 3000 C for 1 h and then at 5000 C for 1h to
obtain desired NC samples in powder form. The NC samples prepared from 5 and 10% of Fe

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doped NiO henceforth are named as NC5 and NC10.

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Structural analysis of the NC samples was undertaken by using a Bruker X-ray
diffractometer (Model: D8 Advance) working with CuKα radiation (λ= 1.5406 Å). Raman

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spectra of the NC samples were recorded using Jobin Yvon Horibra Raman spectrometer
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(LABRAM-HR). The magnetization measurements of the samples were performed using a
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cryogen-free PPMS vibrating sample magnetometer (VSM, Cryogenic Pty, Ltd) insert.
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3. Results and Discussion

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3.1. Structural Analysis by XRD

Figure 1 illustrates the XRD pattern of both the samples. The XRD pattern confirms the
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appearance of major peaks matching to the cubic phase of NiO along with two additional phases
comprising of NiFe2O4 (JCPDS Card No-86-2267) and α-Fe2O3 (JCPDS Card No-89-8103)). It
seems that both the additional phases are embedded in the NiO matrix in forming the composite
system. It is observed that the intensity of NiFe2O4 and α-Fe2O3 increases with increasing Fe
concentration during synthesis i.e., for the NC10 sample. Since these additional phases (NiFe2O4
and α-Fe2O3) bear low intensity peaks, we, therefore, calculate the crystallite size of the NiO
phase only using Debye-Scherrer formula (D = 0.9 /  cos ) . The crystallite size of the NiO
matrix is ~26 and 25 nm for NC5 and NC10 samples, respectively, whereas the same for the pure
NiO is ~29 nm [47]. It is found that the Fe doping in NiO disturbs the crystal lattice and hence,
prevents the growth of crystal. A similar type observation has also been seen by Wang et al. [48].
The decrease in particle size with Fe doping in NiO could be due to the presence of Fe3+, which
leads to increase of nucleation points in the NiO nanoparticles [49]. Since, all the phases are in
the nanometer regime, the synthesized samples comprising of NiO/NiFe2O4/α-Fe2O3 are ternary
NC sample.

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Figure 1: XRD pattern of NC5 and NC10 samples.

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3.2. Transmission Electron Microscope (TEM) Analysis

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Figure 2 illustrates the TEM images of NC5 and NC10 samples. TEM image of NC5
samples indicates that all the nanoparticles are spherical nature with little agglomeration. The
agglomeration is seemed to be increased with increasing of Fe concentration could be due to the
more magnetic nature of the samples. In addition, the shape transformation from spherical to
elliptical nature is evidenced.
 Figure 2: TEM image of (a) NC5 and (b) NC10 samples.

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3.3. Structural Analysis by Raman Spectroscopy

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Figure 3 represents the Raman spectra of the NC samples. The appearance of peaks at

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~226 cm-1 correspond to A1g mode of Fe2O3 phase [50]. The peak at ~292, 409 and 809 cm-1
attributed to Eg modes of Fe2O3 phases in NC5 and NC10 samples [50,51]. The appearance of a
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peak at ~697 in the samples signifies the presence A1g mode of NiFe2O4 [19,52] phase. The
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presence of peak at ~653 cm-1 could be attributed to the Ag mode of Fe3O4 phase [53]. The peaks
at ~548 and 695 cm-1 corresponds to LO and TO mode of NiO, respectively. The appearance of
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TO and LO mode directed the occurrence of nickel vacancy at the zone center of the samples due
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to parity breaking defects [47]. The peak at 1066 cm-1 was attributed to 2LO mode of NiO and
this peak shifted to a higher wave number (~1126 cm-1) with increasing Fe concentration from 5
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to 10%. The shifting of 2LO mode to higher wavenumber with increasing size of NiO has been
reported due to size induced phonon confinement [54–56]. Since the crystallite size in the
present case is larger to see the confinement effect and the crystallite size is slightly decreased
with Fe concentration, we, therefore, believe that this shifting could be due to Fe induced
modification in the crystal environment. The preservation of AFM background through the Ni2+-
O2--Ni2+ superexchange interaction is also probed through the presence of 2M mode [47,57,58].
Further, the shifting of 2M mode NiO present at ~1514 cm-1 to a higher wave number with
increasing Fe doping concentration could be due to the chemical substitution induced
suppression of local symmetry at Ni2+ site [57]. It has been reported the 2Eu(LO) mode of α-
Fe2O3 phase at 1320 cm-1 could be shifted to higher wavenumber with increasing pressure [59].
We, therefore, believe that the occurrence of the peaks at ~1369 and 1330 cm-1 in Raman spectra
corresponds to Fe concentration induced change in the chemical environment around the α-Fe2O3
phase [60]. A reduction in chemical pressure around the α-Fe2O3 phase could lead to a shift in
this band to a lower wavenumber with increasing Fe concentrations from 5 to 10 % in the NiO
matrix [59].

