Polymer Composites

Optimization of Dielectric Properties of PVDF-CFO

Nanocomposites

Journal: Polymer Composites

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Manuscript ID PC-17-1961

Wiley - Manuscript type: Research Article

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Date Submitted by the Author: 31-Oct-2017

Complete List of Authors: Supriya, Sweety; IIT Patna, Physics

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Kumar, Lawrence; Central University of Jharkhand, Centre for

Nanotechnology
Kar, Manoranjan; Indian Institute of Technology Patna, Physics;
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composites, core-shell polymers, crystal structures, dielectric properties,

Keywords:
FT-IR
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3 Optimization of Dielectric Properties of PVDF-CFO Nanocomposites
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5 Sweety Supriya, Lawrence Kumar and Manoranjan Kar*
6 1Department of Physics, Indian Institute of Technology Patna, Bihta, Patna-801103, India
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8 Centre for Nanotechnology, Central University of Jharkhand Ranchi, Ranchi 835205, Jharkhand, India
9 mano@iitp.ac.in, 91-612-3028013
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11 Abstract: The addition of different types of nanofillers in the PVDF (polyvinylidene difluoride) matrix exhibits
12 promising dielectric, magnetic, piezo, pyro and ferroelectric properties for various applications. Hence a novel
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14 nanocomposite has been developed by using PVDF and CoFe2O4 (CFO) with different particle size of CFO for
15 dielectric applications. The nanocomposite has been characterized by the XRD(X-ray Diffraction Pattern),
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17 AFM(Atomic Force Microscopy), TEM (Transmission Electron Microscopy), FTIR (Fourier Transform Infra-red
18 Spectroscopy), FE-SEM (Field Emission Scanning electron Microscopy) and, frequency and temperature dependent
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dielectric measurement. The space charge effect at the CoFe2O4/PVDF nanocomposite interface offers the interfacial
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21 polarization, which contribute to tune the dielectric response of nanocomposite along with low dielectric loss. The
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filler size has been optimized to have better formation of polar β phase in PVDF along with high dielectric
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24 properties. The dielectric constant in nanocomposite has increased 3 times compare to that of PVDF. It is interesting
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to note that the core-shell type structure has been observed. The 20 nm core size (CFO) filler in PVDF matrix
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27 exhibits optimized dielectric properties.
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30 Introduction:
31 In order to enhance the performance of the dielectric material, i.e. to have an improved capacitive effect of the
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33 ferrite and polymer based nanocomposite films have grabbed the researchers’ attention in the recent years. The
34 nanocomposite films having good flexibility, strength and compactness can be used to make portable and durable
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36 devices [1]. To fulfill these requirements, PVDF (Polyvinylidene difluoride) polymer has been utilized because of its
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37 unique properties like thermal stability, good chemical resistance and extraordinary pyroelectric and piezoelectric
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39 properties, flexibility, high dielectric breakdown field, etc. [1,2]. PVDF is a semicrystalline polymer i.e. both
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40 crystalline and amorphous phases are present in the bulk PVDF. PVDF consists of carbon as the backbone,
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42 hydrogen and fluorine as substituent, which is depicted in the figures 1(a) and 1(b) for α and β phases of PVDF
43 respectively. It has four unique crystalline phases called α (in trans-gauche twist conformation TGTGˈ), β (in all
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45 trans planar zigzag conformation TTTT), γ (three trans linked to a gauche conformation TTTGTTTGˈ, in an
46 intermediate conformation of the PVDF α and β phases) and δ (a polar version of the α phase) [2]. Percentages of
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48 individual phases present in PVDF depend on the processing conditions, chain conformation and molecular packing
49 [2]. Among all the crystalline phases, α (paraelectric) and β (ferroelectric) phases are most significant. α is the non
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51 polar phase and rest are polar phases, among which β phase exhibits very strong polarization. The dielectric,
52 piezoelectric and ferroelectric properties of PVDF lies in these phases, but especially polar β phase is responsible for
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high dielectric properties of PVDF. This is due to its polarized structure of all-trans planar zigzag conformation
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55 between positive hydrogen ion and negative fluorine ion. The total potential energy due to intramolecular and
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intermolecular interaction of the β phase of PVDF is higher than that of α and γ phases of PVDF [3]. The α-phase
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3 has trans gauche (TGTG) bond conformation obtained generally by solvent cast method. In this phase, hydrogen and
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5 fluorine are at ± 60º to each other and connected to carbon atom shown in the figure 1(a)[2]. The β-phase has all
6 trans (TTT) bond conformation with hydrogen and fluorine atoms are on opposite side (at 180o) and forms the net
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8 non zero dipole moment[1,2] as shown in (b)[2]. The polar β phase, intensively contribute to dipole formation and
9 enhance the dielectric properties and hence the capacitive performance for versatile application in electronic
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11 industry. However, the properties of PVDF need to be improved for the industrial needs[4]. And that requires to
12 fabricate PVDF based nanocomposites with better dielectric properties compared to PVDF without losing its
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14 mechanical strength and other physical properties. Nanocomposites are opted for better tunability of the physical
15 properties for nano scale portable devices as today’s requirement. For this, one can deal in order to have nano sized
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17 core within the shell of polymer matrix for getting miniaturized film dimension and that includes the study of filler
18 (core) geometry and surface interaction on the overall nanocomposite response for technological applications.
