Structural and Dielectrical Study of PZT/PVDF Film Composites
Structural and Dielectrical Study of PZT/PVDF Film Composites
Structural and Dielectrical Study of PZT/PVDF Film Composites
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International Journal of Application or Innovation in Engineering& Management (IJAIEM)
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Volume 2, Issue 4, April 2013 ISSN 2319 - 4847
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3.4 Dielectric Relaxation
The relaxation effect of frequency on dielectric constant and dielectric loss for neat PVDF film and PZT/PVDF film
composites are described in the following sections.
3.4.1 Neat PVDF
The frequency dependence of the dielectric constant and dielectric loss at room temperature at 1.E+02- 1.E+07 Hz for
neat PVDF film with different poling conditions are given in Fig. 9 and Fig.10 respectively.
Two features are observed, firstly, the dielectric constant shows appreciable increase with poling procedures and it is
nearly stable along the frequency up to 1MHz. For instance at thermal poling and field of 6.5 kV the increase of
dielectric constant is due to the amount of polar - phase present in the crystalline PVDF; whereas the high
r
value
when corona charging by a field of 20 kV.
A consequence of the transformation to the oriented polar - phase could be due to the arrangement of dipoles with
electric field direction.
Secondly, from Fig. (10) high dielectric loss is observed at low frequency (1KHz) and high frequency (beyond 1MHz),
whereas minimum dielectric loss is observed at 50KHz. High loss at low frequency results from the interfacial
polarization which increases with the alignment of crystalline regions with direction of poling field, whereas the loss at
high frequency is due to the crystal region wall vibration which results from vibration of CH-CF dipoles of amorphous
region in crystal region [13].
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3.4.2 PZT/PVDF Films Composites
The frequency dependence of dielectric constant and loss at room temperature for unpoled PZT/PVDF film composites
are shown in Fig. (11) and Fig.(12) respectively.
It is observed that both dielectric constant and loss increase with high PZT volume fraction due to high dielectric
constant value of PZT ceramic [23].Different from neat PVDF, PZT/PVDF composites show decline in dielectric
constant at higher frequencies especially for the high PZT volume fractions caused by the domains of PZT.
The dielectric loss for PZT/PVDF films composites show similar behavior to neat PVDF, however, PZT/PVDF films
composites, higher loss results about 10 times for neat PVDF was observed due to domain-wall motion of PZT in
composite whose natural frequency coincides with the frequency of the applied field [22].
Fig.11 Frequency dependence of dielectric constant of unpoled neat PVDF nd PZT/PVDF film composites
3.5 Dependence of Dielectric Constant on PZT Volume Faraction
It is observed that poling of PVDF or PZT/PVDF films causes an appreciable increase in the dielectric constant. It is
also noticed that values of dielectric constant of PZT, PVDF, and PZT/PVDF film composites are nearly in line with
the results published by many references [21, 13].
Dependence of dielectric constant on PZT volume fraction for unpoled and poled neat PVDF, PZT/PVDF film
composites are shown in Fig.(13).The dielectric constant increased markedly with increasing PZT volume fraction
before and after polarization.
However, for the unpoled films, PVDF might have formed an insulating layer over the grains of PZT at low volume
fraction of PZT in PZT/PVDF films composites, andthereby blocking the contribution coming from PZT. This is why
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the dielectricconstant for these samples before polarization are lower. High dielectric constant have been obtained at
high PZT volume fraction, since the PZT powder used was in tetragonal phase as identified by XRD and the dielectric
constant of this phase is highest. Therefore the high dielectric constant of the binary system PZT/PVDF of high volume
fraction of PZT is due to high dielectric constant value of PZT ceramic [22].
Fig. 13 Dielectric constant of unpoled and poled PZT/PVDF film composites as a function of PZT volume fractions at
1kHz
3.6 Mathematical Models of Dielectric Constants
3.6.1 Furukawa Mathematical Model
Furukawa et al [24] has considered two phases system, which is composed of continuous phase (polymer) and a
piezoelectric spherical phase (PZT).
The dielectric constants were calculated by using the (Furukawa mathematical model phase) for comparing
theoretical with experimental results of dielectric constants for PZT/PVDF film composites equation (1) [24].
(1)
Where
is the volume fraction of spherical particles.
and are the dielectric constant of the two phases.
