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Research Article | Open Access

Effect of nano- and micron-sized K0.5Na0.5NbO3 fillers on the dielectric and piezoelectric properties of PVDF composites

Bharathi PONRAJRajasekhar BHIMIREDDIK. B. R. VARMA( )
Materials Research Centre, Indian Institute of Science, Bangalore-560012, India
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Polymer nanocrystal composites were fabricated by embedding polyvinylidene fluoride (PVDF) with K0.5Na0.5NbO3 (KNN) nanocrystallites of different volume fraction using the hot-pressing technique. For comparison, PVDF–KNN microcrystal composites of the same compositions were also fabricated which facilitated the studies of the crystallite size (wide range) effect on the dielectric and piezoelectric properties. The structural, morphological, dielectric, and piezoelectric properties of these nano and micro crystal composites were investigated. The incorporation of KNN fillers in PVDF at both nanometer and micron scales above 10 vol% resulted in the formation of polar β-form of PVDF. The room temperature dielectric constant as high as 3273 at 100 Hz was obtained for the PVDF comprising 40 vol% KNN nanocrystallites due to dipole–dipole interactions (as the presence of β-PVDF is prominent), whereas it was only 236 for the PVDF containing the same amount (40 vol%) of micron-sized crystallites of KNN at the same frequency. Various theoretical models were employed to predict the dielectric constants of the PVDF–KNN nano and micro crystal composites. The PVDF comprising 70 vol% micron-sized crystallites of KNN exhibited a d33 value of 35 pC/N, while the nanocrystal composites of PVDF–KNN did not exhibit any piezoelectric response perhaps due to the unrelieved internal stress within each grain, besides the fact that they have less domain walls.

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Wang Q, Zhu L. Polymer nanocomposites for electrical energy storage. J Polym Sci Pol Phys 2011, 49: 1421-1429.
Siddabattuni S, Schuman TP. Polymer–ceramic nanocomposite dielectrics for advanced energy storage. In Polymer Composites for Energy Harvesting, Conversion, and Storage. Li L, Wong-Ng W, Sharp J, Eds. Washington, DC, USA: American Chemical Society, 2014: 165-190.
Tan D, Irwin P. Polymer based nanodielectric composites. In Advances in Ceramics—Electric and Magnetic Ceramics, Bioceramics, Ceramics and Environment. Sikalidis C, Ed. InTech, 2011, .
Barber P, Balasubramanian S, Anguchamy Y, et al. Polymer composite and nanocomposite dielectric materials for pulse power energy storage. Materials 2009, 2: 1697-1733.
Ramadan KS, Sameoto D, Evoy S. A review of piezoelectric polymers as functional materials for electromechanical transducers. Smart Mater Struct 2014, 23: 033001.
Chang J, Dommer M, Chang C, et al. Piezoelectric nanofibers for energy scavenging applications. Nano Energy 2012, 1: 356-371.
Varghese J, Whatmore RW, Holmes JD. Ferroelectric nanoparticles, wires and tubes: Synthesis, characterization and applications. J Mater Chem C 2013, 1: 2618-2638.
Bowen CR, Kim HA, Weaver PM, et al. Piezoelectric and ferroelectric materials and structures for energy harvesting applications. Energy Environ Sci 2014, 7: 25-44.
Li Z, Wang J, Wang X, et al. Ferro- and piezo-electric properties of a poly(vinyl fluoride) film with high ferro- to para-electric phase transition temperature. RSC Adv 2015, 5: 80950-80955.
Cui Z, Hassankiadeh NT, Zhuang Y, et al. Crystalline polymorphism in poly(vinylidenefluoride) membranes. Prog Polym Sci 2015, 51: 94-126.
Satapathy S, Pawar S, Gupta PK, et al. Effect of annealing on phase transition in poly(vinylidene fluoride) films prepared using polar solvent. Bull Mater Sci 2011, 34: 727-733.
Lando JB, Olf HG, Peterlin A. Nuclear magnetic resonance and X-ray determination of the structure of poly(vinylidene fluoride). J Polym Sci Pol Chem 1966, 4: 941-951.
