J Mater Sci: Mater Electron

DOI 10.1007/s10854-016-5834-1

Development of multiferroic polymer nanocomposite from PVDF

and (Bi0.5Ba0.25Sr0.25)(Fe0.5Ti0.5)O3
C. Behera1,2 • R. N. P. Choudhary1 • P. R. Das3

Received: 1 June 2016 / Accepted: 5 October 2016

Ó Springer Science+Business Media New York 2016

Abstract Thin films of some polymer–ceramics multifer- obtained first order magnetoelectric coefficient (aME) is
roic nanocomposites (in 0–3 connectivity) of compositions found to encouraging for multifunctional application. The
(1 - x)PVDF–x((Bi0.5Ba0.25Sr0.25)(Fe0.5Ti0.5)O3 (x = 0., improved conductivity and dielectric properties suggest
050.1,0.15)) have been prepared using a standard solution some promising applications in the embedded capacitors.
casting method. The basic structure and surface morphol-
ogy of the materials were studied using X-ray diffraction 1 Introduction
and scanning electron microscopy technique respectively.
Structural investigation confirms the presence of polymeric Multiferroic materials with high magneto-electric (ME) cou-
electro active b-phase of matrix (PVDF) and nano filler pling coefficient have attracted much attention of scientists
perovskite phase of the incorporated nano-ceramics. The and technologists because of some potential applications of
high resolution transmission electron micrograph of the the materials in different emerging technological fields such
prepared nano-ceramic thin film composite has shown as spintronics, sensor fabrication, magnetic storage, novel
distinct and uniformly distributed particles (with less circuits and high power applications. The design and devel-
agglomeration). This has been observed in SEM micro- opment of such type of materials with strong magneto electric
graphs also. The flexible nano-composites fabricated with coupling between magnetic and electric polarizations are very
polymer (PVDF), bismuth ferrite (BiFeO3) and ferroelec- much required for the above applications. It is a very rare
tric (BST) exhibit high dielectric constant and low tangent phenomena where magnetic ordering (associated with
loss. The electric response investigated by impedance unpaired or partly filled d or f electron) and ferroelectric
spectroscopy technique in terms of electric circuit has ordering (where an empty outer shell ‘d’ electron) exist in a
provided some interesting results on contributions of grain single phase of the materials. Many attempts have been made
and grain boundary in the restive characteristics of the to overcome the difficulty to fabricate hybrid multiferroic
composites. The study of ac conductivity as a function of composite materials of diverged properties. Some composite
frequency obeys Jonscher’s power law. The experimentally structures of ferrite–piezoelectric ceramics, ferrite–lead zir-
conate–titanate, ferrite–lead iron niobates, etc., have been
found to exhibit much higher ME coupling coefficient as
& C. Behera compared to that of mono-phase multiferroics. As PVDF has
[email protected] many interesting properties and advantages over other poly-
1
mers, it has been selected to fabricate inorganic–organic nano-
Multifunctional and Advanced Materials Research
composites in PVDF matrix with expectation to provide
Laboratory, Department of Physics, Institute of Technical
Education and Research, SOA University, excellent dielectric and required properties as compared to
Bhubaneswar 751030, India traditional multilayer ceramics, polymer-based multiferroic
2
Present Address: Department of Physics, NIT Agartala, composites in the thin film form offers several advantages
Tripura, India such as easy and cost effective processing, mechanical flexi-
3
Department of Physics, V S S University of Technology, bility, light weight and the ability to form any desired shape
Burla, Sambalpur, Odisha, India and size of samples required for devices.