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Figure 3: Raman spectra of NC5 and NC10 samples.

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3.4. Magnetic Characteristics

Figure 4 represents the variation of magnetization (M) as a function of temperature (T)
for NC5, and NC10 samples under zero field cooled (ZFC) and field cooled (FC) conditions at
the constant applied field (H) of 0.01T. In the NC samples, both ZFC and FC magnetization
continuously decreases with the decrease of T up to ~50 K. Thereafter, the ZFC and FC
magnetization increases with decreasing T, which is due to the freezing process of surface spins
with reduced coordination [61]. The appearance of a sharp peak at 250 K in both of the curve
(ZFC and FC) in NC5 sample could be due to the Morin transition associated with the α-Fe2O3
phase [62] present in the NC sample. This peak in both ZFC and FC curves is suppressed with
increasing Fe concentration which could be due to the enhancement of NiFe2O4 phase fraction in
the sample. Further, the Morin transition is not only suppressed but also the magnetic moment is
increased when the measurement is undertaken at high applied magnetic fields (Fig. 4 (c)). This
could be due to the high field induced biasing of magnetic moments. It is worth mentioning here
that ZFC and FC curves overlap when measured at an applied field higher than the coercive field
[63]. We therefore observed the merging of ZFC and FC curves measured at 0.05T.

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Figure 4: Variation of M as a function of T under ZFC and FC condition for (a) NC5 (b) NC10
(c) ZFC and FC curve as mentioned for NC5 sample at different applied constant H.

In order to further probe into the magnetic properties of the NC samples, the hysteresis
loop (M vs. H) (Fig. 5) was recorded at different T. The presence of distinct hysteresis loop at
different T and the absence of saturation magnetization even at high magnetic field regions
demonstrate the presence of a weak FM/FiM phase in the background of AFM NiO matrix. The
non-saturation magnetization behaviour of samples due to the presence of AFM phase, which is
also confirmed 2M band presence in Raman spectra associated with Ni2+-O2−-Ni2+ super-
exchange interaction [47,64]. In bulk phase NiO exhibits AFM behaviour. When the size of NiO
is shortened to nanoscale, its magnetic properties drastically changes and shows different
anomalous magnetic features such as superparamagnetic, ferromagnetic, spin glass and core-
shell etc. [65]. The presence of a clear hysteresis loop in NiO nanostructures has been reported
by Panigrahi et al. [47], which could be due to the presence of core-shell structure along with the
high anisotropy associated irregular shape of NiO nanoparticles. Wang et al. [48] attributed that
the RT ferromagnetism (RTFM) in Fe doped NiO nanoparticles is due to FM clusters and

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FM/AFM coupling due to the composition inhomogeneity. Mallick et al. [66] reveals that the
same in Fe doped NiO nanoparticles to finite size effect and magnetic inhomogeneity.

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Ponnusamy et al. [49] demonstrated that the RTFM in Fe doped NiO is linked with the

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dependency of shape, magnetic direction, crystallinity and particle size. We, therefore, believe
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that the observation of hysteresis loop in the NC samples could be due to the particle size and
magnetic inhomogeneity effects.
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Figure 5: M-H curve of (a) NC5 (b) NC10 samples measured at different temperature and inset
showing amplified person of corresponding M-H curve.

As stated above, the EB characteristic is one of the interesting features appeared in the magnetic
NC systems. We therefore calculated the exchange bias field ( H EB ) for the present study using
H EB = (H1 + H 2 ) / 2 . Here H 1 and H 2 are left and right fields in hysteresis loop when the value
of M becomes zero. Figure 6 illustrates the variation of H EB with T for NC5 and NC10 samples.
Since the α-Fe2O3 phase is expected to show AFM features below its Morin transition (at ~ 250
0
C), therefore both α-Fe2O3 and NiO would contribute as AFM phases, whereas the NiFe2O4
would contribute as the FiM phase. So, the interaction between AFM and FiM would give rise to
the EB effect in the samples. The samples show negative H EB at all T could be due to pinning of
uncompensated surface spin of AFM surface interfaced with the FiM spin of NiFe2O4 [67]. The
evolution of the H EB with T in the present case could be associated with the magnetic interaction

of different phases present in the NC samples. The decrease in H EB with increasing T and

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completely vanishing of the same at and above 150K has also been reported in similar type of

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systems [68,69]. Therefore, the persistence of robust H EB at 300K in the present study is an
important observation.
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Figure 6: Variation of HEB vs T for NC5 and NC10 samples.