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CoFe2O4 is a hard ferrimagnetic material having spinel structure and have a cubic phase of crystal symmetry. It has
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21 very good electric[5,6] and magnetic properties [6,7] which are very useful for technological applications [5-8]. The
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parameters such as filler size, method of preparation, type of solvent, annealing condition and the dispersion of
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24 nanoparticles into the polymer matrix affect the crystallization behavior and morphology of the resulting composite
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[9, 10]. A faster crystallization rate has been observed in the blends is due to the nucleating ability of cobalt ferrite
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27 nanoparticles[11]. The nucleation effect strongly depends on filler size and surface interface. The space charge
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interface between cobalt ferrite and PVDF strongly affects the dielectric response. The polar β-phase shows the
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30 largest piezoelectric, pyroelectric and ferroelectric coefficients, as well as a high dielectric constant [11].
31 S. F. Mendes et. al. have reported the effect of filler size and concentration on the structure and properties
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33 of poly(vinylidene fluoride)/BaTiO3 nanocomposites[12]. They found that 10 nm filler particle size has greater
34 dielectric constant than that of 500 nm particle size of the filler. Hence, concluded that smaller particle size (10 nm)
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36 has a significant role as nucleating agents during polymerization of PVDF compared to that of the larger particles
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37 (500 nm), because reduction of relative interaction area for a given volume concentration leads to defect
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39 formation[12]. They reported that 10 nm BTO particle act as a better nucleation center for PVDF crystallization. It
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40 indicated that nm size of filler could provide better dielectric response than the bulk. P. Martins et. al. reported that
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42 CoFe2O4/PVDF composites have the full phase nucleation often β-phase occurs for much lower concentration (5%)
43 than that of NiFe2O4/PVDF(50%) composites[13]. It means only 5 to 10 wt% of CoFe2O4 for CoFe2O4/PVDF
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45 nanocomposite has been reported best for α to β-phase transformation[13]. Prabhakaran et. al. investigated the
46 magneto-electric properties of flexible PVDF/NiFe2O4 nanocomposite for device applications[14]. Laurence Ourry
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48 et. al show the small variation of size and content affects the crystallization of the electroactive polar phase of
49 PVDF. And also a higher percentage of polar PVDF has been reported for bigger (9 nm) CoFe2O4 nanoparticles as
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51 compared to (6nm)[15]. This indicates that filler size has to optimize for better nanoparticle and PVDF interaction in
52 order to have superior dielectric value. An extensive literature survey and above discussion reveal that (i) Low %
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(5% to 10%) of cobalt ferrite nanoparticle is suitable for obtaining maximum β phase by preparing PVDF in a
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55 simple method. The percentage of cobalt ferrite has to be maintained 10% in order to avoid agglomeration of the
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nanoparticle in CFO/PVDF composite and, (ii) The larger particle size of cobalt ferrite can not fit properly in the
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3 matrix of PVDF and segregate form the nanocomposites, which may lead to agglomeration of CFO in the
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5 composite. Hence, nanosize of filler is good for surface interaction and better dielectric response as compared to
6 bulk and, comparatively bigger nanosize CFO filer gives a higher percentage of polar PVDF i.e. β phase in the
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8 nanocomposite. The above discussion motivate to optimize the effect of different size nanocrystalline cobalt ferrite
9 distribution in PVDF matrix for forming core-shell structure by avoiding agglomeration due to weak intermolecular
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11 interaction between CoFe2O4 and PVDF. Therefore, the present article accounted the variation in filler size that is
12 between 30 nm to 10 nm to optimize the filler grain size to accomplish better performance of this composite as
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14 dielectric material. In other hand, 10 % of filler content has been considered to avoid agglomeration effect. It is
15 worth to note that the maximum dielectric constant was obtained for 20 nm CFO in PVDF marix whose dielectric
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17 constant is approximately 4 times larger than that of PVDF.