123
 J Mater Sci: Mater Electron

After the discovery of piezoelectricity in polyvinylidene proportion of high-purity ingredients ([99.9 %): Bi2O3,
floride (PVDF), the interest has been generated for its piezo- BaCO3, SrCO3, Fe2O3, and TiO2 (from M/S Loba Chem-
electric and pyroelectric application [1, 2]. There are three icals Co. In) along with 4 % extra Bi2O3 in order to avoid
different type of relaxation process in the, b and c phases of the the bismuth loss during high-temperature processing.
material. The relaxation processes appear from high temper- Above raw materials were milled in a high-energy ball mill
ature to the low temperature side and from low frequency to (M/s Retsch-Planetary Ball Mill, Model PM 100, Ger-
high frequency side. The primary relaxation process is many) in the toluene media with different milling param-
attributed to the rotation of dipoles from one quasi-stable state eters (i.e., milling speed = 450 rpm; milling time: 90 h
to another in which the diffusion motion of the segment ball to mass ratio 10:1; diameter of ball 10 mm in zirco-
occurs. The b relaxation is associated with the partial orien- nium vial of 125 ml capacity). After 90 h of milling the
tation of the dipoles in the range of local environments where milled powders were calcined at an optimized temperature
the large scale arrangement of the main chain is frozen. Earlier 1000 °C for 4 h to form the desired phase of the com-
the molecular vibration of the a, b and c phases of PVDF have pound. Then the prepared powder was subsequently thor-
been investigated [3]. The distribution of relaxation times oughly mixed with a small amount of binder material
from dielectric spectroscopy, using Monte Carlo simulation, (polyvinyl alcohol) and compacted into disks (10 mm in
in a-PVDF reveals two relaxation process i.e., aa—relaxation diameter, 1 mm thickness) at an iso-static-pressure of
process associated with glass transition and ac—relaxation 5 9 108 kg/m2. The discs (pellets) were sintered at
process due to changes in confirmation in the crystalline 1050 °C for 4 h. That ceramic powder sample was taken
region [4]. As it is well known that PVDF possesses low without any further purification for the synthesis of
acoustic impedance having excellent matching with water and ceramics polymer nanocomposites. The composites of the
human tissue, making this polymer very useful for underwater composition (1 - x)PVDF–x(Bi0.5Ba0.25Sr0.25)(Fe0.5
acoustics and medical imaging application. All these fasci- Ti0.5)O3 (x = 0.05, 0.1 and 0.15) were fabricated by a
nating properties of PVDF can be used for device application. solution-casting method. For the fabrication of composites,
It is very important to mention that the different form and film NMP-(N-Methyl-2-Pyrrolidone) was used as a solvent for
processing methods of PVDF material are very important. As PVDF. The solution for the composite was prepared at
many technique such as injection modeling, die-casting, 60–70 °C under constant stirring with the help of a mag-
solution casting, solution evaporation technique hot rolling netic stirrer until the complete dissolution of the polymer
etc., solution casting is one of the desired and economical and ceramic was obtained. The homogenous suspension
method for preparing desired thickness thick as well as thin was then poured on the glass substrate of laboratory-fab-
film. In order to increase the dielectric constant of a polymer ricated micrometer-controlled tape caster, and then allowed
the strategy is to follow by increasing the incorporation of to dry in air for few days to remove solvent traces. The thin
perovskite ceramic filler (such as BaTiO3, BaxSr1-x TiO3, film was then peeled off from the glass substrate. Phase
Pb(Zr,Ti)O3) with high dielectric constant into the polymer analysis of the fired samples as well as the prepared
matrix [5–7]. But the ability of spherical ceramic particles to polymer thin films were carried out using diffraction data
increase the dielectric constant is very weak at low volume collected by an X-ray powder diffractometer at a scanning
fraction based on Maxwell-Garnett model rule of mixture [8]. rate of 3°/min in the range of 20° \ 2h \ 80 °C using
Higher loading of the ceramic fillers is usually needed to CuKa radiation. The surface morphology of the sintered
realize a high dielectric constant, and in such a case the, pellets and fabricated ceramic–polymer composite thin film
composite exhibit deteriorated break down strength, samples were investigated by scanning electron micro-
mechanical and processing properties. That is why we have scopy (ZEISS-SEM). The ferroelectric and magnetic
prepared the ceramic polymer nano-composite (1 - x) properties of the ceramic–polymer nanocomposite were
PVDF–x((Bi0.5Ba0.25Sr0.25)(Fe0.5Ti0.5)O3 (x = 0.05,0.1, carried out by P–E loop tracer (M/S-Radiant Technology,
0.15)) still we have achieved encouraging dielectric properties USA) and SQUID (EverCool SQUID VSM DC magne-
and multiferroic properties for suitable device application. tometer Quantum Design, USA) respectively. Then the
pellet samples were polished and electrode with high purity
silver-paste for electrical the measurements of electrical
2 Experimental parameters such as capacitance, impedance, tangent loss
and other dielectric parameters using computer-controlled
The complex nono-ceramics of (Bi0.5Ba0.25Sr0.25)(Fe0.5 phase sensitive meter (LCR/impedance analyzer) (M/S
Ti0.5)O3 (BFO–BST) multiferroic was fabricated by N4L model PSM 1735, UK) in a wide frequency range
mechanical alloying method followed by thermal treatment (1 kHz–1 MHz) different temperatures (25–125 °C). All
and has been reported by us in our previous report [9]. The the above electrical parameters of the ceramic–polymer
synthesis started with the ball milling of required composite have been measured with the pre-mentioned

123
J Mater Sci: Mater Electron

instrument. Magneto-electric measurement was performed (1 - x)PVDF–x(Bi0.5Ba0.25Sr0.25)(Fe0.5Ti0.5)O3 (x =