The value of saturation magnetization ( M s ) of the samples can be determined by fitting

M-H curve at the high field to following relation [70–72]:

  8  K1  
2

M = M S 1−   + kH (1)
 105  M S H  
 
where K1 is the anisotropic (cubic) constant and k is the susceptibility at high field regime.
Figure 7 represent the M-H data taken in 1st interval (i.e., 0 to H) at different temperatures for the
NC samples fitted to Eq. (1) beyond 20000 Oe. The K1 is one of the valuable parameters for
FM/FiM material which facilitates to utilize them in magnetic recording media application [9].
The values of M S , K1 and k extracted from the fitting of the experimental data are reflected in

Table 1. It is observed that these values are amplified from NC5 to NC10, i.e., with increasing

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Fe concentration from 5 to 10% in NiO. The calculated values of K1 is nicely matched with the

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previously reported work [9]. Though the value of K1 decreases slightly with the rise in
temperature, but the value of the same is significant at 290K. Our calculated values of K1 is

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consistent with the reported literature [73,74]. This could be useful for designing a thermal stable
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magnetic device with enhanced performance [75].
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Figure 7: Variation of M with H for (a) NC5 and (b) NC10 samples taken in first interval (i.e., 0
to H) recorded at different temperature. The solid line represents to the fitted data to the
experimental data as per Eq. (1).
Table 1: The value of M s , K1 and k for NC5 and NC10 samples obtained from fitting of M-H
curve with Eq. (1).

T (K) NC5 NC10

Ms K1 (×104) k Ms K1 (×104) k
(emu/g) (erg/g) (erg/g) (erg/g)
10 1.251 2.822 1.562 1.643 3.467 1.783
50 1.245 2.653 1.428 1.655 3.414 1.648
100 1.223 2.619 1.359 1.626 3.364 1.687
200 1.175 2.619 1.378 1.539 3.118 1.745
280 0.999 1.942 1.569 1.394 2.984 1.666
290 1.021 2.160 1.431 1.394 2.984 1.666

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Figure 8 displays the variation of M s with T which is fitted to modified Bloch’s as stated below

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[76]:
  T  
M S (T ) = M S (0) 1 −   
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  T0  

For the magnetic nanoparticles, the reported value of critical exponent (  ) is close to 2. In our
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case, we found the  value is equal to 2.96 and 2.23 for NC5 and NC10 samples respectively.
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This result indicates that our samples exhibit some type of defects.
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Figure 8: Variation of M s vs T for NC5 and NC10 samples. The solid/dotted line represents the
fitted curve as per Eq. (2).
 Since our samples exhibits some type of defects, therefore we have fitted M-H data of the
samples using modified Brillouin function and it can be expressed as [9,77,78]:

M Brillouin−( H − A ) mod el = M Brillouin + M ( H − A ) mod el (3)

AH
M ( H − A ) mod el = (4)
(B + H )
 2J + 1  (2 J + 1)x  1  x 
M Brillouin = NgJ B  coth  − coth   (5)
 2J  2J  2J  2 J 
where A and B are the H-A model parameters and N represents the number of cation sites per

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gram. As per Brown's theory, the H-A model can explain the magnetization of the materials

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embracing random defects [77]. Since the major phase fraction of the NC samples is NiO and
J = 4 for Ni2+ ion [79,80], we therefore fitted the M-H curve (Fig. 9) of NC samples to J = 4 . It

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is observed that the data nicely fitted to Eq. (3) and obtained values ( N , A and B ) from fitting
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for the NC samples at different T are reflected in Table 2. It is observed that the value of N
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increases with increasing T for both the NC samples while the same decreases with increasing Fe
concentrations from 5 to 10 %.
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Figure 9: Variation of M vs H for (a) NC5 and (b) NC10 samples taken in first interval (i.e. 0 to
H) measured at different temperature. The solid line represents the fitted data to corresponding
experimental data as per Eq. (3).
Table 2: The values of N, A and B for NC5 and NC10 samples obtained from fitting of the M-H
curve with Eq. (3) at different T.

T (K) NC5 NC10

N (1021) A (emu/g) B (Oe) N (1021) A (emu/g) B (Oe)
10 2.719 1.105 1642.075 2.336 1.464 1440.675
50 2.794 1.059 972.934 2.441 1.459 1236.235
100 2.879 1.032 1049.086 2.456 1.453 1383.093
200 2.916 0.999 1183.606 2.533 1.419 1631.151
280 2.993 0.918 1332.605 2.725 1.302 1950.768
290 3.146 0.921 1481.545 2.715 1.298 1925.763

There are several models such as double exchange, Rudermann–Kittel–Kausya–Yoshida

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(RKKY) interaction, free carrier- mediated exchange, super exchange, Bound Magnetic Polaron
(BMP) and sp–f exchange mechanism available in literature to explain the origin of