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20 Experiments:
21 Cobalt ferrite has been prepared by the Sol-gel method[16-18], and heated to 1000 oC. The synthesized sample was
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ball milled for 24, 48, 72 and 96 hours respectively in order to have different size nanoparticles using steel balls at
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24 the speed of 300 rpm. The ball milled samples were heated to 200 OC in order to remove the moisture which may be
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absorbed by the sample meanwhile ball milling process. The 10% cobalt ferrite to that of PVDF for each grain size
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27 as used to prepare the nanocomposite (PVDF and CoFe2O4). The 10% weight of cobalt ferrite of all grain sizes are
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individually dissolved in 10 ml of DMF (Dimethyl Formamide) solvent using ultra sonicator. Similarly PVDF is
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30 also ultrasonicated in DMF solvent to have proper dispersion. The ultra-sonication has been carried out for 6 hours
31 so that both the cobalt ferrite and PVDF get fully dissolved. The separate solution of the CoFe2O4 and PVDF has
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33 been mixed and again sonicated for proper mixing. The solution is cast in the petridish and allowed to dry at 80 oC
34 in oven for 12 hours. An independent film of nanocomposite has been prepared can be easily separated from the
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36 petridish. The X-ray diffraction patterns have been recorded using Rigaku TTRX III Diffractometer in the 2θ range
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37 of 5 to 80 degrees. TEM micrograph (model JEM 2100 JEOL ) and FESEM micrograph (S-4800) has been studied
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39 for surface morphology and structure. FTIR spectra has been recorded using the Perkin Elmer model no. 400
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40 machine. The uniformity of PVDF-CFO of nanocomposite films has been investigated by recording AFM
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42 micrographs. The nanocomposite films were prepared in the desired shape and painted both sides of film with silver
43 paste to make electrodes and allowed to dry at room temperature. The films with electrodes of thickness 0.4 mm are
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45 kept into the sample holder in capacitive geometry for electrical measurement. The N4L NumeriQ 1735 PSM
46 impedance analyzer and the temperature controlled furnace is interfaced with a computer using Lab View program
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48 was used for automated dielectric measurement.
49 Results:
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51 There are two sets of samples. One set is CFO (Cobalt ferrite) with different crystallite size, which has prepared by
52 ball milling and another set is CFO-PVDF nanocomposite. Samples are named as; Bulk CFO(120), CFO (30),
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CFO(20), CFO(15), CFO(11), PVDF-CFO(10), PVDF-CFO(11), PVDF-CFO(15) and PVDF-CFO(20). The number
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55 in bracket represents the crystallite size of the CFO. The XRD patterns of pure cobalt ferrite with different ball
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milling times, i.e. different grain size are shown in figure 2(a). XRD patterns reveal that the samples are crystallized
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to simple cubic spinel ferrite. All the observed peaks could be indexed to the Fd3m space group for all the samples.
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5 It is observed that the most intense peak (311) smear with the increase in milling time. It reveals the decrease in
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crystallite size with milling time. Crystallite size has been calculated by employing the W-H method [19] and values
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8 are enlisted in table 1. The (311) peak shifted towards lower 2θ values with the decrease in particle size. The lattice
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parameter has been calculated by the least square method and listed in table 1. The lattice parameter increases with
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11 the decrease in the crystallite size. Similar result has been reported in the litereature [8,13,16]. The XRD patterns of
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nanocomposites are shown in figure 2(b). Two different crystal phases (α and β phases) of PVDF have been
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14 observed along with the phase of cobalt ferrite which indicates the formation of nanocomposite. The α, γ and β
15 phases of PVDF are marked along with the peaks of cobalt ferrite in the figure 2. The high intensity peak at
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17 2θ=20.40 (summation of (110) and (200) planes) and low intensity peak at 36.50 ((020) and (101) planes), 36.10
18 (120) and 56.080 (221) correspond to β phase of PVDF, peak at 18.50 (020) marked as γ phase of PVDF and peaks at
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20 2θ=17.70 (100), 18.40 (020), 19.90 (021), 26.50 (001) 32.20 (121), 33.10 (130), 38.610 (002)and 46.300 (230)
21 represent the α phase of the PVDF[20, 21].
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23 Figures 4 (a) and 4(b)-4(f) represent the micrograph of PVDF and PVDF-CFO nanocomposite. Pure PVDF
24 has no core shell formation. The incorporation of nanoparticle in the PVDF matrix is uniformly distributed in
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26 PVDF-CFO(20). The interaction of CFO nanoparticle with PVDF expected to form the core shell structure and also
27 depicted in figure 4(b). Here nanoparticle behaves like a core and PVDF as a shell. A perfect core-shell structure has
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29 been observed from the figure 4(b). But for the samples having core size either greater than 20 nm or lower than 20
30 nm are found to be agglomerated from the micrographs 4(b) and 4(d)-4(f). It could be due to improper size of
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32 nanoparticles to that of matrix size of PVDF. The core size greater than 20 nm anticipated being larger than the
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33 matrix size and for the core sizes lower than 20 nm, it is expected to have two or more nanoparticles agglomerate in
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35 one place in the single PVDF matrix.