by a ME set up (Marine India) connected to a lock in 0.05,0.1 and 0.15) composite with different volume frac-
amplifier. In this experiment, the DC magnetic field up to tion of BFO–BST fillers. It shows the presence of both
7 kOe was produced by an electromagnet whereas AC PVDF and BFO–BST phases (as marked by # and *). Due
magnetic field was produced by a Helmholtz coil having to low level of filler concentration (x = 0.05 and 0.10),
200 turns with a radius of 2.5 cm. For the magneto-electric strong diffraction peak of PVDF is found to be dominate.
measurement of the ceramic–polymer composite were But in case of x = 0.15 of ceramic filler the perovskite
placed in the magnetic field with its faces perpendicular to phase seems to dominate which is due to the strong
the field direction. The ME voltage developed across the diffraction of the incorporated ceramic. This confirms that
sample was measured using a Lock in Amplifier (SR830). the proper incorporation of the ceramic powder into the
PVDF matrix. This type of observation was reported by
others also [14].
3 Results and discussion The SEM micrograph of BFO–BST and PVDF nano-
composite are shown in Fig. 2 and shows that the BFO–
3.1 Structural and micro-structural analysis BST particles are well dispersed in the PVDF polymer
matrix with negligibly small agglomeration of fine ceramic
The room temperature XRD pattern along with its refined particle. The HRTEM micrograph of the BFO–BST
parameters of (Bi0.5Ba0.25Sr0.25)(Fe0.5Ti0.5)O3 indicate that ceramics reveals the nanonature of the particle with less
is crystallizes in Rhombohederally distorted crystal system agglomeration. More pores are observed in the composite
with R3c space group having lattice parameters: a = 5.6115 which may be due to the contraction of PVDF during the
and c = 13.7357 Å which is consistent with the reported solidification process [15].
ones [10] as well as with our previous report [9].
Figure 1 compares the X-ray diffraction patterns of 3.2 Dielectric properties
PVDF and BFO–BST and (1 - x)PVDF–x(Bi0.5Ba0.25
Sr0.25)(Fe0.5Ti0.5)O3 (x = 0.05,0.1 and 0.15) ceramic– Figure 3 Shows the variation of relative dielectric constant
polymer nano-composite. The pure PVDF spectra show the (er) and tangent loss (tan d) with frequency of BFO–BST,
presence of both crystalline and amorphous phases of PVDF and (1 - x)PVDF–x((Bi0.5Ba0.25Sr0.25)(Fe0.5Ti0.5)
PVDF. The pattern also shows that the PVDF exists in O3 (x = 0.05,0.1,0.15)) composite at room temperature.
mixed a- and c-phase. The most prominent peak of the The values of dielectric constant and loss of pure PVDF
material appears for all the phases around 20° but for a- has already been published by one of the authors in the
and c-phase a second peak appears around 18° which previous report [16]. The values of dielectric constant of
makes them easy to distinguish from the b-phase. There are PVDF is 7–13 as reported by other [17, 18], and loss value
two intense peaks appearing at diffractions angle 2h cor- is also very small. Here we have also same agreement with
responding to 20° and 39.3° assigning to b(110) plane and the previously reported dielectric value and it is found to be
a(002) plane [11, 12]. The peaks at 2h corresponding to within 10. The value of dielectric constant of different filler
18.4° (020) and 36.2° (200) could be indexed to the a- and concentration loaded ceramic–polymer nano-composite is
c-phase of PVDF respectively [13]. The XRD patterns of comparably high than that of pure PVDF and lower than
that of BFO–BST ceramic. The inset of Fig. 3 provides the
dielectric data of BFO–BST nano-ceramic. When the filler
(ceramics) concentration of composites increases from 5 to
15 %, then the dielectric constant decreases. From X-ray
data it has been confirmed that a- and c-phases are present
in PVDF (which are both non-polar). Because of the non-
polar nature of PVDF and the constrained polymer chain
which obstructs the formation of electrical polarization, the
value of dielectric constant of (1 - x)PVDF–x((Bi0.5
Ba0.25Sr0.25)(Fe0.5Ti0.5)O3 (x = 0.05,0.1,0.15)) is less than
the that of BFO–BST ceramics [19] where as the opposite
trend is observed in case of tan d spectrum. The decreasing
its value on increasing frequency can be attributed to the
fact that the motion and rotation of dipoles in the PVDF
Fig. 1 Represents the XRD of (i) pure PVDF, (v) BFO–BST
ceramics and (1 - x)PVDF–x BFO–BST with (ii) x = 0.05, (iii) phase cannot keep up with the change in the frequency of
x = 0.10 and (iv) x = 0.15 of the polymer nanocomposite the electrical field. In other words, at higher frequency, the

123
 J Mater Sci: Mater Electron

Fig. 2 SEM Micrograph PVDF–BFO–BST (5 %) and HRTEM micrograph along with SAED pattern of BFO–BST nanoceramics

Fig. 3 Temperature dependent

tangent loss (a) and dielectric
constant (b) of (1 - x)PVDF–
xBFO–BST
(x = 0.05,0.10,0.15)
nanocomposite compared at
1 kHz

electric field changes with faster rate. It sustains the regions of the studied materials could be understood by using
polarization effect resulting in the reduction of the the complex impedance spectroscopy (CIS) technique.
dielectric constant [20]. The dielectric constant increases The variation of both real (Z0 ) and imaginary part of
with rise in temperature for (1 - x)PVDF–x((Bi0.5Ba0.25 impedance (Z00 ) with frequency from 25 °C temperature to
Sr0.25)(Fe0.5Ti0.5)O3 (x = 0.05,0.1,0.15)) which suggests 150 °C with an interval of 25 °C of (1 - x) PVDF–
that due to conductive increase of BFO–BST and thermal x(BFO–BST) (x = 0.05,0.10,0.15) presented in Fig. 4. It
expansion of PVDF with increasing temperature. At low has clearly been observed that Z0 has higher value at lower
frequency, the molecules have enough time to polarize. But frequencies and it decreases monotonically with rise in
in case of high frequency, the polarization of molecules frequency and attain a constant value at higher frequencies
does not have enough time to catch up with the change in at most of the temperatures. This trend (attainment of
electrical field frequency, which leads to the weak depen- constancy of Z0 value) appears to be shifting gradually
dence of dielectric constant on temperature [21]. towards the high frequency side with rise in temperature,
and its value for all temperatures merge in the high fre-
3.3 Impedance spectroscopy quency domain. The decrement in the real part of impe-
dance (Z0 ) with the rise in temperature and frequency may
The origin of dielectric relaxation mechanism associated with be due to the increase in ac conductivity with rise in
dynamics of bound or mobile charges in the bulk or interfacial temperature and frequency. The merger of the real part of

