JID:PLA AID:24295 /DIS Doctopic: Condensed matter [m5G; v1.199; Prn:2/02/2017; 12:40] P.

1 (1-7)
Physics Letters A ••• (••••) •••–•••

Contents lists available at ScienceDirect

Physics Letters A
www.elsevier.com/locate/pla

Discussion

Multiferroic properties of Indian natural ilmenite

Truptimayee Acharya ∗ , R.N.P. Choudhary
Department of Physics, Siksha ‘O’ Anusandhan University, Bhubaneswar 751030, India

a r t i c l e i n f o a b s t r a c t

Article history: In this communication, the main results and analysis of extensive studies of electric and magnetic char-
Received 1 November 2016 acteristics (relative dielectric constant, tangent loss, electric polarization, electric transport, impedance,
Received in revised form 10 January 2017 magnetic polarization and magneto-electric coupling coefficient) of Indian natural ilmenite (NI) have been
Accepted 12 January 2017
presented. Preliminary structural analysis was studied by Rietveld refinement of room temperature XRD
Available online xxxx
Communicated by L. Ghivelder
data, which suggests the rhombohedral crystal system of NI. Maxwell–Wagner mechanism was used to
explain the nature of the frequency dependence of the relative dielectric constant. The impedance anal-
Keywords: ysis reveals that below 270 ◦ C, only the bulk contributes, whereas at higher temperature, both grain
X-ray diffraction boundary and the bulk contribute to the resistive characteristics of the material. The magnitude of the
Maxwell–Wagner mechanism depression angles of the semicircles in the Nyquist plot has been estimated. The correlated barrier hop-
Impedance ping model has been used to explain the frequency dependence of ac conductivity of the material. The
Magneto-electric coefficient activation energy of the compound has been estimated using the temperature dependence of dc con-
ductivity plot. The obtained polarization hysteresis loops manifest improper ferroelectric behavior of NI.
The existence M–H hysteresis loop supports anti-ferromagnetism in the studied material. The magneto-
electric voltage coupling coefficient is found to be 0.7 mV/cm Oe. Hence, other than dielectric constant,
electric polarization, magnetization and magneto-electric studies support the existence of multiferroic
properties in NI.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Ilmenite, an interesting and economically important mineral, is
abundantly available in nature. It is an igneous rock derived from
the upper mantle level at about a depth of 400 km, and thus with-
stands pressure of 12–13 GPa [1]. Though it is mainly iron, tita-
nium oxide (with the idealized formula FeTiO3 ), it contains appre-
ciable amount of magnesium and manganese with the full chemi-
cal formula (Fe, Mg, Mn, Ti) O3. Since its discovery, its importance
has grown manifold, and now-a-days it is considered as the most
important ore of titanium. It is upgraded to titanium dioxide (TiO2 )
to be used for many applications, such as, catalysts, solar batter-
ies, ceramic materials, paper, and plastic, paint color and cosmetic
industries [2–4]. Due to its efficiency to scatter visible light, it is
widely accepted as the most important white pigment in the coat-
ing industry. Unlike the lead pigment, this white pigment is com-
pletely safe for human health. This is also used to provide color for
cosmetics, leather, ceramics, ink, textiles, plastics rubber, and pa-
per. Again, titanium (Ti) is a strong, lightweight and non-corrosive
metal with very high strength. Therefore, it can also withstand
* Corresponding author. Fax: +91 674 2351217.
E-mail address: truptiacharya18@gmail.com (T. Acharya).
temperature extremes due to its high melting point (1800 ◦ C). Due
to its high strength/weight ratio and ability to maintain its me-
chanical properties at high temperatures, alloys and compounds
of Ti are used in space vehicles, high tech airplanes, missiles and
also in surgical implants. Titanium and titanium compounds are
also used in electrical components, desalination plants, glass prod-
ucts, artificial gemstones, jewelry and even as smoke screens. As
titanium metals are nonreactive, these are suitably used in the
human body for orthopedic applications and also in pacemakers.
Detailed studies of temperature dependence of various properties
of the natural and synthesized ilmenite have provided some inter-
esting data useful for applications [5–8]. The effect of microwave
heating on electrical properties of low grade Panzhihua and natu-
ral ilmenite has also been reported [9]. Based on the first principle,
Wilson et al. [1] have reported the crystal structure and some elec-
trical properties of natural ilmenite. The basic crystal structure and
some electrical characteristics of bismuth-modified Indian natural
ilmenite have been reported by Choudhury et al. [10]. Nowadays,
much emphasis is given to the discovery and development of ma-
terials with simultaneous occurrence of multiple phenomenon’s
(ferroelectricity and magnetism in a distorted system) and ordering
in a single phase, usually referred as multiferroics. Detailed liter-
ature survey on multiferroic properties of natural ilmenite could
not provide much work on multiferroic properties of the natural

