Electric properties, PVDF ferroelectric

In this book those ferroelectric solids that respond to shock compression in a purely piezoelectric mode such as lithium niobate and PVDF are considered piezoelectrics. As was the case for piezoelectrics, the pioneering work in this area was carried out by Neilson [57A01]. Unlike piezoelectrics, our knowledge of the response of ferroelectric solids to shock compression is in sharp contrast to that of piezoelectric solids. The electrical properties of several piezoelectric crystals are known in quantitative detail within the elastic range and semiquantitatively in the high stress range. The electrical responses of ferroelectrics are poorly characterized under shock compression and it is difficult to determine properties as such. It is not certain that the relative contributions of dominant physical phenomena have been correctly identified, and detailed, quantitative materials descriptions are not available. 

The unique dielectric properties and polymorphism of PVDF are the source of its high piezoelectric and pyroelectric activity.75 The relationship between ferroelectric behavior, which includes piezoelectric and pyroelectric phenomena and other electrical properties of the polymorphs of polyvinylidene fluoride, is discussed in Reference 76. 

We have shown how Electrostatic Force Microscopy can be an extremely useful tool to investigate and to modify the electric properties of sample surfaces on a microscopic and even nanoscopic scale and we have presented a phenomenological model to help relating the experimental data to the material properties. Ferroelectric domains can locally be reoriented and their time evolution can be followed, as was shown for PZT. We have also demonstrated how the ferroelectric polymer PVDF-TrFe could be locally modified which can be used to locally vary the optical properties of a LC cell. Finally, we have demonstrated that rubbing polymer substrates can indeed result in electrostatic charging, in particular for PMMA and PI, while no charging is found for PVA. 

Application of the concepts obtained in the study of PVDF and its copolymers has been made for other types of novel polymers with similar polar chemical structure. For example, poly(vinylidene cyanide) (PVDCN) and its copolymer with vinyl n-fatty acid ester have ciMmical structures close to that of PVDF F atoms arc displaced by CN groups. These polymers are also attracting attention because of their characteristic electric properties. Odd-numbered members of nylon (nylon 7, nylon 11, etc.) and ferroelectric liquid-crystalline polymers (FLCP) are also the candidates for ferroelectric polymers. These substances are still new. and their structural study has not yet been developed extensively compared with the study of PVDF and its copolymers. 

Since a ferroelectric material is crystalline, with a polar unit cell in which the di> rection of polarization can be changed by the application of an electric field, it was necessary to show that the direction of polarization of the crystalline phase of the PVDF films was being changed by the poling process. It was well estabUshed that fi-phase PVDF has a polar unit cell long tefore its interesting electrical properties were discovered (19]. 

The spectroscopic analysis and various physical, dielectric, and electrical properties of odd-numbered nylons have been sumtxtarized. Odd-numbered nylons sb polymorphism. Nylon-11 shows at least live different crystal forms. The y form seems to be the most common polymorph in many odd-numbered nylons. The piezoelectric and ferroelectric behaviors fA odd-numbered nylons such as nylon-7 and nykm-11 are comparable or belter than for PVDF and depend on the crystal form. The desired stability of the piezoelectric response in odd-munbered nylons is related to the ferroelectric reorientation of the amide group dipoles followed by densely packed hydrogen-bonded sheets in the crystalline regions induced by poling and annealing. 

In order to anticipate problems and to interpret observations under the extreme conditions of shock compression, it is necessary to consider structural and electronic characteristics of PVDF. Although the phenomenological piezoelectric properties of PVDF are similar to those of the piezoelectric crystals, the structure of the materials is far more complex due to its ferroelectric nature and a heterogeneous mixture of crystalline and amorphous phases which are strongly dependent on mechanical and electrical history. 