123
J Mater Sci: Mater Electron

Fig. 4 Frequency dependent Z0

and Z00 spectrum of
(1 - x)PVDF–x(BFO–BST)
(x = 0.05,0.10,0.15)

impedance (Z0 ) for all temperatures in the high frequency Figure 5 shows the Nyquist plots between Z0 (f) and
0
domain indicates a possibility of the release of space Z ’(f) for ceramics and ceramic polymer nano-composite
charge as a result of lowering in the barrier properties of from room temperature to 150 °C. The impedance spec-
the composite. This dispersion region spreads to a higher trum comprising of one or more semicircles distinguishes
frequency with increase in temperature. the contributions of grains (g) and grain boundary (gb) in
From the frequency dependence of the imaginary part plot the resistive characteristics of the materials. The two
of impedance (Z00 ) of (1 - x)PVDF–x(BFO–BST) semicircles in the figure represent two types of relaxation
(x = 0.05,0.10,0.15) a characteristic frequency (xmax = 2- processes occurring in the material that corresponds to
pfmax) peak appears which depends on temperature as well as grain (in the high-frequency range) and grain boundary (in
filler concentration. The appearance of double relaxation in the low-frequency range). The electrical properties of the
x = 0.05 composite suggests the relaxation process is quite sample could be represented by an equivalent circuit
dependent on temperature as well as filler concentration. comprising of parallel combination of two RC and RCQ
This peak can be related to the type and strength of the circuits. Where Q being the constant phase element. The
electrical relaxation phenomena in the material. Peaks are different configuration of ceramic–polymer nano-com-
more prominent at higher temperature and progressively posite shows decrease of slope on increasing temperature.
become more obvious as the temperature increases and the The bending of curve towards real Z0 axis shows a ten-
concentration of filler. With the increase in filler concen- dency of formation of a semicircular arc. The bulk resis-
tration the resistance of the composite increases because of tance (Rg) of the composite increases compared to PVDF
the high resistive BFO–BST nanoparticles. For that reason and BFO–BST nano-ceramics. The value of grain and
the resistance decreases with increase in filer concentration. grain boundary contribution to the total resistance of the
This is a clear indication of stronger relaxation at higher nanocomposite are compared in Table 1. It can be clearly
temperature. It can be seen that the curves display broad and noticed that the value of Rg decreases with rise in tem-
symmetric peak. Relaxation occurs over several frequency perature for all samples with a clear indication of NTCR
decades. This symmetric shape of the peaks can be assigned behavior of the sample. It is evident from Nyquist plots;
to the multiple relaxation and deviation from Debye that multiple relaxation times and processes are associated
behavior. As the temperature increases, the maximum of Z00 with grain and grain boundaries. The multiple broad
shifts to higher frequency. At higher frequency, the space dielectric relaxations is interrelated to various factors
charge has less time to relax and the recombination would be including size-distribution, wall-motion and orientation of
faster. At higher frequency, the space charge polarization domains, defect dipoles created causing diffuse dielectric
reduced so the curves merge there. transition.

123
 J Mater Sci: Mater Electron

Fig. 5 Nyquist plot of

(1 - x)PVDF–x(BFO–BST)
(x = 0.05,0.10,0.15)

Table 1 Comparison of resistance and capacitance of grain (Rg and Cg) and grain boundary (Rgb and Cgb) contribution to the total resistance and
capacitance of (1 - x)PVDF–x(BFO–BST) (x = 0.05,0.10 and 0.15) nanocomposite
Composite name Temp. (°C) Rg (X) Cg (F) Rgb (X) CPE Cgb (F)

(1 - x)PVDF–x(BFO–BST) (x = 0.05) 25 4.737E4 3.486E-7 8.720E4 3.470E-8 1.058E-10

50 5.295E4 8.784E-8 5.662E5 1.296E-7 1.067E-10
75 3.477E3 3.467E-8 1.000E7 1.111E-6 1.044E-10
100 9.551E3 3.365E-10 7.336E8 5.833E-8 1.425E-10
125 4.510E4 5.004E-10 1.000E8 1.387E-8 1.214E-10
150 3.196E4 3.312E-6 1.000E8 1.707E-6 1.252E-10
(1 - x)PVDF–x(BFO–BST) (x = 0.10) 25 1.000E7 1.569E-10 – 1.216E-10 –
50 1.000E2 1.023E-10 – 1.023E-10 –
75 1.435E2 9.474E-10 2.258E7 1.175E-8 9.946E-11
100 1.742E5 3.906E-10 3.824E8 1.878E-8 1.032E-10
125 2.526E3 2.382E-8 2.733E8 4.592E-7 1.027E-10
150 2.480E1 1.766E-8 1.468E6 9.773E-10 1.042E-10
(1 - x)PVDF–x(BFO–BST) (x = 0.15) 25 1.000E7 3.470E-8 1.987E6 1.409E-10 9.418E-11
50 2.122E1 7.240E-9 1.000E8 5.957E-8 9.986E-11
75 1.000E7 1.193E-5 7.013E6 1.007E-9 9.631E-11
100 1.866E6 8.948E-10 1.000E8 2.235E-7 1.000E-10
125 2.216E1 8.052E-11 5.751E8 5.803E-7 1.009E-10
150 2.762E0 4.063E-8 6.386E8 1.070E-6 1.034E-10