The dependence of the dielectric constant on PZT volume fraction is shown in Fig.(14). It is observed that the
experimental values of dielectric constant for PZT/PVDF film composites areabout3 times larger than calculated values
at higher volume fraction of PZT. This suggests that the Furukawa model which treats spherical dispersions does not
apply to this case since the domains of PZT particles are anisotropic [24].
Fig.14. Calculated and experimental dielectric constants of poled PZT/PVDF film composites as a function of PZT
volume fraction
3.6.2 Yamada mathematical model
Yamada et al [25 ] has considered a binary system consists of continuous phase (polymer) of the dielectric constant
1
and the ellipsoidal particles (PZT) of the dielectric constant
2
.
The calculated values of dielectric constants of PZT/PVDF film composites with different PZT volume fraction with
Yamada mathematical model is given by equation ( 2).
1
e=e
e e + e
e e
+
) 1 ( ) (
) (
1
1 2 1
1 2
q n
nq
(2)
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where
q is the volume fraction for the ellipsoidal particles.
n is the parameter attributed to the shape of the ellipsoidal particles.
The dependence of the dielectric constant on PZT volume fraction is shown in Fig.(15).It is observed that the
experimentalvalues ofdielectric constants for PZT/PVDF film composites are comparatively less than calculated values.
The deviation in experimental values from the calculated ones may be due to pores present in PZT/PVDF film
composites [25].
The parameter n in equ.(2) was taken in accordance with the consideration by Yamada mathematical model
calculation of dielectric constant. A value of n =8 instead of 8.5 taken by Yamada et al. [25] was found to better fit
with the experimental values, indicating that the shape of the particles are nearly identical [26].
0.00 0.20 0.40 0.60 0.80
PZT Vol. Fraction
0
40
80
120
160
200
c
Exp. Unpload
Exp. Poled
Exp. Corona
Cal. Unpoled
Cal. Poled
Cal. Corona
r
Fig. 15 Calculated and experimental dielectric constants of unpoled and poled PZT/PVDF film composites as a
function of PZT volume factions
4. CONCLUSIONS
1-Poling procedures whether thermal or corona proved to induce changes in the structure of PVDF towards - phase
manifested by monitoring the intensity of X- ray reflections.
2- The dielectric constant of the composite films seem to be influenced by PZT ceramic powder rather than PVDF
polymer in addition tothe status of the films being poled.
3- In contrast to neat PVDF, PZT/PVDF films composites show decline in dielectric constant at high frequency for
high PZT volume fractions. Dielectric loss is also influenced by the presence of PZT in the composites and increase it
to about 10 times that of neat PVDF.
4- The mathematical models devised to simulate the experimental dielectric constants appear to be in reasonable
agreement of the ellipsoidal phase model. Slight deviation due to porespresent in the PZT/PVDF film. The
experimental dielectric constants appear to be larger 3 times than calculated values of the spherical phase model for
High volume fraction of PZT. Deviations is thought to be due to anisotropic nature of PZT particles.
REFERENCES
[1.] Y. Erol charvey, Design, Fabrication and Testing of Piezoelectric Polymer PVDF microstructures online at sacks
15, 141-146, (2006).
[2.] S.Chand and M.S.Bhatnagar, A text Book chemistry and Technology of polymers, Volume-1 Basic concept,
India, publishing com. LTP First edition (2004).
[3.] W. Ki Lee and Chang-Sik Ha , Miscibility and surface crystalmorphology of blends Contain Poly (Venylidene
Fluoride) by atomic force microscopy, Polymer 39(26), 7131-7134, (1998).
[4.] W. Ki Lee and Chang-Sik Ha , Miscibility and surface crystal morphology of blends Contain Poly (Venylidene
Fluoride) by atomic force microscopy, Polymer 39(26), 7131-7134,(1998).
[5.] Y. Yadong Jiang, Phase Transition of poly(vinylidene fluoride) Under Electric Field , Taylor and Francis
Group-Artice.htm, 80, 245- 251, (2006).
[6.] B. A. Newman, C. H. Yoon, K. D. Pae, & J. I. Scheinbeim, Piezoelectric Activity and Field-Induced Crystal
Structure Transition in poled PVDF Films, J. Appl. Phys., 50(10), 6095-6100, (1979).