36 The FTIR provides structural information that helps in distinguishing the different crystal forms of polymer
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38 based nanocomposites. The typical FTIR spectra of pure cobalt ferrite has been shown in figure 5(a). The two bands
39 have been observed around 395 cm-1 and 584 cm-1 which correspond to the octahedral site(O) and tetrahedral site(T)
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of cobalt ferrite respectively. And the results are consistent with the XRD pattern analysis. The FTIR quantifies the
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42 percentage of β phase in PVDF. Also, the change in chemical environment in the crystal can be observed from the
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FTIR spectra analysis. FTIR spectra of PVDF and PVDF-CFO nanocomposites are depicted in the figure 5(b). The β
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45 and α phases peak are identified. It is worth noting that the peak positions for α and β phases in PVDF are not
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shifted either to lower or higher wavelength. It ruled out the chemical reaction between CFO and PVDF interface. It
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48 is possible due to crystallization of PVDF at lower temperature which is not sufficient to activate the CFO for
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reaction. It is interesting to note that the intensity of α and β phases varies with the size of CoFe2O4 nanoparticles in
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51 the nanocomposite film. The peak intensity of α phase decreases, however intensity of β phase increases. The
52 fraction of β phase F(β) with respect to α-phase could be regulated through particle size varies and is determined by
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54 Lambert–Beer's law as follows[20];
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Aβ
4 F( β ) = (1)
5 Kβ
( ) Aα + Aβ
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8 Where Kβ (7.7x104 cm2 mol-1) and Kα (6.1x104 cm2 mol-1) are the absorption coefficients at the respective wave
9 numbers. Aβ and Aα are absorbance at 835 cm-1 and 761 cm-1 respectively. The variation in β phase with the increase
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11 in size of filler nanoparticle size is enlisted in table II. And it is interesting to note that the fraction of β phase F(β)
12 increases with the increase in crystallite size of CFO nanoparticle incorporation in PVDF matrix as the
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14 comparatively larger size of filler (20 nm) (within nm range) has the larger electroactive β phase compare to that of
15 CFO size <20nm. Although the β phase increases with the increase of particle size of CFO (>20nm), but it is not
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uniform in the PVDF matrix. Hence, the dielectric constant decreases for filler size > 20nm in the PVDF matrix.
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18 Hence, it conclude that, not only electroactive β is responsible for increasing dielectric constant in PVDF, but also it
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is highly depends on size and physical properties of filler.
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21 The surface morphology of nanocomposites has been studied using AFM. Good dispersion of the ferrite
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nanoparticles within the polymer is achieved at all grain sizes with no defects like cracks, voids or pores in the
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24 nanocomposite films. Figure 6 (a) shows the AFM picture of pure PVDF. Figure 6(b) to 6(d) shows the AFM picture
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25 with decreasing grain size of filler (CoFe2O4) of the composite. Due to the interaction between CoFe2O4 and PVDF
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27 forms core-shell structure, where CoFe2O4 is the core and PVDF is the shell. The expected figure of core-shell has
28 been depicted in figure 1(c)[22]. The decreasing grain size of nanocomposite with the decrease in CFO particle size
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30 has been observed from the AFM micrographs (figure 6). The all above characterizations and analysis of XRD,
31 TEM, FTIR and AFM results reveal that below 20 nm of filler size, the nanocomposite behave differently to that of
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34 The dielectric permittivity (εˈ) of the PVDF/CoFe2O4 films (thickness ≈ 0.4 mm) were measured over the
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36 frequency range from 100 Hz to 1 MHz. Figure 7 shows the frequency dependent dielectric constant at different
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37 temperatures. The dielectric constant of the nanocomposite films shows a monotonous increase as a function of filler
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39 size from 10 nm to 20 nm which is due to the increase of β phase (largest polarization phase in PVDF) with the size
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40 of cobalt ferrite filler (evidenced from XRD, TEM, and FTIR analysis). The similar result of dielectric constant of
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42 pure PVDF lower than that of PVDF-CFO composite has been reported in the literature[23]. It is worth to note that
43 the increase of dielectric constant is linear with the increase in filler grain size as observed from the figure 6. The
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45 details of the above observation have been discussed later (discussion section). The dielectric constant
46 corresponding to the filler size of 30 nm and 120 nm are sometimes shows higher value than 20 nm filler towards
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48 high temperature and lower towards room temperature than that of 20 nm filler size, which indicates that the 30 nm
49 and 120 nm constituted PVDF-CFO nanocomposites because of randomness in the behavior as the nanoparticles are
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not fitted in the PVDF matrix because of the greater size of filler than 20 nm filler size. Also 20 nm to 10 nm filler
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52 size constituted PVDF-CFO nanocomposite shows consistent results with decreasing filler size as per their surface
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interaction. Hence among 20 nm to 10 nm nanoparticles, 20 nm CFO filler size in PVDF-CFO nanocomposite is the
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55 optimum size to enhance the dielectric behavior.