123
J Mater Sci: Mater Electron

3.4 Electrical modulus study peak maxima and the peak are much broader than that
would be predicted by ideal Debye behavior. The broader
The Fig. 6 show the variation of real part of dielectric nature of the peaks can be interpreted as the consequence
modulus (M ‘) and imaginary part (M ‘‘) as a function of of the distribution of relaxation time because of non-Debye
frequency over a range of temperature for all three composite type relaxation behavior of the material. In the low fre-
of (1 - x)PVDF–x(BFO–BST) (x = 0.05,0.1,0.15). At low quency region (to the left side of the peak) the charge
frequencies and temperatures, M0 tends to be very small but carriers can be regarded as mobile over long distances and
not approaching zero. This indicates that electrode polar- as performing successful hopping from one site to another.
ization makes a significant contribution at lower temperature At higher frequencies (to the right side of the peaks),
and space charge accumulates at the interface. Moreover, a however the charge carrier motion is confined and only
continuous increase in the value of M0 has been observed localized movement is observed. The frequency region in
with increasing frequency, with a tendency to level off at which the peak occurs is indicative of the transition from
higher frequencies, in the usual sigmoidal manner, for all the long-range to short range mobility of the ions [23].
temperatures and all composites. This observation may Moreover, the maximum of the peak frequency shifts
possibly be related to a lack of restoring force governing the towards higher frequencies with increasing temperature as
mobility of charge carriers under the action of an induced well as BFO–BST wt% or concentration. The shifting of
electric field [22]. As increase in the value of M0 with the peak suggests that the relaxation in which the hopping
increasing frequency may be attributed to the relaxation of charge carriers may occur is thermally activated. This
phenomena, because of the short range mobility of the charge behavior also suggests that the relaxation time decreases
carrier, which is spread over a range of frequency. with increasing temperature as well as wt% of the BFO–
Figure 6 also compares the variation of the imaginary BST concentration.
part of the dielectric modulus (M00 ) as a function of fre-
quency at different temperature of (1 - x) PVDF–x(BFO–
BST) (x = 0.05, 0.1, 0.15). The variation of M00 with fre- 3.5 Electric and magnetic hysteresis study
quency at different temperature gives useful information
about the mechanism of charge transport, foe the example Figure 7 Shows the P–E hysteresis loop of pure PVDF and
electrical transport and conductivity relaxation. In all (1 - x)PVDF–x((Bi0.5Ba0.25Sr0.25)(Fe0.5Ti0.5)O3
temperature range for the entire composite the modulus (x = 0.05,0.1,0.15)) nanocomposite at 50 Hz at room
plot are characterized by well defined asymmetric peaks at temperature. In order to have a clear idea regarding the
different frequencies. For all the samples, the plots polarization behavior; all the composites were pooled at an
obtained in each temperature; asymmetric relative to the applied unique field i.e., about 60 kV/cm. There is the

Fig. 6 Frequency dependent M0

and M00 spectrum of
(1 - x)PVDF–x(BFO–BST)
(x = 0.05,0.10 and 0.15)

123
 J Mater Sci: Mater Electron

Fig. 7 Hysteresis loop of pure PVDF and (1 - x)PVDF–x(BFO–

BST) (x = 0.05, 0.10 and 0.15) nanocomposite Fig. 8 H-H loop of (1 - x)PVDF–x(BFO–BST) (x = 0.15)

formation of a well defined non-linear, unsaturated loop for magnetization. The possible reason of the decrease in
PVDF. The value of saturation polarization for the case of magnetization may be as follows: firstly, the non magnetic
pure PVDF is found to be [1 lc/cm2 and for all other PVDF polymer coating layer, can be envisaged as a mag-
composite it is also found that the saturation polarization in netic dead layer on the ceramic, thus affecting the magni-
the same range. Small values of saturation polarization of tude of magnetization due to the quenching of the surface
PVDF have been consistent with the earlier reported one moment [25]. Secondly, the magnetization of the com-
[24]. The observed well defined ferroelectric hysteresis posite is related to the volume fraction of the ferrite particle
loops for (x = 0.05) demonstrate that the nanocomposite by the relation Ms = /ms, where /the volume fraction of
film retains good ferroelectric properties. The remnant the ferrite particle and ms is the saturation moment of a
polarization for (x = 0.05) is more than that of x = 0.10 single particle [26]. On increasing non-magnetic PVDF
and x = 0.15 and the saturation polarization is almost same concentration in the composite films, the BFO–BST ferrite
for all three nanocomposite. The appearance of lossy loop phase volume fraction in composite decreases thereby
for x = 0.05 suggests that the composite may not be suit- decreasing the total magnetization.
able for capacitive energy storage device as the area under
the loop is quite more than that of x = 0.10 and x = 0.15 3.6 ME measurement
of composite. Whereas the slim loop of x = 0.10 and
x = 0.15 are quite encouraging for the application of the Magneto-electric effect, a coupled ferroelectric and mag-
composite in capacitive energy storage device. In the other netic effect refers to the electric field inspired magnetiza-
hand it is found that the x = 0.05 composite is suit- tion and magnetic field induced electric polarization. The
able candidate for memory device application. The slim coupling of ME effect is generally characterized by ME
loop of x = 0.15, nanocomposite is equivalent shape to voltage coefficient aE which can be defined as [27, 28].
that of the virgin PVDF. The possible reason for the
dE 1 dV Vout
appearance of proper ferroelectric loop in case x = 0.05 The ME coefficient ¼ ¼ ¼
dH d dH ho d
composite can be attributed to the critical filler load beyond
which it cannot commensurate with the field. This suggests where E is the induced electric field, H is the applied
that there is a critical point for the filler BFO–BST con- magnetic field, V is the ME voltage developed across the
centration and which suggests that the long-range ordered sample, ho is the magnitude of the AC magnetic field and d
dipole chains of the copolymer phase are not destroyed as is thickness of the sample. ME coefficient has been mea-
long as the BFO–BST particle fraction is below the critical sured by dynamic method involving simultaneous appli-
point. Beyond this critical point, however the remnant cation of AC as well as DC magnetic field [29]. The
polarization decreases. That is why it becomes virtually voltage developed across the (1 - x)PVDF–xBFO–BST
impossible to obtain saturated hysteresis loop at the mea- (x = 0.05,0.10,0.15) samples were measured using a ME
sured frequency. The value of saturation polarization of the set up with lock-in-amplifier. In our experiment, 15.37 Oe
synthesized nanocomposite is quite less than the pure AC magnetic fields and 1 kHz frequency were applied
PVDF. From Fig. 8 it is found that the M–H loop of the along with a DC magnetic field of varying magnitude (-5
x = 0.15 is not encouraging because PVDF matrix is itself to ?5 kOe). The variation of ME voltage coefficient with
a non magnetic polymer which causes the reduction in applied DC magnetic field of (1 - x)PVDF–