http://dx.doi.org/10.1016/j.physleta.2017.01.025
0375-9601/© 2017 Elsevier B.V. All rights reserved.
JID:PLA AID:24295 /DIS Doctopic: Condensed matter
2 T. Acharya, R.N.P. Choudhary / Physics Letters A ••• (••••) •••–•••
Fig. 1. (a) Observed (blue dot), calculated (black solid line) patterns and difference curve (bottom black line) of the Rietveld refinement results of NI at room temperature.
(b) Williamson Hall Plot of NI at room temperature. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this
article.)
ilmenite (collected from Kerala (India)). Basically, the most techno-
logically appealing multiferroics are those where the ferroelectric-
ity and ferromagnetism coexist in the same phase. The coupling
between theses ferroic orders, known as the magneto-electric cou-
pling holds promise to produce new interesting functional appli-
cations. The magneto-electric coupling implies the possibilities of
controlling the magnetic properties by electric field [11] and vice-
versa [12] and hence, pioneers new opportunities in the sphere of
magnetic memories, sensors, transducers and other technological
applications [13]. In NI, with off centre distortion of 3d0 state of
B-site (on ABO3 type of perovskite), Ti ions of ilmenite (FeTiO3 )
dominates to get ferroelectric polarization, and magnetic ordering
may arise due to partially filled d shell of A-site transition metal
ions (like Fe, Mn, Ni, etc.). In view of this, there is a possibility of
ilmenite being multiferroic. Therefore, we have carried out exten-
sive studies of ferroelectric, magnetic and magneto-electric effect
of the material.
2. Experimental details
The natural ilmenite (NI) was obtained from Indian Rare Earth
Ltd., Kerala. The major chemical composition of the natural il-
menite ore is: TiO2 (31.04%), Fe2 O3 + FeO (35%), SiO2 (17.32%). All
the details regarding pallets formation and characterizations (like
structural, micro-structural, dielectric, impedance, conductivity, fer-
roelectricity analysis) were already given in some of our earlier
publications [14,15]. The magneto-electric coefficient of the mate-
rial was obtained by using magneto-electric equipment interfaced
with a lock-in amplifier (SR830) provided by M/s Marine India PVT
Limited.
3. Results and discussion
3.1. Structural studies
The Rietveld refinement technique was used to determine the
phase and basic crystal structure of NI using XRD profiles collected
in a wide range of Bragg angles with slow scan (3◦ /min) and Cu
target. Fig. 1 exhibits the observed (blue dotted line), calculated
(solid black line) and the difference (shown at the bottom) peaks
of the X-ray pattern obtained from the Rietveld refinement of NI
at room temperature. Here MAUD program [16] was used to de-
termine the crystal structure, lattice parameters along with the
space group of NI. The previously prepared CIF file was used in
the Rietveld refinement of the sample. The lowest reliability pa-
rameters (unit weighted residual factor (R exp ), weighted residual
factor ( R w )) and the goodness of fit indicator (σ = R w / R exp ) are
used to check the rationality and validity of the final structural
[m5G; v1.199; Prn:2/02/2017; 12:40] P.2 (1-7)
refinement, However, the best method of judging the accomplish-
ment of Rietveld refinement is obtained by observing the best fit
between the observed and calculated intensity patterns (Fig. 1)
[17]. A rhombohedral (hexagonal) crystal symmetry with space
group R3-H (H = hexagonal) was obtained for NI with refined unit
cell parameters: a = 5.076 Å and c = 14.032 Å which are consis-
tent with those of multiferroic bismuth ferrite. The refinements
of parameters with several cycles led the refined value of resid-
ual parameters as: R w = 7.85%, R nw = 0.0785%, R exp = 3.223% and
sigma = 2.43 which are very much acceptable for accurate refine-
ment.
We have also calculated the coherently scattered grain size ( D )
of NI, by putting the full peak width at half maximum (FWHM =
β1/2 ) in the Williamson–Hall relationship [18],
λ
β1/2 cos θ = 2ε sin θ + (1)
D
where all the terms have the usual meaning. The particle size
has been calculated from the intercept and the slope determines
the strain. From the graph, the calculated crystallite/particle size
and strain are 76 nm and 0.00129 respectively. The instrumental
broadening of the diffractometer was ignored in the calculation of
particle size.
3.2. Micro-structural studies
Fig. 2(a), (b) exhibits the energy dispersive X-ray spectra (EDS)
spectra and scanning electron micrograph of NI. From EDX spectra,
we can conclude that NI contains only Fe, Ti, O, and Si elements.
Thus, from analysis of EDX, the composition of NI was obtained
as: FeO (19.96%), Fe2 O3 (15.27%), TiO2 (31.04%) and SiO2 (17.36%).
These compositions of NI were found slightly different from their
actual composition, as EDX is a semi-quantitative method with
some inherent limitations to detect of light elements including
oxygen. The weight percentage of oxygen, silicon, titanium and
iron is found to be 35.12, 6.61, 19.9, and 38.37%, respectively,
with respective atomic weight percentages of 62.13, 6.67, 11.76 and
19.44%. So, the obtained atoms per formula unit of O, Si, Ti, and
Fe are respectively 9.31, 1.0, 1.76, and 2.91. The microstructure of
NI (Fig. 2(b)) reveals the presence of almost rectangular grains of
non-uniform size distributed throughout the sample.
3.3. Dielectric properties
3.3.1. Frequency effect
Fig. 3(a)–(b) exhibits the frequency–temperature dependence of
εr (relative dielectric constant) and tan δ (loss tangent) of nat-
ural ilmenite. The behavior of graphs of εr shows a general di-
electric behavior (decreasing with an increase in frequency) of NI.
JID:PLA AID:24295 /DIS Doctopic: Condensed matter [m5G; v1.199; Prn:2/02/2017; 12:40] P.3 (1-7)
T. Acharya, R.N.P. Choudhary / Physics Letters A ••• (••••) •••–••• 3