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ferromagnetisms in oxide materials as well as composite material [81]. Among them, the BMP is

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one of the model which partially explain the origin of ferromagnetism in our samples. To
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understand the source of ferromagnetism in our samples, we fitted the M-H data to BMP model.
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According to this model [82–85], the M is expressed as

M = M 0 L(x ) +  m H (6a)
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The first term in the expression signifies the contribution of the BMP’s and 2nd term represent
the matrix contribution. In this case, M 0 = N ms , N  is the number of BMPs involved, ms is the
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effective spontaneous moment per BMP and  m is the susceptibility of the matrix. The Langevin
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function, L(x ) is given by [86];

L( x ) = coth ( x ) −
1
(6b)
x
meff H
with x= (6c)
K BT
Now Eq. (6a) would turn out to be
 1
M = M 0  coth ( x ) −  +  m H (7)
 x
Figure 10 demonstrated the experimental M-H data of NC samples taken in 1st interval (i.e. 0 to
H) measured at different T. The line (solid) resembles to the fitted curve to the experimental data
as per the Eq. (7). At higher T, we have taken m s = meff by neglecting BMPs interaction. The

fitted values of M 0 , m eff and  m are listed in Table 3. It is found that the values of M 0 and N 
increased with increasing Fe doping concentration in NiO. Further, in particular sample, the M 0

is decreased and m eff is increased with increasing measuring temperature. Also, the number of

BMP is decreased with increasing temperature. The decrease of m eff and considerable increase

in  m at low temperature could be associated with the reduction in BMP size [86]. The decrease

of number of BMP with the rise of temperature could be due to increase of BMP size as well as
due to increase in competing interaction between different magnetic phases present in the
sample. In addition, for the perfect percolation and long-range FM order, the order of BMP
should be ~1020 per cm-3. We however obtain the order of BMP is 1017 per cm-3 which is three

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orders of magnitude lesser than the required concentrations. Therefore, the BMP model alone is
not able to explain the occurrence of ferromagnetism in our case [9,87].

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Figure 10: BMP model fitting of M-H data of (a) NC5 (b) NC10 samples at different T fitted
with Eq. (7).
Table 3: The BMP model fitting parameter ( M 0 , m eff ,  m and N  ) of Fe doped NiO samples at
different temperatures.
T NC5 NC10
(K) M0 m eff m N M0 m eff m N  (×1017
17
(emu/g) ( × 10-17 (×10 (emu/g) ( × 10-17 cm-3)
emu) cm-3) emu)
10 1.008 0.168 0.023 40.036 1.348 0.187 0.026 48.125
50 0.992 1.247 0.022 5.305 1.356 1.066 0.025 8.486
100 0.970 2.651 0.021 2.441 1.342 1.938 0.025 4.618
200 0.932 4.422 0.021 1.405 1.297 3.356 0.025 2.578
280 0.851 5.553 0.020 1.023 1.175 4.035 0.023 1.943
290 0.848 5.271 0.019 1.073 1.173 4.229 0.023 1.849
4. Conclusion
The NC5 and NC10 samples were successfully synthesized by a simple wet chemical
route. Structural characterization indicated the NiFe2O4 and α-Fe2O3 phases embedded in the
NiO matrix in forming the ternary nanocomposite system. Magnetic characterization revealed the
occurrence of weak ferromagnetism in the AFM background. The presence of 2M mode in the
Raman spectra further supported the persistence of the background AFM ordering of the NiO
matrix. The NC samples show exchange bias characteristics. The occurrence of ferromagnetic-
like features in the NC samples could be due to the combine effect of BMP formation and the
magnetic inhomogeneity. The amplification of anisotropic constant in the NC10 sample could be

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ideal for device applications like magnetic recording media.

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Acknowledgements

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PM acknowledges the DST, Govt. of Odisha for providing financial support to carry out this
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work. BS acknowledges OURIIP, OSHEC, Govt. of Odisha for financial support. CRS, AREPS
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and PM acknowledge the financial support from the South African National Research
Foundation (Grant No: 88080) and the URC/FRC, University of Johannesburg (UJ), South
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Africa.
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➢ NiO/NiFe2O4/α-Fe2O3 nanocomposite is synthesized by a cost effective wet chemical
route.
➢ Occurrence of weak ferromagnetism in the AFM background is confirmed.
➢ Temperature dependence of saturation magnetization revealed the presence of magnetic
inhomogeneity in the system.
➢ Samples show robust exchange bias characteristics at room temperature.
➢ Amplification of anisotropic constant with higher Fe concentration in the NC sample
could be ideal for magnetic device applications.

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Declaration of interests

☒ 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.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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.

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