123
J Mater Sci: Mater Electron

The AC field (h) superimposed into the DC field (H) can

be written as; h = h0sin xt and the total magnetic field can
be expressed as:
Htotal ¼ H þ h0 sin xt ð3Þ
The magnitude of the AC field (h0 ) can be calculated
from the following expression.
NI
h0 ¼ 0:899  ð4Þ
R
where N is the number of turns of the Helmholtz coil, I is
the current in Ampere and R is radius of the coil in cm.
From the above equation the value of found to be 15.37
gauss. At zero magnetic field the ME voltage coefficient
Fig. 9 M–E loop of (1 - x)PVDF–x(BFO–BST) (x = 0.05, 0.10 (aME) was found to be 16.4, 17.6 and 18.4 mV/cm. Oe for
and 0.15)
(1 - x)PVDF–x(Bi0.5Ba0.25Sr0.25)(Fe0.5Ti0.5)O3
(x = 0.05,0.1 and 0.15). The lowest value of ME coeffi-
x(Bi0.5Ba0.25Sr0.25)(Fe0.5Ti0.5)O3 (x = 0.05,0.10 and 0.15)
cient for x = 0.05 can be attributed to the lower value of
sample is shown in Fig. 9. As reported earlier [30], the ME
filler concentration in the PVDF matrix. This result can be
voltage developed across the sample due to the application
correlated with the consistent results that were obtained
of magnetic field can be written as:
from dielectric, magnetic and polarization study.
E ¼ V=d ¼ f ðH Þ ¼ constant þ aH þ bH 2 þ cH 3 þ dH 4 þ
ð1Þ 3.7 AC conductivity
dE
) ¼/ þ2bH þ 3cH 2 þ 4dH 3 þ ð2Þ The activation energy Ea, based on a thermally activated
dH process, can be calculated using the relation:

Fig. 10 Temperature
dependent AC conductivity of
(1 - x) PVDF–x(BFO–BST)
(x = 0.05, 0.10 and 0.15)
nanocomposite

123
 J Mater Sci: Mater Electron

rac ¼ r0 exp ðEa =kTÞ ð5Þ The observed increase in ionic conductivity with the
increase of temperature is ascribed to the decrease in vis-
where k = Boltzmann constant and r0 = pre-exponential cosity and hence to the increased chain flexibility [34]. The
factor. The temperature dependence of ac conductivity of segmental motion either allows the ions to hop from one
different polymer nano-composite at different frequencies site to another or provide an alternative for ions to move.
is shown in Fig. 10. The Arrhenius plot (log rac vs. Thus the segmental motion of (1 - x)PVDF–x(BFO–BST)
1000/T) in which the value of log rac increases linearly facilitate the translational motion [34]. The activation
with the increase in temperature. The estimated (using energy calculated in the high temperature range using the
linear fitting) value of activation energy can be calculated above Eq. (5) is presented in Table 2. From the table it is
from different region of the plot. For each frequency in the clear that the change in activation energy with increase in
plots, occurrence of different slopes in the different tem- filler concentration. Over all from the activation energy it is
perature regions suggests the presence of multiple con- evident that the predominant electron conduction mecha-
duction processes in these samples with different activation nism is playing in the composite because of low value of
energy. Study of frequency dependence of electrical con- activation energy. Beside this in x = 0.05 composite
ductivity provides the vital information on dominant con- somehow show a mixed conduction mechanism (electron
stituents or charge species involved in the conduction as well as polaron hoping) is found because of little high
process. Such study was carried out for our samples using value of activation energy (more thn 0.4 eV at 25 kHz in
double Jonscher’s power law. all three composite). From activation energy it is also clear
The increasing nature of conductivity with temperature that with increase in frequency the activation energy
can be well understood by the help of free-volume model decreases.
[31]. With increases in temperature, the polymer can Figure 11 shows the variation of rac with frequency at
expand easily and it is easy to produce free volume. As, a selected temperatures from 25 to 125 °C with a difference of
result with increase in temperature, the free volume 25 °C (1, 25, 100, 500 kHz and 1 MHz) of (1 - x)PVDF–
increases. The resulting conductivity, represented by the x(BFO–BST) (x = 0.05,0.10 and 0.15). It is observed from
overall mobility of ions and the polymer, is determined by both figures that the frequency dependence of conductivity
the free volume around the polymer chains. Hence, as spectra shows two regimes, (a) the low-frequency plateau
temperature increases, ions, solvated molecules, or poly- region and (b) the high-frequency dispersion region. The
mer segments can move into the free volume. This leads to low-frequency plateau region corresponds to the frequency-
an increase in ion mobility and segmental mobility that will independent conductivity ro (or) rdc.
assist ion transport and virtually compensate for the All the data were well agreement with Jonscher power
retarding effect of the ion clouds [32, 33]. law: rac = rdc ? Axn (0.1Bn B 1.0) where rdc = dc-
conductivity and A is temperature dependent factor. Gen-
erally, ac conductivity increases on increasing frequency
Table 2 Activation energy calculated from temperature dependent ac and temperature in polycrystalline materials. It is observed
conductivity that ac conductivity is almost frequency independent at
lower frequencies, forming a plateau region [15, 16]. The
Composite name Frequency Ea (eV)
frequency independent conductivity is considered as dc
(1 - x)PVDF–x(BFO–BST) (x = 0.05) 1 kHz 0.431 conductivity of the materials, which can be due to ther-
25 kHz 0.374 mally assisted space charge carriers. Hence, it can be
100 kHz 0.325 concluded that further increase of ceramics filler concen-
500 kHz 0.283 tration in the PVDF matrix can further reduce the electrical
1 MHz 0.250 properties, and hence materials may not be useful for
(1 - x)PVDF–x(BFO–BST) (x = 0.05) 1 kHz 0.407 meaningful devices.
25 kHz 0.292
100 kHz 0.228
500 kHz 0.153 4 Summary and conclusion
1 MHz 0.112
(1 - x)PVDF–x(BFO–BST) (x = 0.05) 1 kHz 0.405 Pure PVDF and (1 - x)PVDF–x(Bi0.5Ba0.25Sr0.25)(Fe0.5
25 kHz 0.319 Ti0.5)O3 (x = 0.05, 0.1 and 0.15) nano-composites were
100 kHz 0.256 prepared by a solution casting method using NMP as sol-
500 kHz 0.196 vent. Structural analysis confirms the co-existence of a and
1 MHz 0.149 c-phase in pure PVDF polymer. In all the composition of
ceramic–polymer nano-composite both the phase has