Fig. 2. (a) EDX spectra and (b) SEM micrograph of NI.

Fig. 3. Variation of relative (a) dielectric constant (εr ) and (b) tan δ with frequency at different temperature of natural ilmenite.

Fig. 4. Variation of (a) relative dielectric constant (εr ) and (b) tangent loss (tan ð) with temperature at different frequency of natural ilmenite.

The value of relative dielectric constant of the sample at 1 kHz
(400 ◦ C) is found to be 7380. This large value can be explained
by the Maxwell–Wagner (M–W) mechanism of space charge po-
larization. During the impedance analysis of NI, it was observed
that the grains have low resistances as well as low activation en-
ergies, whereas the grain boundaries posses high resistances and
activation energies. The main reason of large values of εr at low
frequency may be explained with a model (internal barrier layer
capacitor (IBLC)) connected to the conducting grains with the in-
sulating grain boundaries ( gb ) [19]. The value of tangent loss of
NI also decreases with increase in frequency in the similar fash-
ion as of dielectric constant, which can also be explained by M–W
mechanisms [14,20]. As per M–W mechanism, electrons are more
dynamic at gb at low frequency, whereas in the high-frequency re-
gion they became more dynamic at grains. From the impedance
analysis, it was seen that grain boundaries posses higher resis-
tances than grains. So, in the low frequency region motion of
charge carriers requires more energy due to the high values of re-
sistance and hence, in this region, the loss tangent (tan δ) is also
high. Because of the low resistances of grains at high temperatures,
the motion of charge carriers requires less energy, and as a result,
we observed low tangent loss.
3.3.2. Temperature effect
Fig. 4(a)–(b) shows the temperature–frequency dependence of
εr and tan δ of natural ilmenite. It was observed that with in-
JID:PLA AID:24295 /DIS Doctopic: Condensed matter
4 T. Acharya, R.N.P. Choudhary / Physics Letters A ••• (••••) •••–•••
Fig. 5. Variation of Z  with Z  of natural ilmenite at different temperatures.
Fig. 6. Variation of (a) grain and (b) grain boundary resistances of NI with inverse of absolute temperature.
creasing temperature, the value of εr first increases and then de-
creases at a temperature usually referred as transition temperature
(T c ). With a rise in temperature, the space charge carriers become
more mobile and thus the space charge polarization increases. This
leads to increase in conductivity and dielectric constant. Above
T c the domains disappear, and hence dielectric constant decreases
[21]. This phase transition may be assumed to be related to the
ferroelectric–paraelectric transition which needs to be confirmed
by polarization measurement. Again, rapid increase of dielectric
constant at higher temperatures (≥400 ◦ C) indicates the increased
space charge conduction, which relates to the movement of defects
such as oxygen vacancies toward the dielectric–electrode interface.
Microwave treated natural ilmenite shows the phase transition at
167 ◦ C by Chiteme et al. [9]. But the transition temperature of the
studied NI is found out to be 344 ◦ C in the present study. The
temperature dependent plot of tan δ (Fig. 3(b)) has well defined
peak.
3.4. Impedance studies
Fig. 5 exhibits Z  vs. Z  (Nyquist) plots of natural ilmenute as
a function of temperature and frequency (1 kHz–1 MHz). High-
frequency semicircles of the insulating ceramics depict the bulk
effect, whereas semicircles formed at low frequency is due to
gb (grain boundary) resistance. These arcs represent the type of
the relaxation mechanism in the system. An occurrence of perfect
semicircular arc with its centre on the Z  axis at any temperature
confirms the existence of single relaxation time with homogeneous
grain distribution. The depressed and asymmetric semicircular arcs
indicate the distribution of relaxation time due to inhomogeneity
[m5G; v1.199; Prn:2/02/2017; 12:40] P.4 (1-7)
in grain size and electromagnetic diffusion [22]. The depressed an-
gle of natural ilmenite suggests the displacement of the impedance
plane below the real axis; it suggests the deviation of the mech-
anism from the ideal Debye-type response [23]. Only a single
semicircle is observed at 270 ◦ C, whereas at the higher temper-
atures (≥275 ◦ C), a clear semicircular arc with tendency to form
a second semicircle (with center below the real axis) is observed.
Thus at higher temperatures, the grain boundary effect appears the
grain contributions are stronger than the grain boundary contribu-
tion in NI. The intercepts of the semicircular arcs on the real axis
( Z  ) give a value of bulk resistance (R b ) and grain boundary re-
sistance ( R gb ). These values of the samples are given in Table 1.
The values of R b and R gb decrease with the rise in temperature
indicating negative temperature coefficient of resistance (NTCR)
behavior [24]. Higher value of R gb and R g compared at higher
temperatures suggests that the M–W mechanism dominates in the
high-temperature and low-frequency region, and thus results in
the occurrence of the huge εr value of the material. As per M–W
mechanism [25], it is assumed that the material is composed of
the less resistive/semiconductor grains and more resistive/insulat-
ing grain boundaries. The activation energy ( E a ), of the grain and
grain boundary has been estimated separately by plotting the bulk
resistance vs. temperature and the grain boundary resistance vs.
temperature individually (Fig. 6(a)–(b)). The nature of variation of
resistances follows the simple relations’, R = R 0 + Ae E a / K B T , where
symbols have their usual meaning. The activation energies can be
obtained from the slopes of the plots was found to be 0.67 eV and
0.88 eV respectively for grain and grain boundary respectively. This
provides a potential barrier of 0.21 eV.
JID:PLA AID:24295 /DIS Doctopic: Condensed matter [m5G; v1.199; Prn:2/02/2017; 12:40] P.5 (1-7)
T. Acharya, R.N.P. Choudhary / Physics Letters A ••• (••••) •••–••• 5