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3 The dielectric loss arises from dielectric damping loss and the conduction loss in the material. The loss
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5 tangent with varying frequency at different temperatures has been shown in the figure 8. It is worth to note that the
6 dielectric loss of PVDF-CFO nanocomposite is found lower as compared to PVDF. This behavior reveals the better
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8 use of PVDF-CFO nanocomposite compare to that of PVDF due to low ac loss. It is observed that the dielectric loss
9 is almost constant (not significant decrease is from 20-10 nm filler) with the crystallite size of CFO from 10 nm to
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11 20 nm. Another very interesting feature to note that the dielectric loss is minimum for 30 nm filler size, even
12 compare to 120 nm and 20 nm filler size.
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14 The loss tangent is exponentially decreasing in the whole span of the frequency range for all nanocomposite films.
15 As compared to a higher frequency dipole can easily orient at low frequency. This phenomena are attributed to
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17 intermolecular vibration or friction which led to an exponential decrease of tanδ. When frequency increases dipole
18 fails to follow fast changing frequency of the electric field and eventually there is hardly any tangent loss[24]. The
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above dielectric results conclude that the 20 nm CFO filler in PVDF matrix is the optimized nanocomposite for
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21 technological applications.
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Discussion:
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24 The high dielectric constant and dielectric breakdown strength play a very significant role in the capacitors and
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electric energy storage devices with high volume efficiency and high density [10] which can be accomplished by the
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27 polymers and ceramics fillers nanocomposite formation. The crystallite size of the nanoparticle has been determined
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via XRD results and confirmed through TEM micrographs. The present article presents the incorporation of cobalt
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30 ferrite in PVDF matrix and, it has reported that the nanocrystalline filler has ability to nucleate the ferroelectric
31 phase (β phase) of the PVDF in the resulting nanocomposite. The modulation of ferroelectric phase of PVDF has
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33 been studied as a function of the size of nanoparticle within the nano range CFO filler in the PVDF matrix. The
34 crystallization of different phases of PVDF polymer due to nano filler leads to an effect on dielectric properties of
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36 thick film. The samples are prepared by solution cast method.
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37 The polymer composites emphasize on the enhancement of the dielectric permittivity using ferrite metal
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39 oxides. The availability of high dielectric ferrite material as an inorganic filler to make it very appealing to introduce
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40 in the polymer chain (having the dielectric constant less than 10) resulting into better dielectric performance
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42 nanocomposite. Here filler (CoFe2O4) has a greater permittivity than that of PVDF polymer, so most of the effective
43 dielectric constant originate from the increase in the average field in the PVDF matrix. The nano range of filler grain
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45 size modifies the interface of two phases as the surface area of nano filler amplified the interface and achieve better
46 dispersion of the filler nanoparticle in the PVDF matrix.
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48 Cobalt ferrite nanoparticle exhibit negative surface charges indicated in figure 1[22]. The nucleation arises
49 due to interaction between negatively charged CFO nanoparticle and the positively charged CH2 bond of PVDF
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51 causes larger electrostatic interaction. This interaction causes the PVDF chain to align on the surface of the cobalt
52 ferrite nanoparticles and form the shell in extended TTTT conformation and results in the β-phase formation with
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piezoelectric and ferroelectric properties. This nucleation effect has been observed all along the sample as confirmed
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55 by the FTIR. Far from these interfaces, nonpolar α phase may grow during the processing conditions without
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nanoparticles, which leads to the co-existence of α phase and β-phase inside the nanocomposites. And it has been
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3 also observed from XRD and FTIR results shown in the above section. Therefore the addition of cobalt ferrite is
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5 responsible for inducing more ferroelectric polar β-phase in the nanocomposite. The observed FTIR spectra with
6 different grain size filler are depicted in figure 4. The evolution of β-phase and suppression of α phase with the
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8 CoFe2O4 filler is clearly observed, which confirms the result obtained from the XRD analysis. The bands at 795 cm-1
9 and 973 cm-1 corresponds to α phase and bands at 761, 835 and 875 corresponds to β-phase[13]. As discussed
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11 earlier, the cobalt ferrite content is responsible for the induced polar β-phase in the nanocomposite.