[7.] B. L. Cheng and M. J. Reece, Stress relaxation and estimation and activation volume in a commercial had PZT
piezoelectric ceramic, Bull, Mater. Sci. 24(2), 165-167, (2001).
[8.] B.Schaufele, and K. Heinz, Ferroelastic properties of Lead Zirconate Titanate ceramics, Journal of the
American Ceramic Society 79(1) 225-232, (1996).
[9.] G.Advani Suresh, Process Modeling in Composites Manufacturing, Marcel Dekker, INC. New York, (2003).
International Journal of Application or Innovation in Engineering& Management (IJAIEM)
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Volume 2, Issue 4, April 2013 ISSN 2319 - 4847
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[10.] Y. Roh, and V. V. Varadan, Characterization of All the Elastic, Dielectric, and Piezoelectric Constant of
Uniaxial Oriented Poled PVDF Films, J. Institute of Electrical and Electronics Engineers, inc., (2002).
[11.] M. A. Marcus, Orientation effect on electric and piezoelectric properties of polyvenylidene fluoride films, IEEE
Trans. Elec. Ins., vol. E I21(3) p519, (1986)
[12.] E. Venkaragavaraj, B. Satish, and P. R. Vinod, Piezoelectric properties of ferroelectric PZT-polymer
composites , Issue PSG College of Technology, India(2001).
[13.] D. Sinha, & P.K.C.Pillai, The Conductivity Behavior in Lead Zirconate Titanate Polyvinylidene Fluoride
Composites, J.Appl.Phys., 64(5), 2571-2574, (1988).
[14.] S. N. Fedosov andA. E. Sergeeva, Corona poling of ferroelectric and nonlinearoptical polymers, Moldavian
Journal of Physical Science, 2, (2002).
[15.] Y. Bar-Cohen and X. Boa, Characterization of the Electromechanical Properties of IonomericPolymer-Metal
Composite (IPMC), EAPAD Conference, (2002).
[16.] G.T. Davis, J.E. Mekinny, M.G. Broadhurst, and S.C.Roth, Electric- Field-induced phase changes in
polyvenylidene fluoride, J. Appl. Phys., 49(10), 4992- 4997, (1978).
[17.] K. Tashio and K. Takano, Phase transition at a temperature immediately below the melting point of
poly(vinylidene fluoride) form I: A proposition for the ferroelectric Curie point , Polymer, 24, 199-204, (1983).
[18.] Y. Yadong Jiang, Phase Transition of poly(vinylidene fluoride) Under Electric Field , Taylor and Francis
Group-Artice.htm, 80, 245- 251, (2006).
[19.] D. Sinha and P. K. C. Pillai, Investigations of Structural And Thermal Properties of Lead Zirconate Titanate-
Polyvinylidene Fluoride Composites , J. Mate. Sci., 25, 944-949, (1990).
[20.] X. Zheng, Y. Zhou, and Z. Uan, Dependence of Crystalline ferroelectric and Fracture toughness on annealing in
Pb(Zr Ti)O thin films deposited by metal organic decomposition, Mat. Res., 4, 1648- 1655, (2003).
[21.] J. Runt, and E. C. Galgoci, Polymer/ Piezoelectric Ceramic Composites: Polystyrene and Poly(methyl
methacrylate) with PZT , J. Appl. Poly. Sci., 29, 611-617, (1984).
[22.] B. Hilczer, J. Kutek and E.Markiewicz, Dielectric and PyroelectricResponse of Ceramic-Polymer
Nanocomposites, Processing of Electroceramics, (2003).
[23.] C.Mualidhar, and P.K.C.Pillai, Pyroelectric Behavior in Bari Titanate/Polyvinylidene Fluoride Composites,
IEEE Trans. Elect. Insul., El-21( 3), 501-504, (1986).
[24.] T. Furukawa, J. Aiba, & E. Fukada, Piezoelectric Relaxation in Polyvinylidene Fluoride, J. Appl. Phys., 50(5),
3615-3621, (1979).
[25.] T.Yamada, T.Ueda, & T. Kitayama, Piezoelectricity of a High- Content Lead Zirconate Titanate/Polymer
Composite, J. Appli. Phys., 53(6) 4328-4332, (1982).
[26.] F. Noori Study the dielectric and piezoelectric properties for PZT/ PVDF composltes,Ph.D thesis Physics
Department ,College of Science, University of Baghdad( 2007).