Fig. 7. Variation of ac conductivity of NI (a) with frequency at different temperature and (b) with temperature at different frequency. (c) Variation of dc conductivity of NI
with temperature.

Table 1
Value of frequency exponent s at different temperature in various frequency ranges and Comparison of grain resistance (R b ), grain capacitance (C b ), grain boundary resistance
( R gb ), grain boundary capacitance (C gb ) of NI at some selected temperatures.
Temp. Frequency exponent ‘s’ Rb Cb R gb C gb
in ◦ C Low freq. Intermediate High freq. (in  cm2 ) (in F/cm2 ) (in  cm2 ) (in F/cm2 )
region freq. region region
100 0.38 – 0.54 2.169 × 106 1.15 × 10−10 – –
150 0.26 – 0.41 2.949 × 105 1.14 × 10−10 – –
200 0.13 – 0.3 3.798 × 104 1.12 × 10−10 – –
250 0.19 – 0.26 5999 7.26 × 10−10 – –
300 0.18 0.02 0.22 1272 5.58 × 10−10 1501 7.45 × 10−10
350 0.17 0.01 0.13 239 1.71 × 10−9 358.2 1.12 × 10−10

3.5. Electrical conductivity
The following simple relation is used to calculate electrical
(ac) conductivity of material using measured dielectric parame-
ters σac = ω tan δ ε0 εr where symbols have their usual meaning.
Fig. 7(a) exhibits the frequency–temperature dependence of elec-
trical conductivity (σac ) of ilmenite. Plots clearly show that σac in-
creases on increasing frequency following the equation, σac = A ω s
(or log σac = log A + s log ω ), where the ω = angular frequency,
A = temperature dependent constant and s = frequency expo-
nent [26]. From plots, we can see that above 300 ◦ C, the curves
may be divided into three distinct frequency regions; (a) low-
frequency (1 kHz–10 kHz), (b) intermediate frequency (10 kHz
to 100 kHz) and (c) high frequency (100 kHz to 1 MHz). Be-
low 300 ◦ C, conductivity curves have two distinct regions. In the
impedance analysis we have seen that up to 275 ◦ C, a single semi-
circular arc (corresponding to grain effect) was observed. However,
at higher temperatures two semicircles are observed in the Nyquist
plot, which correspond to the grain boundary effect. At higher
frequency, the grains or bulk mainly dominates, but at low fre-
quencies the grain boundary is more effective. Thus grain boundary
resistance is mainly responsible for the conductivity of the mate-
rial at low-frequency and high-temperatures. These situations of
transport properties can be explained by the M–W mechanism.
The electrical conductivity of the intermediate frequency region on
the low-temperature can be explained using the said mechanism.
The values of the slopes and the frequency exponent (Table 1) in
the low, intermediate and high-frequency range change suggest
the existence of different types of conduction mechanisms such
as small polaron hopping [27], correlated barrier hopping (CBH)
[28], overlapping large polaron tunneling (OLPT) [29] and Quantum
mechanical tunneling model (QMT) [30]. With increasing tempera-
ture, the value of s decreases at all the temperature and frequency.