123
J Mater Sci: Mater Electron

Fig. 11 Frequency dependent

ac conductivity of
(1 - x)PVDF–x(BFO–BST)
(x = 0.05, 0.10 and 0.15)
nanocomposite

equally a priority depending on their percentage value. The annealing: application to a–PVDF. Phys. Rev. B 60, 12764
HRTEM micrograph of the prepared ceramic is found to be (1999)
5. K. Kakimoto, K. Fukuta, H. Ogawa, Fabrication of fibrous
in nano-regime with less agglomeration. Study of SEM BaTiO3-reinforced PVDF composie sheets for transducer appli-
micrograph shows excellent distribution of BFO–BST nano cation. Sens. Actuators, A 200, 21 (2013)
ceramic in the PVDF matrix without. The enhanced 6. T. Zhou, J.W. Zha, R.Y. Cui, B.H. Fan, J.K. Yuan, Z.M. Dang,
dielectric constant of the PVDF based polymer nano Improving dielectric properties of BaTiO3/ferroelectric polymer
composites by employing surface hydroxylated BaTiO3
composite could be suitable for energy storage devices. nanoparticles. ACS Appl. Mater. Interfaces 3, 2184 (2011)
Nyquist plot shows a tendency of differencing grain and 7. W.M. Xia, Z. Xu, F. Wen, Z.C. Zhang, Electrical energy density
grain boundary effect in the polymer nano-composite. All and dielectric properties of poly(vinylidene fluoride-chlorotriflu-
the extracted properties of the multiferroic polymer nano- oroethylene)/BaSrTiO3 nanocomposite. Ceram. Int. 38, 1071
(2012)
composites suggest that this composite can be a promising 8. H. Hammami, M. Arous, M. Lagache, A. Kallel, Study of the
candidate for room temperature multiferroic devices. interfacial MWS relaxation by dielectric spectroscopy in unidi-
rectional PZT fibres/epoxy resin composites. J. Alloys Compd.
Acknowledgments The authors gratefully acknowledge the grant 430, 1 (2007)
received from DRDO (Grant Number: ERIP/ER/1102202/M/01/1438 9. C. Behera, R.N.P. Choudhary, P.R. Das, Structural, dielectric,
dated 25/07/2012) Government of India to carry out this work. The impedance and magneto-electric properties of mechanically
authors also grateful to CRF, IIT Kharagpur and Dr. Ashok Kumar, synthesized(Bi0.5Ba0.25Sr0.25)(Fe0.5Ti0.5)O3 nano-electronic sys-
Senior Scientist of NPL, New Delhi, for providing some experimental tem. Mater. Res. Express 3, 035005 (2016)
facilities. 10. H. Khelifi, M. Zannen, N. Abdelmoula, D. Mezzane, A. Maalej,
H. Khemakhem, M. Es-Souni, Dielectric and magnetic properties
of (1 - x)BiFeO3–xBa0.8 Sr0.2TiO3 ceramics. Ceram. Int. 38,
5993 (2012)
References 11. S. Liu, S. Xue, W. Zhang, J. Zhai, G. Chen, Significantly
enhanced dielectric property in PVDF nano-composites flexible
1. A.J. Lovinger, Ferroelectric polymers. Science 220, 115 (1983) films through a small loading of surface-hydroxylated Ba0.6-
2. H. Kawai, The piezoelectricity of poly(vinylidene fluoride). Jpn. Sr0.4TiO3 nanotubes. J. Mater. Chem. A 2, 18040 (2014)
J. Appl. Phys. 8, 975 (1969) 12. A. Tawansi, A.H. Oraby, H.I. Abdelkadar, M. Abdelaziz, FeCl3–
3. M. Kobayashi, K. Tashiro, H. Tadokoro, Molecular vibrations of CoCl2 mixed fillers effects on the structural, electrical and
three crystal forms of poly(vinylidene fluoride). Macromolecules magnetic properties of PVDF films. J. Magn. Magn. Mater. 262,
8, 158 (1975) 203 (2003)
4. A. Bello, E. Laredo, M. Grimau, Distribution of relaxation times 13. I.S. Elashmawi, E.M. Abdelrazek, H.M. Ragab, N.A. Hakeem,
from dielectric spectroscopy using Monte Carlo simulated Structural, optical and dielectric behavavior of PVDF filled with