Hasegawa R, Kobayashi M, Tadokoro H. Molecular conformation and packing of poly(vinylidene fluoride). Stability of three crystalline forms and the effect of high pressure. Polym J 1972, 3: 591-599.
Chen S, Yao K, Tay FEH, et al. Ferroelectric poly(vinylidene fluoride) thin films on Si substrate with the β phase promoted by hydrated magnesium. J Appl Phys 2007, 102: 104108.
Qi Y, McAlpine MC. Nanotechnology-enabled flexible and biocompatible energy harvesting. Energy Environ Sci 2010, 3: 1275-1285.
Kulek J, Hilczer B, Burianova L, et al. Dielectric, piezoelectric and pyroelectric response of PbTiO3–PVDF composites. J Korean Phys Soc 1998, 32: S1079-S1081.
Seema A, Dayas KR, Varghese JM. PVDF–PZT–5H composites prepared by hot press and tape casting techniques. J Appl Polym Sci 2007, 106: 146-151.
Jain A, Prashanth KJ, Sharma AK, et al. Dielectric and piezoelectric properties of PVDF/PZT composites: A review. Polym Eng Sci 2015, 55: 1589-1616.
Chan HLW, Chen Y, Choy CL. A poling study of PZT/P(VDF-TrFE) copolymer 0–3 composites. Integr Ferroelectr 1995, 9: 207-214.
Luo B, Wang X, Zhao Q, et al. Synthesis, characterization and dielectric properties of surface functionalized ferroelectric ceramic/epoxy resin composites with high dielectric permittivity. Compos Sci Technol 2015, 112: 1-7.
Choy SH, Li WK, Li HK, et al. Study of BNKLBT-1.5 lead-free ceramic/epoxy 1–3 composites. J Appl Phys 2007, 102: 114111.
Sareein T, Thamjaree W, Nhuapeng W, et al. Fabrication of 0–3 non-lead based piezoceramic/polymer composites using suction technique. Adv Mater Res 2008, 55–57: 141-144.
Jadidian B, Hagh NM, Winder AA, et al. 25 MHz ultrasonic transducers with lead-free piezoceramic, 1–3 PZT fiber-epoxy composite, and PVDF polymer active elements. IEEE T Ultrason Ferr 2009, 56: 368-378.
Le DT, Do NB, Kim DU, et al. Preparation and characterization of lead-free (K0.47Na0.51Li0.02)(Nb0.8Ta0.2)O3 piezoceramic/epoxy composites with 0–3 connectivity. Ceram Int 2012, 38: S259-S262.
Kumar P, Mishra P, Sonia S. Synthesis and characterization of lead-free ferroelectric 0.5[Ba(Zr0.2Ti0.8)O3]– 0.5[(Ba0.7Ca0.3)TiO3]–polyvinylidene difluoride 0–3 composites. J Inorg Organomet Polym 2013, 23: 539-545.
Egerton L, Dillon DM. Piezoelectric and dielectric properties of ceramics in the system potassium–sodium niobate. J Am Ceram Soc 1959, 42: 438-442.
Guo Y, Kakimoto K-i, Ohsato H. Phase transitional behavior and piezoelectric properties of (Na0.5K0.5)NbO3– LiNbO3 ceramics. Appl Phys Lett 2004, 85: 4121.
Wu J, Xiao D, Wang Y, et al. Compositional dependenceof phase structure and electrical properties in (K0.42Na0.58)NbO3–LiSbO3(K0.42Na0.58)NbO3–LiSbO3 lead-free ceramics. J Appl Phys 2007, 102: 114113.
Hollenstein E, Davis M, Damjanovic D, et al. Piezoelectric properties of Li- and Ta-modified (K0.5Na0.5)NbO3 ceramics. Appl Phys Lett 2005, 87: 182905.
Park H-Y, Ahn C-W, Song H-C, et al. Microstructure and piezoelectric properties of 0.95(Na0.5K0.5)NbO3– 0.05BaTiO3 ceramics. Appl Phys Lett 2006, 89: 062906.
Wang K, Li J-F. (K,Na)NbO3-based lead-free piezoceramics: Phase transition, sintering, and property enhancement. J Adv Ceram 2012, 1: 24-37.