This behavior of electrical conduction can be explained by the CBH
model [28]. Using CBH model, the frequency exponent ‘s’ can be
calculated by
6kT
s=1− (2)
W m + kT ln(ωτ0 )
where, W m = maximum barrier height at infinite inter site sepa-
ration, k = the Boltzmann constant and τ0 = the relaxation time.
Fig. 7(b) exhibits the change of electrical conductivity of NI with
the inverse of absolute temperature at some selected frequency.
The activation energies were calculated from the slope of the plot
on the basis of the Arrhenius equation
 
−Ea
σ = σ0 exp (3)
kB T
The calculated activation energy of the material at high tempera-
ture is found to be 0.3 eV in the wide range of study frequency.
But in the intermediate temperature range, activation energy de-
creases from 0.7 eV at 1 kHz to 0.5 eV at 1 MHz for NI sample.
The value of activation energy more than 0.2 eV confirms that the
conduction mechanism is of hopping type [18].
Fig. 7(c) shows the temperature dependence of DC conductivity
which governs the Arrhenius relation,
σ DC = σ0 exp(− E a / K B T ) (4)
where σ0 = pre-exponential factor, K B = Boltzmann constant and
E a = activation energy of the mobile charge carriers. The calcu-
lated activation energies 0.4 and 0.9 eV correspond to low and
high temperature regions respectively. These high values of acti-
vation energies suggest that a small amount of energy activates
charges carriers for conduction process. The nature of temperature
dependent DC conductivity suggests the semi-conducting nature of
the material. During high temperature sintering, oxygen vacancies
are created with two trapped electrons [31]:
JID:PLA AID:24295 /DIS Doctopic: Condensed matter [m5G; v1.199; Prn:2/02/2017; 12:40] P.6 (1-7)
6 T. Acharya, R.N.P. Choudhary / Physics Letters A ••• (••••) •••–•••

Fig. 8. Room temperature (a) P–E hysteresis loop; (b) M–H hysteresis loop; (c) Variation of ME voltage coefficients with DC magnetic field of NI.

O0 → 1/2O2 ↑ + V 0 + e− (5) opening of the hysteresis loop is not very large, the nature of the
curve supports the field induced alignment of canted spins in the
here V 0 denotes oxygen vacancies. In the reduction reaction, two
sample. As a non-rectangular shape of hysteresis loop represents a
excess electrons are created and thus electrons may bond with
canted anti-ferromagnetic material [36,37], NI sample shows anti-
Ti4+ to form Ti3+ as: Ti4+ + 1e ↔ Ti3+ [32]. These oxygen va-
ferromagnetic behavior with a coercivity of (2HC ) of 180 Oe and
cancies and the trapped electrons can be activated thermally, and
a remnant magnetization (2M r ) of 0.104 emu/g, which in turns
in turns, enhanced the conduction process. Hence, in most of the
indicates that the magnetic properties in NI are observed to be
titanates, these oxygen vacancies and mobile charges play a vital
enhanced than some of the synthetic ilmenites like NiTiO3 [38],
role in the conduction process [32].
synthesized FeTiO3 [39] etc.