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14 When the grain size of nanofiller is greater (> 20 nm), no chain formation takes place because of larger size
15 of the filler nanoparticle that could not fit properly in the PVDF matrix. As a result nanoparticle segregate and
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17 agglomeration takes place which is prone to be settled in the amorphous phase of PVDF in nanocomposite. If the
18 grain size of nanoparticle is lower (<20 nm), the surface distortion became large as the dynamics of surface charges
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causes loss of polar β-phase nucleation ability. The poor surface modification of the nanoparticles arises as the low
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21 value of filler particle size, which breaks the long chain of PVDF. It implies that lower grain size nanoparticle gives
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a poor base to the surface interaction and is responsible for the suppression for the nucleation of the β -phase of the
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24 polymer. Therefore the critical size of filler nanoparticle that is 20 nm provides better nucleation than other sizes
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of filler nanoparticles as indicated in the figure 10. It is Among all the nanocomposites, 20 nm nanoparticle size
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27 PVDF-CFO(20) nanocomposites has highest β phase percentage, expected to be better surface interaction and results
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in high value of dielectric constant. Also the dielectric loss is very low for lower filler size as compared to greater
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30 grain size of nanofiller (> 20 nm) as shown in figure 9(c). But one can’t over ruled the perception of Boundary layer
31 Capacitance (BLC’s) Model to understand the PVDF-CFO nanocomposite. According to (BLCs) model, core
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33 (CoFe2O4) is semiconducting in nature, but shell (PVDF) work as insulating boundary and it can be explained by
34 the simple expression as[25]
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36 ε re = ε r t g /t b (2)
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38 Where ߝ௥ is relative permittivity, tg is the thickness of core (as grain) and tb is the thickness of shell (grain
39 boundary) respectively. This expression implies that the thickness of core and shell would determine the dielectric
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41 behavior.
42 As per BLCs model, when an electric field is applied on the nanocomposite film, the charge carriers within
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44 the semiconductor core (or grain or CoFe2O4) would pile up at the two edges of the shell (or insulating grain
45 boundary or PVDF thin layers) and this heterogenous microstructure results in high dielectric constant. However,
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47 there would be a major role of grain size, which provides a base for forming the interface and eventually the impact
48 on the dielectric. Also the filler size incorporation in PVDF matrix has an impact on the thickness of the core (grain)
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and the thickness of shell (grain boundary), henceforth the impact on surface interaction of nanofiller and PVDF.
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51 The expected structure with the increasing grain size is depicted in figure 8. It could be seen that, when the particle
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size is > 20 nm, the surface interaction is in distorted form due to uneven distribution of particle size due to the
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54 agglomeration of nanoparticle, results in some random result in dielectric constant value as indicated in the figure 9
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(b) and also the dielectric loss is very high for the same as shown in figure 10(c). Despite the formation of core
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57 shell, it cannot be ruled out the presence of nanoparticle (≤20nm) in the amorphous phase of PVDF in
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3 nanocomposite. However the contribution of these structure in the tuning of dielectric is small compare to that of
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5 coreshell structure.
6 When the filler size is 20 nm, which is able to fit properly in the PVDF matrix, the distance (d) between the
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8 two electrode seems to be optimum, which will be beneficial for high capacitance value as per the relation
9 C = ε o A d where εo is the dielectric permittivity in the vacuum, A is the area of the sample and d is the distance
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11 between two electrodes. The effect of standard size of nanofiller could also observe from the plots of figures 7, 8
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and figure 10(b) and 10(c), which show nanocomposite with 20 nm filler has highest dielectric constant with low
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14 dielectric loss. Here, the thickness of PVDF is the distance d, that is tb. So, the comparatively larger size of
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nanoparticle which fit properly in PVDF matrix causes increased tg and decrease in the thickness of tb , which
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17 results high dielectric constant value. Hence the result obtained validates the equation (2) and BLC’s model. Also,
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we could say that lower grain size (below 20 nm) causes decrease in tg and increase in tb results in a lower dielectric
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20 constant and low dielectric loss (figures 7, 8, 10(b) and 10(c)). This is due to the agglomeration of smaller
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nanograins as filler and also poor surface interface interaction as the lower grain gives poor polarization because of
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23 less number of charge carriers present at the interface. With this discussion, it is concluded that the 20 nm is the
24 critical size of nanofiller that incorporated with better surface interaction, maximum PVDF nucleation, greater β
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26 phase formation and results in enhanced dielectric constant value with low loss. Above 20 nm size of the nanofiller
27 causes loss of chain formation and also lowers surface contact area provides in deteriorate the dielectric behavior
28
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29 by giving random value because of non-uniform distribution of PVDF and nanofiller. Below 20 nm of filler size,
30 agglomeration takes place, results in a poor surface interface and reduction in dielectric constant value. With
31
32 extremely lower grain size grains can accumulate in the PVDF matrix as seen in figure 9 (c) for sample PVDF-
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33 CFO(11) and PVDF-CFO(10) and poor surface interaction lowers the electrical conductivity. A single figure is
34
35 incorporated for 11 nm and 10 nm filler sized nanocomposite because, there would be hardly any variation in the
36 expected figure as the size of filler size are very close.