Zhang P, Wang M, Zhu J, et al. Lead-free piezoelectric composites with high piezoelectric performance and high dielectric constant caused by percolation phenomenon. J Mater Sci: Mater Electron 2014, 25: 4225-4229.
Seol J-H, Lee JS, Ji H-N, et al. Piezoelectric and dielectric properties of (K0.44Na0.52Li0.04)(Nb0.86Ta0.10Sb0.04)O3– PVDF composites. Ceram Int 2012, 38: S263-S266.
Janas VF, Safari A. Overview of fine-scale piezoelectric ceramic/polymer composite processing. J Am Ceram Soc 1995, 78: 2945-2955.
Shrout TR, Schulze WA, Biggers JV. Simplified fabrication of PZT/polymer composites. Mater Res Bull 1979, 14: 1553-1559.
Skinner DP, Newnham RE, Cross LE. Flexible composite transducers. Mater Res Bull 1978, 13: 599-607.
Venkatragavaraj E, Satish B, Vinod PR, et al. Piezoelectric properties of ferroelectric PZT–polymer composites. J Phys D: Appl Phys 2001, 34: 487-492.
Satish B, Sridevi K, Vijaya MS. Study of piezoelectric anddielectric properties of ferroelectric PZT–polymer composites prepared by hot-press technique. J Phys D: Appl Phys 2002, 35: 2048-2050.
Zhang D-Q, Wang D-W, Yuan J, et al. Structural and electrical properties of PZT/PVDF piezoelectric nanocomposites prepared by cold-press and hot-press routes. Chinese Phys Lett 2008, 25: 4410-4413.
Senthilkumar R, Sridevi K, Venkatesan J, et al. Investigations on ferroelectric PZT–PVDF composites of 0–3 connectivity. Ferroelectrics 2005, 325: 121-130.
Mendes SF, Costa CM, Caparros C, et al. Effect of filler size and concentration on the structure and properties of poly(vinylidenefluoride)/BaTiO3 nanocomposites. J Mater Sci 2012, 47: 1378-1388.
Mendes SF, Costa CM, Sencadas V, et al. Effect of the ceramic grain size and concentration on the dynamical mechanical and dielectric behavior of poly(vinilidene fluoride)/Pb(Zr0.53Ti0.47)O3 composites. Appl Phys A 2009, 96: 899-908.
Lee H-G, Kim H-G. Ceramic particle size dependence of dielectric and piezoelectric properties of piezoelectric ceramic polymer composites. J Appl Phys 1990, 67: 2024.
Yamada T, Ueda T, Kitayama T. Piezoelectricity of a high-content lead zirconate titanate/polymer composite. J Appl Phys 1982, 53: 4328.
Stavber G, Malič B, Kosec M. A road to environmentally friendly materials chemistry: Low-temperature synthesis of nanosized K0.5Na0.5NbO3 powders through peroxide intermediates in water. Green Chem 2011, 13: 1303-1310.
Thomas P, Varughese KT, Dwarakanath K, et al. Dielectric properties of poly(vinylidene fluoride)/CaCu3Ti4O12 composites. Compos Sci Technol 2010, 70: 539-545.
Thomas P, Satapathy S, Dwarakanath K, et al. Dielectric properties of poly(vinylidene fluoride)/CaCu3Ti4O12 nanocrystal composite thick films. eXPRESS Polym Lett 2010, 4: 632-643.
Malecki J, Hilczer B. Dielectric behaviour of polymers and composites. Key Eng Mat 1994, 92–93: 181-216.
Sekar R, Tripathi AK, Pillai PKC. X-ray diffraction and dielectric studies of a BaTiO3:PVDF composite. Mat Sci Eng B 1989, 5: 33-36.
Muralidhar C, Pillai PKC. XRD studies on barium titanate (BaTiO3)/polyvinylidene fluoride (PVDF) composites. J Mater Sci 1988, 23: 410-414.
Esterly DM, Love BJ. Phase transformation to β-poly(vinylidene fluoride) by milling. J Polym Sci Pol Phys 2004, 42: 91-97.
Kim GH, Hong SM, Seo Y. Piezoelectric properties of poly(vinylidene fluoride) and carbon nanotube blends: β-phase development. Phys Chem Chem Phys 2009, 11: 10506-10512.