3.6. Multiferroicity
3.6.3. Magneto-electric study
The magneto-electric (ME) effect refers to the induction of mag-
Multiferroicity is defined as the simultaneous ordering of elec-
netic polarization by applying an external electric field and vice
trical and magnetic degrees of freedom. So, NI can be considered
versa. As both electric and magnetic ordering have been observed
as multiferroic, if it will exhibit more than one primary ferroic pri-
in NI, we have carried out the study of ME effect in the material.
mary order parameter simultaneously. Thus, to manifest multifer-
Fig. 8(c) shows ME voltage co-efficient as a function of magnetic
roicity in NI, detailed experimental studies on the field dependent
field from −5 to 5 kOe for NI at room temperature. In the as per
electric polarization, magnetization and magneto-electric coupling
the impedance analysis, only the bulk contribution was effective
coefficient of the sample at room temperature have been carried
even in the coupling between electric polarization and magneti-
out.
zation in the bulk of the sample at room temperature. The ME
voltage coefficient, βe is given as [40],
3.6.1. Polarization study
Fig. 8(a) shows the room temperature polarization hysteresis βe = dE /dH = V /h0 d (6)
loop (P–E loop) of NI, measured at various fields at a constant
frequency of 100 kHz. The occurrence of the P–E hysteresis loops where, E, H , V , h0 and d are the induced electric field, mag-
confirms the ferroelectricity in NI, which is supported by the tem- netic field applied, the magneto-electric voltage developed across
perature dependent dielectric anomaly. It is observed that on the the sample, the magnitude of the AC induced magnetic field and
increasing electric field the polarization first increases, and then it thickness of the sample respectively. Magneto-electric coupling co-
decreases on attaining a maximum value. The decrease of polariza- efficient (βe ) was measured by using the dynamic method, where
tion from its maximum value may be due to time delay between both AC and DC magnetic fields were applied simultaneously [41].
electric field and polarization. Though we had observed the PE Here 15.37 Oe alternating current induced magnetic field was ap-
hysteresis loops for NI, still the obtained loops don’t exhibit sat- plied at a frequency of 1 kHz. A Helmholtz coil (driven by an AC
uration effect and such type of unsaturated hysteresis loops are current) of 200 turns, 25 mm radius, and resistance of coil 23.4 
characteristics of leaky capacitors. Hence, NI can be considered produced the AC field. The value of h0 at the center of the coil was
as of an improper ferroelectric. The improper ferroelectricity was estimated using the following formula:
also reported earlier in some compounds like SmFeO3 [26], GdFeO3 μ0 2π N Ir 2 μ0 N I NV
[33], some of the rare earth orthoferrites [34,35] etc. It can be ob- h0 = 2 3
×2= 3
= 8.99 × 10−3 ∗ Oe (7)
4π (r 2 + ) 2
r
(4)2 r
5 rR
served that the remnant polarization ( P r ) and coercive field (E C ) 4
increased with increasing electric field. The remnant polarization
Here, we had applied 5 V AC amplitude to the coil to obtain a
(2P r ) measured at 4 kV and 5 kV (at 100 Hz) is found to be
magnetic field of 15.37 Oe. The following relation was used to de-
0.04 μC/cm2 and 0.05 μC/cm2 respectively.
termine the magneto-electric voltage developed across the sample
[42]:
3.6.2. Magnetization study
Fig. 8(b) exhibits the field dependence of magnetization of NI V
at room temperature carried out between fields of −12.5 kOe to
E= = f ( H ) = constant + α H + β H 2 + γ H 3 + δ H 4 + · · ·
d
12.5 kOe. The magnetic hysteresis loop does not show a tendency dE
for saturation with increasing applied magnetic field. Though the ⇒ =∝ +2β H + 3γ H 2 + 4δ H 3 + · · · (8)
dH
JID:PLA AID:24295 /DIS Doctopic: Condensed matter
T. Acharya, R.N.P. Choudhary / Physics Letters A ••• (••••) •••–•••
The total magnetic field is H total = H + h0 sin ωt. Initially ME co-
efficient increases with increasing magnetic field (DC) because of