123
 J Mater Sci: Mater Electron

different concentration of iodine PVDF-PZT nanocomposite film tantalite(LT)/poly(vinyledene fluoride) (PVDF) nanocomposite.
based self-charging power cell. Phys. B 405, 94 (2010) J. Phys. D Appl. Phys. 42, 055402 (2009)
14. S. Sen, S.K. Mishra, Electrical behavior of PMN-PT-PVDF 25. R. kaiser, G. Miskolczy, Magnetic properties of stable dispersion
nanocomposite. J. Phys. D Appl. Phys. 41, 165305 (2008) of subdomain magnetic particle. J. Appl. Phys. 41, 1064 (1970)
15. Y. Zhang, Y. Zhang, X. Xue, C. Cui, B. He, Y. Nie, P. Deng, Z.L. 26. G.D. Prasannaa, H.S. Jayannaa, A.R. Lamania, S. Dash,
Wang, Structural, electrical and dielectric properties of Polyaniline/CoFe2O4 nanocomposite: a novel synthesis, charac-
(Sr1 - xCaX)MnO3(0 B xB1.0) ceramic. Nanotechnology 25, terization and magnetic properties. Synth. Met. 161, 2306 (2011)
105401 (2014) 27. Y. Zhanga, J.P. Zhou, Q. Liu, S. Zhang, C.Y. Deng, Dielectric,
16. S. Dash, R.N.P. Choudhary, M.N. Goswami, Modification of magnetic and magnetoelectric properties of Ni0.5Zn0.5Fe2O4–
ferroelectric and resistive properties of (Bi0.5Na0.5)(Nb0.5 Pb(Zr0.48Ti0.52)O3 composite ceramics. Ceram. Int. 40, 5853
Fe0.5)O3–PVDF composite. J. Polym. Res. 22, 54 (2015) (2014)
17. P. Mishra, P. Kumar, Dielectric properties of 0.25(BZT– 28. M. Shi, R. Zuo, Y. Xun, L. Wang, C. Gu, H. Su, J. Zhong, G Yu
BCT) - 0.75[(1 - x)PVDF–xCCTO](x = 0.02,0.04,0.06,0.08 Preparation and multiferroic properties of 2–2 type CoFe2O4/
and 0.1) composites for embedded capacitor application. Com- Pb(Zr, Ti)O3 composite films with different structures. Ceram.
pos. Sci. Technol. 88, 26 (2013) Int. 40, 9249 (2014)
18. L.L. Sun, B. Li, Y. Zhao, G. Mitchell, W.H. Zhong, Structure- 29. G.V. Duonga, R. Groessinger, M. Schoenhart, D. Bueno-Basques,
induced high dielectric constant and low loss of CNF/PVDF The lock-in technique for studying magnetoelectric effect.
composites with heterogeneous CNF distribution. Nanotechnol- J. Magn. Magn. Mater. 316, 390s (2007)
ogy 21, 305702 (2010) 30. J. Miao, H. Yang, W. Hao, J. Yuan, B. Xu, X.Q. Qiu, L.X. Cao,
19. A.K. Zak, W.C. Gan, W.A. Majid, M. Darroudi, Experimental B.R. Zhao, Temperature dependence of the ferroelectric and
and theoretical dielectric studies of PVDF/PZT nanocomposite dielectric properties of the B0.5Sr0.5 TiO3/La0.67 Sr0.33 MnO3
thin films. Ceram. Int. 37, 1653 (2011) Heterostructure. J. Phys. D Appl. Phys. 38, 5 (2005)
20. F.C. Loh, K.L. Tan, E.T. Kang, Y. Uyama, Y. Ikada, Structural 31. S. Rajendran, T. Uma, Lithium ion conduction in PVC-LiBF4
studies of polyethylene, poly(ethylene terephthalate) and poly- electrolytes gelled with PMMA. J. Power Sources 88, 282 (2000)
styrene films modified by near u.v. light induced surface graft 32. D. Saikia, Y.W. Chen-Yang, Y.T. Chen, Y.K. Li, S.I. Lin,
copolymerization. Polymer 36, 21 (1995) Investigation of ionic conductivity of composite gel polymer
21. Y. Deng, Y. Zhang, Y. Xiang, G. Wang, X. Huibin, Bi2S3- electrolyte membranes based on P(VDF-HFP), LiClO4 and silica
BaTiO3/PVDF three-phase composites with high dielectric per- aerogel for lithium ion battery. Desalination 234, 24 (2008)
mittivity. J. Mater. Chem. 19, 2058 (2009) 33. K. Tsunemi, H. Ohno, E.A. Tsuchida, Mechanism of ionic con-
22. M. Pant, D.K. Kanchan, N. Gondaliyam, Transport properties and duction of poly (vinylidene fluoride)-lithium perchlorate hybrid
relaxation studies in BaO substituted Ag2O–V2O5–TeO2 glass films. Electrochim. Acta 28, 833 (1983)
system. Mater. Chem. Phys. 115, 98 (2009) 34. S. Ramesh, O.P. Ling, Effect of ethylene carbonate on the ionic
23. J. Liu, C.G. Duan, W.G. Yin, W.N. Mei, R.W. smith, J.R. Hardy, conduction in poly(vinylidenefluoride-hexafluoropropylene)
Dielectric permittivity and electric modulus in Bi2Ti4O11. based solid polymer electrolytes. Polym. Chem. 1, 702 (2010)
J. Chem. Phys. 119, 2812 (2003)
24. S. Satpathy, P.K. Gupta, K.B.R. Verma, Enhancement of non-
volatile polarization and pyroelectric sensitivity in lithium

123