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38 The nanocomposite CFO/PVDF has a microcapacitor type working principle. The two neighboring cobalt
39 ferrite filler nanoparticle in the insulated PVDF matrix can behave as microcapacitor. Here, cobalt ferrite is
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41 semiconducting in nature acting as grain and PVDF is insulating in nature acting as a grain boundary. The
42 contribution from each capacitor presents in the nanocomposite could behave as large capacitor. Therefore, this
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44 large capacitance could be correlated with a significant increase in effective dielectric constant of the
45 nanocomposite. Also an increase in dielectric constant due to increase in grain size. Larger grain size leads to
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increase in the mobile charge concentration inside the grain(core), which results in more charge accumulation at the
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48 interface of two insulating layers act as a micro-parallel capacitor and results in huge dielectric constant. Therefore,
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the PVDF-CFO(20) has a filler grain size of 20 nm shows larger dielectric constant among all, which assist in
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51 various dielectric applications.
52
The polarization in ferrites originates from electronic exchange Fe2+ ↔ Fe3+ and Co2+ ↔ Co3+ via oxygen
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54 in the spinel phase which could not follow the alternating external beyond certain frequency. The high dielectric
55
constant at low frequency is due to interfacial polarization occurred in the interfaces between insulating shell
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57 (PVDF) and semiconducting material as the core(CoFe2O4). The entrapment of charge carrier at the interface of
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3 CoFe2O4 and PVDF polymer is relative to Maxwell–Wagner–Sillar effect (MWS)[26]. As per the Maxwell–
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5 Wagner–Sillar effect when current flows at the interface of two materials having a different electrical conductivity,
6 charges are piled up at the interface of dielectric materials. The charge carriers are trapped at the interfaces due to
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8 MWS effect, which in turn enhanced the dielectric permittivity. This interfacial polarization increases with the
9 optimize filler nanoparticle of 20 nm, hence the dielectric as discussed in earlier sections. The high dielectric
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11 constant at low frequencies due to sufficient time for polarizaion[26] The space charge carrier fail to keep up with
12 the field and lag behind the alternation of its direction, dipole response is being restricted with the increasing
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14 frequency and saturates towards the higher frequency due to ineffective interfacial and dipolar polarization at high
15 frequency. The internal individual dipoles contribution is due to active electronic polarization at the higher
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17 frequency[21]. Hence, the PVDF-CFO(20 nm) has highest dielectric constant because of its optimized filler grain
18 size of 20 nm size as it has high electroactive phase as discussed in the earlier part of the same section. The
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dielectric constant values reported are greater than the values reported elsewhere[27]. The overall dielectric behavior
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21 consistent with the results obtained from XRD and FTIR results.
22
Conclusion
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24 Nanocomposite of PVDF-CFO with different filler sizes (10-120nm) of CFO has been suscessfully prepared.
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Granular structure of PVDF has been observed for all the composites. The grain size decreases with the decrease in
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27 crystallite size of CFO as obtained from the AFM micrographs. Cobalt ferrite nanoparticles are homogeneously
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distributed within the nano composite. The co-existence of nonpolar α and polar β phase in PVDF has been observed
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30 by employing the XRD and FTIR analysis. Both results are consistent to each other. AFM and FESEM study
31 reveals a core-shell type structure of PVDF-CFO nanocomposite. The dielectric constant of all the nanocomposites
32
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33 is higher than that of PVDF. The dielectric constant of all nanocomposites decrease with the decrease in grain size
34 of filler nanoparticles. The PVDF-CFO (20) with 20 nm grain size filler has highest dielectric constant. The loss of
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36 the PVDF-CFO is found to be very low as compared to pure PVDF. The observed modulation in the dielectric
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37 properties of the films depends on the space charge, grain size, geometrical shape and extent of agglomeration of the
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39 nanoparticles in the PVDF polymer matrix. It is concluded that 20 nm is an optimized value of cobalt ferrite in
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40 PVDF matrix for tuning the dielectric properties. The dielectric behavior in PVDF-CFO can be explained by
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42 Boundary layer Capacitance (BLC’s) model. As a dielectric material, PVDF-CFO nanocomposite films with
43 optimized filler grain size of 20 nm could be a potential candidate for the fabrication of high charge-storing
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45 multilayer capacitors and can be of significant use in electronic industry.
46 Acknowledgement
47
48 Authors are thankful to CSIR, DST and DAE, India vide sanction number 03/1183/10/EMR-II, SR/FTP/PS-
49 103/2009 and 2011/20/37P/03/BRNS/007 respectively, for financial assistance and also UGC-ref. No.: 4050/ (NET-
50
51 JUNE 2013) for financial assistance as JRF.The authors also acknowledge IIT Patna for providing the working
52 platform.
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55 References:
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1. P. Martins, A.C. Lopes, and S. Lanceros-Mendeza, Progress in Polymer Science, 39, 683 (2014).