the enhancement in elastic interaction with increasing magnetic
field [43]. It attains a maximum value of 0.7 mV/cm Oe at 1 kOe,
and then gradually decreases. Beyond 1 kOe the magnetization
and thus the strain would produce a constant electric field in the
piezoelectric phase. This leads to decrease in dE /dH with increas-
ing in magnetic field [44,45].
4. Conclusion
An extensive experimental work was executed to evince multi-
ferroicity in the Indian natural ilmenite. The rhombohedral struc-
ture of NI was confirmed from the XRD analysis and through
the Rietveld refinement of the sample. Using the Williamson–Hall
relationship, the calculated crystallite/particle size and strain are
determined as 76 nm and 0.00129 respectively. The scanning elec-
tron micrograph images show the presence of almost rectangular
grains of non-uniform size distributed throughout the sample. The
EDX analysis of composition and the presence of elements of the
sample confirmed the formation of the desired compound. The
dielectric parameters of NI are found to be strongly depending
on temperature and frequency. The analysis of Nyquist plots of
the sample shows the major contribution of bulk or grains below
270 ◦ C, whereas both grain/bulk and grain boundary contribute
towards the polarization of the material at high temperatures. De-
tailed studies of resistance of the sample due to grain/bulk and
grain boundary resistances suggest that natural ilmenite can easily
and appropriately be characterized by a relatively insulating grain
boundaries and conducting grains. Based on the M–W mechanism
we can easily observe the major contribution of grain boundary at
the low frequency and high temperatures. From our detailed study
of the temperature dependence of resistance, the estimated po-
tential barrier (separating the grain and grain boundary) is found
to be 0.21 eV. The formation of IBLC (internal barrier layer ca-
pacitor) layer at the boundary explains the existence of huge di-
electric constant of NI in the said experimental conditions. Study
of temperature dependence of transport properties shows nega-
tive temperature coefficient of resistance behavior in NI in wide
temperature range. Based on detailed studies of electric polariza-
tion (P–E loop) and magnetization (M–H hysteresis loop) in dif-
ferent experimental condition, existence of improper ferroelectric
and anti-ferromagnetism behavior of natural ilmenite is confirmed.
From magneto-electric measurements provided magneto-electric
coefficient or voltage of 0.7 mV/cm Oe. Thus the natural Indian il-
menite (Kerala) exhibits multiferroic characteristics such as high
dielectric constant, low tangent loss and negative temperature co-
efficient of resistance, etc. These properties seem to be helpful
to fabricate some multifunctional devices including semiconduc-
tor devices, sensors, thermal, electrics and microwave-based com-
munication sensors, gate dielectrics, multistate memory devices,
miniature capacitor for telecommunications, actuators, transducers
and energy storage devices, etc.
Summary statement
Conflict of interest: The authors declare that they have no conflict
of interest.
Acknowledgements
The authors are grateful to Prof. R.R. Dash of GIET, Gunpur,
Odisha for providing NI sample and also to Dr. Perumal Alagarsamy
of IIT, Guwahati for his kind helps in some experiments.
References
[1] N.C. Wilson, J. Muscat, D. Mkhonto, P.E. Ngoepe, N.M. Harrison, Phys. Rev. B 71
(2005) 075202.
[m5G; v1.199; Prn:2/02/2017; 12:40] P.7 (1-7)
7
[2] Sayekti Wahyuningsih, Ari Handono Ramelan, Edi Pramono, Ariantama
Djatisulistya, Int. J. Sci. Res. Publ. 4 (11) (2014).
[3] A. Vidal, Chemosphere 36 (1998) 2593–2602.
[4] Y. Wu, J. Du, K.L. Choy, L.L. Hench, Mater. Sci. Eng. A 454–455 (2007) 148–155.
[5] Ling Wu, Xinhai Li, Zhixing Wang, Huajun Guo, Xiaojuan Wang, Feixiang Wu,
Jie Fang, Zhiguo Wang, Lingjun Li, J. Alloys Compd. 506 (2010) 271–278.
[6] Yu-ming Wang, Zhang-fu Yuan, Zhan-cheng Guo, Qiang-qiang Tan, Zhao-yi Li,