PVDF is mainly obtained by radical polymerisation of 1,1-difluoroethylene head to tail is the preferred mode of linking between the monomer units, but according to the polymerisation conditions, head to head or tail to tail links may appear. The inversion percentage, which depends upon the polymerisation temperature (3.5% at 20°C, around 6% at 140°C), can be quantified by F or C NMR spectroscopy [30] or FTIR spectroscopy [31], and affects the crystallinity of the polymer and its physical properties. The latter have been extensively summarised by Lovinger [30]. Upon recrystallisation from the melted state, PVDF features a spherulitic structure with a crystalline phase representing 50% of the whole material [32]. Four different crystalline phases (a, jS, y, S) may be identified, but the a phase is the most common as it is the most stable from a thermodynamic point of view. Its helical structure is composed of two antiparallel chains. The other phases may be obtained, as shown by the conversion diagram (Fig. 7), by applying a mechanical or thermal stress or an electrical polarisation. The / phase owns ferroelectric, piezoelectric and pyroelectric properties. 

Ferroelectric composites are alternatives to standard piezoelectric and pyroelectric ceramics such as lead zirconate titanate (PZT) and BaHOs (BT). They combine the strong ferroelectric and dielectric properties of ceramics with the easy processing and good mechanical properties of polymers. Dispersion of micrometer-sized ferroelectric particles in an electrically passive epoxy matrix was first published by Furukawa et al. [1976] and later extended to ferroelectric matrices such as poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-co-3-fluoroethylene) (PVDF-TrFE) [Hsiang et al., 2001 Hilczer et al., 2002 Gimenes et al., 2004 Lam et al., 2005 Beloti et al., 2006]. However, the necessity of miniaturization of electronic components and... 

Pyro- and Piezoelectric Properties The electric field application on a ferroelectric nanoceramic/polymer composite creates a macroscopic polarization in the sample, responsible for the piezo- and pyroelectricity of the composite. It is possible to induce ferroelectric behavior in an inert matrix [Huang et al., 2004] or to improve the piezo-and pyroelectricity of polymers. Lam and Chan [2005] studied the influence of lead magnesium niobate-lead titanate (PMN-PT) particles on the ferroelectric properties of a PVDF-TrFE matrix. The piezoelectric and pyroelectric coefficients were measured in the electrical field direction. The Curie point of PVDF-TrFE and PMN-PT is around 105 and 120°C, respectively. Different polarization procedures are possible. As the signs of piezoelectric coefficients of ceramic and copolymer are opposite, the poling conditions modify the piezoelectric properties of the sample. In all cases, the increase in the longitudinal piezoelectric strain coefficient, 33, with ceramic phase poled) at < / = 0.4, the piezoelectric coefficient increases up to 15 pC/N. The decrease in da for parallel polarization is due primarily to the increase in piezoelectric activity of the ceramic phase with the volume fraction of PMN-PT. The maximum piezoelectric coefficient was obtained for antiparallel polarization, and at < / = 0.4 of PMN-PT, it reached 30pC/N. 

The ferroelectric property of PVDF form I (and its copolymers) reflects diractly on the hi sl piezo- and pyroelectric effects among the synlh ptri3rmets. Piezoelect strain or stress constant tensor, d or e, are defined, respectively, as follows for the polarization change AP caused by stress a or strain c under the oonditioo of constant temperature and zero electric field ... 

The electrical and mechanical properties trf piezoelectric polymers make them a possible alternative to ferroelectric ceramics such as lead zirconate titanate. For several reasons, they are attractive for transducer design. The mechanical flexibility and conformability of thin-film PVDF means that it can be configured into a wide range of transducer products. The low acoustic impedance of PVDF is companrf>le to body tissues, which makes it useful for acoustic imaging applications. Short impulse response and high axial resolution in acoustic imaging systems arc possible with PVDF-featured devices because of the robustness and broadband characteristics of the polymer. 

The electrical and mechanical properties of piezoelectric polymers make them interesting also in the development of electroacustk or ultrasonic transducers for medical applications. Comparison of tbe representative PVDF material characteristics with a convenlional ferroelectric ceramic as PZT shows several features of piezoelectric polymers which make them attractive in transducer design (TU>le 1). 

---