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3 2. FC. Sun, A. M. Dongare, A. D. Asandei, S. P. Alpay, and S. Nakhmanson, J. Mater. Chem. C, 3, 8389 (2015).
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5 3. T. Nishiyama, T. Sumihara, E. Sato, and H. Horibe, Polymer Journal, 49, 319 (2017).
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9 5. S. Supriya, S. Kumar, and M. Kar, J. Appl.Phys. 120, 215106 (2016).
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11 6. S. Supriya, S. Kumar, and M. Kar, Journal of Materials Science: Materials in Electronics, 28,10652 (2017).
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14 8. R. Kumar, and M. Kar, Journal of Magnetism and Magnetic Materials, 416, 335 (2016).
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17 Polymer Letters, 9, 1104 (2015).
18 10. G. Hua, F. Gao, J. Kong, S. Yang, Q. Zhang, Z. Liu, Y. Zhang, and H. Sun, Journal of Alloys and Compounds,
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619, 686 (2015).
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21 11. V. Sencadas, P. Martins, A. Pitaes, M. Benelmekki, J. L. G. Ribelles, and S. Anceros-Mendez, American
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24 12. S. F. Mendes, C. M. Costa, C. Caparros, V. Sencadas, and S. Lanceros-Me´ndez, J. Mater. Sci., 47, 1378 (2012).
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27 14. T. Prabhakaran, and J. Hemalatha, RSC Adv., 6, 86880 (2016).
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15. L. Ourry, S. Marchesini, M. Bibani, S. Mercone, S. Ammar, and F. Mammeri, Phys. Status Solidi A, 212, 252,
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33 17. L. Kumar, P. Kumar, and M. Kar, J. Alloys Compd., 551, 72, (2013).
34 18. L. Kumar, P. Kumar, and M. Kar, J. Mater. Sci. Mater. Elec., 24(8), 2706, (2013).
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36 19. B. D. Cullity; S. R. Stock, Elements of X-ray Diffraction; Addison-Wesley, Massachusetts, (1956).
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37 20. P. Anithakumari, B. P. Mandal, E. Abdelhamid, R. Naik, and A. K. Tyagi, RSC Adv., 6, 16073 (2016).
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39 21. A. Hartono, S. Satira, M. Djama, R. Ramli, H. Bahar, and E. Sanjaya, Advances in Materials Physics and
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40 Chemistry, 3, 71 (2013).
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42 22. P. Martins, C. Caparros, R. Gonçalves, P. M. Martins, M. Benelmekki, G. Botelho, and S. Lanceros-Mendez, J.
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45 23. X. Liu, S. Liu, MG. Han, L. Zhao, H. Deng, J. Li, Y. Zhu, and L. Elbaum, S. O’Brien, Nanoscale Research
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48 24. A. L. Gayen, B. K. Paul, D. Roy, S. Kar, P. Bandyopadhyay, R. Basu, S. Das, D. S. Bhar, R. K. Manchanda, A.
49 K. Khurana, D. Nayak, and P. Nandy, Materials Research Innovations , 21, 166 (2017).
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51 25. YH. Lin, M. Li, CW. Nan, J. Li, J. Wu and J. He, App. Phys. Lett., 89, 032907 (2006).
52 26. K. Vasundhara, B. P. Mandal, and A. K. Tyagi, RSC Adv., 5, 8591 (2015).
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55 Chemistry and Physics, 131, 698 (2012).
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Figure 2. XRD patterns for (a) CFO(120), CFO (30), CFO(20), CFO(15), CFO(11), CFO(10) and (b) PVDF,
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Figure 5. FTIR Spectra of (a) CFO and (b) PVDF, PVDF-CFO(20), PVDF-CFO (15), PVDF-CFO(11) and CFO-
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Figure 10. (a) β phase content versus filler grain size (b) Dielectric constant (εˈ) versus filler grain size (c)
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Dielectric loss (tan δ) versus filler grain size at temperature130 oC and frequency 100 Hz for CoFe2O4/PVDF
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3 Table I. Crystallite size and Lattice parameters of cobalt ferrite. Errors in lattice parameters are given in the bracket.
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5 Samples Crystallite size Lattice
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(nm) Parameter (Å)
8 CFO (0 h)-1000 oC 120 8.391(1)
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10 CFO (0 h)-600 oC 30 8.387(2)
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CFO (24 h) 20 8.382(2)
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13 CFO (48 h) 15 8.384(1)
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15 CFO (72 h) 11 8.389(2)
16 CFO (96 h) 10 8.398(2)
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3 Table II. β phase content for CoFe2O4/PVDF composite samples as a function of different filler sizes obtained from
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11 PVDF-CFO(120 nm) 0.83
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14 PVDF-CFO(20 nm) 0.43
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16 PVDF-CFO(15 nm) 0.35
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18 PVDF-CFO(11 nm) 0.33
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