Wei-zhong Jiang, Trans. Nonferr. Met. Soc. China 23 (2013) 3462–3469.
[7] Guo Chen, Jin Chen, Shenghui Guo, Jun Li, C. Srinivasakannan, Jinhui Peng,
Appl. Surf. Sci. 258 (2012) 4826–4829.
[8] Chen-hui Liu, Li-bo Zhang, Jin-hui Peng, Bing-guo Liu, Hong-ying Xia, Xiao-
chun Gu, Yi-feng Shi, Trans. Nonferr. Met. Soc. China 23 (2013) 3462–3469.
[9] C. Chiteme, A.F. Mulaba-Bafubiandi, J. Mater. Sci. 41 (2006) 2365–2372.
[10] R.N.P. Choudhury, Biswajit Pati, Piyush R. Das, R.R. Dash, Ankita Paul, J. Electron.
Mater. 42 (2013).
[11] Thomas Lottermoser, Thomas Lonkai, Uwe Amann, Dietmar Hohlwein, Jörg
Ihringer, Manfred Fiebig, Magnetic phase control by an electric field, Nature
430 (2004) 541–544.
[12] T. Kimura, T. Goto, H. Shintani, K. Ishizaka, T. Arima, Y. Tokura, Magnetic control
of ferroelectric polarization, Nature 426 (2003) 55–58.
[13] Reji Thomas, J.F. Scott, Dwarka N. Bose, Ram S. Katiyar, Multiferroic thin-film
integration onto semiconductor devices, J. Phys. Condens. Matter 22 (2010)
423201.
[14] Truptimayee Acharya, R.N.P. Choudhary, Appl. Phys. A 121 (2015) 707–714.
[15] Truptimayee Acharya, R.N.P. Choudhary, Phys. Lett. A 380 (2016) 2437–2444.
[16] http://www.ing.unitn.it/maud/index.html.
[17] A.Z. Simões, L.S. Cavalcanteb, F. Moura, E. Longo, J.A. Varela, J. Alloys Compd.
509 (2011) 5326–5335.
[18] P. Shanthakumar, M. Balasubramanian, D.M. Pease, A.I. Frenkel, D.M. Potrepka,
V. Kraizman, J.I. Budnick, W.A. Hines, Phys. Rev. B 74 (2006) 174103.
[19] P.K. Jana, S. Sarkar, B.K. Chaudhuri, J. Phys. D, Appl. Phys. 40 (556) (2007).
[20] Nidhi Adhlakha, K.L. Yadav, Ripandeep Singh, Smart Mater. Struct. 23 (2014)
105024, 16 pp.
[21] A.S. Fawzi, Adv. Appl. Sci. Res. 2 (2011) 577.
[22] B. Garbarz-Glos, W. Bak, ˛ M. Antonova, M. Pawlik, Mater. Sci. Eng. 49 (2013)
012031.
[23] K.D. Chandrasekhar, A.K. Das, C. Mitra, A. Venimadhav, J. Phys. Condens. Matter
24 (2012) 495901.
[24] Truptimayee Acharya, R.N.P. Choudhary, Mater. Chem. Phys. 177 (2016)
131–139.
[25] George Mathew, S. Nair Swapna, K.A. Malini, P.A. Joy, M.R. Anantharaman,
J. Phys. D, Appl. Phys. 40 (2007) 1593.
[26] Sushrisangita Sahoo, P.K. Mahapatra, R.N.P. Choudhary, J. Phys. D, Appl. Phys.
49 (2016) 035302, 13 pp.
[27] E.V. Gopalan, K.A. Malini, S. Sagar, D.S. Kumar, Y. Yoshida, I.A. Al-Omari, M.R.
Anantharaman, J. Phys. D, Appl. Phys. 42 (2009) 165005.
[28] F.A. Abdel-wahab, H.M. Maksoud, M.F. Kotkata, J. Phys. D, Appl. Phys. 39 (2006)
190.
[29] A. Ghosh, S. Bhattacharya, D.P. Bhattacharya, A. Ghosh, J. Phys. Condens. Matter
20 (2008) 035203.
[30] M. Pollak, T.H. Geballe, Phys. Rev. 122 (1961) 1742.
[31] Konapala Sambasiva Rao, Kuan China Varada Rajulu, Bollepalli Tilak, Anem
Swathi, Nat. Sci. 2 (2010) 357–367.
[32] T. Badapanda, V. Senthil, S.K. Rout, S. Panigrahi, T.P. Sinha, Mater. Chem. Phys.
16 (2012) 863–870.
[33] Sushrisangita Sahoo, P.K. Mahapatra, R.N.P. Choudhary, M.L. Nandagoswami,
Ashok Kumar, Mater. Res. Express 3 (2016) 065017.
[34] X. Wanga, S. Cao, Y. Wanga, S. Yuan, B. Kang, A. Wu, J. Zhang, J. Cryst. Growth
362 (2013) 216.
[35] H.J. Zhao, Y. Yang, W. Ren, A.J. Mao, X.M. Chen, L. Bellaiche, J. Phys. Condens.
Matter 26 (2014) 472201.
[36] D.L. Cortie, A.P.J. Stampfl, F. Klose, Y. Du, X.L. Wang, H.Y. Zhao, H. Kimura, Z.X.
Cheng, Appl. Phys. Lett. 101 (2012) 172404.
[37] R.N. Bhowmik, A. Saravanan, J. Appl. Phys. 107 (2010) 053916.
[38] Truptimayee Acharya, R.N.P. Choudhury, J. Electron. Mater. 44 (2015) 271–280.
[39] Craig J. Fennie, Phys. Rev. Lett. 100 (2008) 167203.
[40] Poonam Pahuja, Chandra Prakash, R.P. Tandon, Ceram. Int. 40 (2014)
5731–5743.
[41] J.G. Wan, X.W. Wang, Y.J. Wu, M. Zeng, Y. Wang, H. Jiang, W.Q. Zhou, G.H. Wang,
J.M. Liu, Appl. Phys. Lett. 86 (2005) 122501.
[42] G.V. Duonga, R. Groessinger, M. Schoenhart, D. Bueno-Basques, J. Magn. Magn.
Mater. 316 (2007) 390.
[43] Ce-wen Nan, Phys. Rev. B 50 (1994) 6082.
[44] S.V. Suryanaryana, Bull. Mater. Sci. 17 (1994) 1259.
[45] K.K. Patankar, R.P. Nipankar, V.L. Mathe, R.P. Mahajan, S.A. Patil, Ceram. Int. 27
(2001) 853–858.