An NL, Liu H, Ding Y, et al. Preparation and electroactive properties of a PVDF/nano-TiO2 composite film. Appl Surf Sci 2011, 257: 3831-3835.
Martins P, Costa CM, Lanceros-Mendez S. Nucleation of electroactive β-phase poly(vinilidene fluoride) with CoFe2O4 and NiFe2O4 nanofillers: A new method for the preparation of multiferroic nanocomposites. Appl Phys A 2011, 103: 233-237.
Martins P, Costa CM, Benelmekki M, et al. On the origin of the electroactive poly(vinylidene fluoride) β-phase nucleation by ferrite nanoparticles via surface electrostatic interactions. CrystEngComm 2012, 14: 2807-2811.
Dang Z-M, Wang H-Y, Peng B, et al. Effect of BaTiO3 size on dielectric property of BaTiO3/PVDF composites. J Electroceram 2008, 21: 381-384.
Sarkar S, Garain S, Mandal D, et al. Electro-active phase formation in PVDF–BiVO4 flexible nanocomposite films for high energy density storage application. RSC Adv 2014, 4: 48220-48227.
Kar E, Bose N, Das S, et al. Enhancement of electroactive β phase crystallization and dielectric constant of PVDF by incorporating GeO2 and SiO2 nanoparticles. Phys Chem Chem Phys 2015, 17: 22784-22798.
Luo B, Wang X, Wang Y, et al. Fabrication, characterization, properties and theoretical analysis of ceramic/PVDF composite flexible films with high dielectric constant and low dielectric loss. J Mater Chem A 2014, 2: 510-519.
Bharathi P, Varma KBR. Effect of the addition of B2O3 on the density, microstructure, dielectric, piezoelectric and ferroelectric properties of K0.5Na0.5NbO3 ceramics. J Electron Mater 2014, 43: 493-505.
Furukawa T, Ishida K, Fukada E. Piezoelectric properties in the composite systems of polymers and PZT ceramics. J Appl Phys 1979, 50: 4904.
Bhimasankaram T, Suryanarayana SV, Prasad G. Piezoelectric polymer composite materials. Current Sci 1998, 74: 967-976.
Yamada T, Ueda T, Kitayama T. Piezoelectricity of a high-content lead zirconate titanate/polymer composite. J Appl Phys 1982, 53: 4328-4332.
Araújo MC, Costa CM, Lanceros-Méndez S. Evaluation of dielectric models for ceramic/polymer composites: Effect of filler size and concentration. J Non-Cryst Solids 2014, 387: 6-15.
Rujijanagul G, Boonyakul S, Tunkasiri T. Effect of the particle size of PZT on the microstructure and the piezoelectric properties of 0–3 PZT/polymer composites. J Mater Sci Lett 2001, 20: 1943-1945.
Paik H, Choi Y-Y, Hong S, et al. Effect of Ag nanoparticle concentration on the electrical and ferroelectric properties of Ag/P(VDF-TrFE) composite films. Sci Rep 2015, 5: 13209.
Dou X, Liu X, Zhang Y, et al. Improved dielectric strength of barium titanate–polyvinylidene fluoride nanocomposite. Appl Phys Lett 2009, 95: 132904.
Aulagner E, Guillet J, Seytre S, et al. (PVDF/BaTiO3) and (PP/BaTiO3) films for energy storage capacitors. In Proceedings of the 1995 IEEE 5th International Conference on Conduction and Breakdown in Solid Dielectrics, Leicester, England, 1995: 423–427.
Singha S, Thomas MJ. Dielectric properties of epoxy nanocomposites. IEEE T Dielect El In 2008, 15: 12-23.
Journal of Advanced Ceramics
Pages 308-320
Cite this article:
PONRAJ B, BHIMIREDDI R, VARMA KBR. Effect of nano- and micron-sized K0.5Na0.5NbO3 fillers on the dielectric and piezoelectric properties of PVDF composites. Journal of Advanced Ceramics, 2016, 5(4): 308-320.








Web of Science






Received: 09 June 2016
Revised: 25 July 2016
Accepted: 25 August 2016
Published: 23 December 2016
© The author(s) 2016

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