Poly(vinylidene fluoride-trifluoroethylene) based high performance electroactive polymers

Making use of defects modification to P(VDF-TrFE) via either high energy electron irradiation treatment or copolymerizing VDF-TrFE with a small amount of chlorinated monomer to form a random terpolymer, we demonstrate that high electromechanical responses can be realized in P(VDF-TrFE) based polymers. It will be shown that in the stretched and irradiated 68/32 mol% copolymer, a transverse strain of 4.5% and a transverse electromechanical coupling factor k/sub 31/ of 0.65 can be induced under a field of 85 MV/m. In addition, the irradiated copolymer also exhibits a high elastic energy density, /spl sim/ 1 J/cm/sup 3/. For PVDF based terpolymers such as P(VDF-TrFE-CFE) terpolymer (CFE: chlorofluoroethylene), an electrostrictive strain of more than 7% can be obtained. To elucidate the microstructure changes due to the defects modification in P(VDF-TrFE) based polymers, synchrotron X-ray measurement was carried out on the irradiated copolymers and the results show that, the irradiation converts the polar-phase into a nonpolar phase. In addition, X-ray date show that the polar-phase can be induced, at the expense of the nonpolar phase, by external fields, confirming that the field induced conformation change is responsible for the observed high electromechanical responses. Although the modified PVDF based polymer exhibits the highest room temperature dielectric constant (60 versus below 10), it is still far below those in the inorganic materials. Experimental results show that by using delocalized electrons in conjugated bonds an all-organic composite with a dielectric constant more than 400 can be achieved. As a result, a strain of near 2% with an elastic energy density higher than 0.1 J/cm/sup 3/ can be induced under a low applied field of 13 V//spl mu/m. The strain is proportional to the applied field and the composite has an elastic modulus near 1 GPa.

[1]  R. D. Gould Structure and electrical conduction properties of phthalocyanine thin films , 1996 .

[2]  F. Xia,et al.  An all-organic composite actuator material with a high dielectric constant , 2002, Nature.

[3]  Karen K. Gleason,et al.  NMR characterization of electron beam irradiated vinylidene fluoride–trifluoroethylene copolymers , 2002 .

[4]  P. Dario,et al.  Micro-systems in biomedical applications , 2000 .

[5]  R. Y. Ting,et al.  Space-charge-enhanced electromechanical response in thin-film polyurethane elastomers , 1997 .

[6]  Paul Moses,et al.  A bimorph based dilatometer for field induced strain measurement in soft and thin free standing polymer films , 1998 .

[7]  Fred B. Bateman,et al.  Dielectric relaxation behavior and its relation to microstructure in relaxor ferroelectric polymers: High-energy electron irradiated poly(vinylidene fluoride-trifluoroethylene) copolymers , 2002 .

[8]  Zhang,et al.  Giant electrostriction and relaxor ferroelectric behavior in electron-irradiated poly(vinylidene fluoride-trifluoroethylene) copolymer , 1998, Science.

[9]  Haiping Xu,et al.  High electromechanical responses in a poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) terpolymer , 2002 .

[10]  Jiangyu Li Exchange coupling in P(VDF-TrFE) copolymer based all-organic composites with giant electrostriction. , 2003, Physical review letters.

[11]  Q. Pei,et al.  High-speed electrically actuated elastomers with strain greater than 100% , 2000, Science.

[12]  Qiming Zhang,et al.  Characteristics of the electromechanical response and polarization of electric field biased ferroelectrics , 1995 .

[13]  K. Tashiro,et al.  Structural study on ferroelectric phase transition of vinylidene fluoride-trifluoroethylene copolymers (III) dependence of transitional behavior on VDF molar content , 1984 .

[14]  Haisheng Xu,et al.  Electrostrictive poly(vinylidene fluoride-trifluoroethylene) copolymers , 2001 .

[15]  Haisheng Xu,et al.  Polarization and structural properties of high-energy electron irradiated poly(vinylidene fluoride-trifluoroethylene) copolymer films , 2000 .

[16]  H. A. Pohl,et al.  Giant polarization in stable polymeric dielectrics , 1984 .

[17]  J. Parker,et al.  Phthalocyanine polymers. II. Synthesis and characterization of some metal phthalocyanine sheet oligomers , 1982 .

[18]  Qiming Zhang,et al.  Structural, Conformational, and Polarization Changes of Poly(vinylidene fluoride−trifluoroethylene) Copolymer Induced by High-Energy Electron Irradiation , 2000 .

[19]  Kenji Omote,et al.  Temperature dependence of elastic, dielectric, and piezoelectric properties of “single crystalline’’ films of vinylidene fluoride trifluoroethylene copolymer , 1997 .

[20]  Qiming Zhang,et al.  Transverse strain responses in the electrostrictive poly(vinylidene fluoride–trifluorethylene) copolymer , 1999 .

[21]  Robert Y. Ting,et al.  TRANSVERSE STRAIN RESPONSES IN ELECTROSTRICTIVE POLY(VINYLIDENE FLUORIDE-TRIFLUOROETHYLENE) FILMS AND DEVELOPMENT OF A DILATOMETER FOR THE MEASUREMENT , 1999 .

[22]  H. Nalwa,et al.  Dielectric properties of copper-phthalocyanine polymer , 1985 .

[23]  C. Hom,et al.  Calculation of quasi-static electromechanical coupling coefficients for electrostrictive ceramic materials , 1994, IEEE Transactions on Ultrasonics, Ferroelectrics and Frequency Control.

[24]  F. Kremer,et al.  Giant lateral electrostriction in ferroelectric liquid-crystalline elastomers , 2001, Nature.

[25]  Haisheng Xu,et al.  Ferroelectric and electromechanical properties of poly(vinylidene-fluoride–trifluoroethylene–chlorotrifluoroethylene) terpolymer , 2001 .