5-phase PVDF

The rate of phenol degradation catalyzed by decatungstate in homogeneous phase and in heterogeneous phase (PVDF-W10 membrane) was similar however, when the catalyst is immobilized in the polymeric membranes a higher mineralization degree of the phenol was observed [42],... 

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]. 

Unlike other synthetic polymers, PVDF has a wealth of polymorphs at least four chain conformations are known and a fifth has been suggested (119). The four known distinct forms or phases are alpha (II), beta (I), gamma (III), and delta (IV). The most common a-phase is the trans-gauche (tgtg ) chain conformation placing hydrogen and fluorine atoms alternately on each side of the chain (120,121). It forms during polymerization and crystallizes from the melt at all temperatures (122,123). The other forms have also been well characterized (124—128). The density of the a polymorph crystals is 1.92 g/cm and that of the P polymorph crystals 1.97 g/cm (129) the density of amorphous PVDF is 1.68 g/cm (130). 

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. 

Copolymer compositions differ from PVDF in that the crystalline P phase is obtained without mechanical deformation. Thus, various thicknesses of the material can be readily produced. Unfortunately, a reproducible copolymer is not yet commercially available. 

In this chapter studies of physical effects within the elastic deformation range were extended into stress regions where there are substantial contributions to physical processes from both elastic and inelastic deformation. Those studies include the piezoelectric responses of the piezoelectric crystals, quartz and lithium niobate, similar work on the piezoelectric polymer PVDF, ferroelectric solids, and ferromagnetic alloys which exhibit second- and first-order phase transformations. The resistance of metals has been investigated along with the distinctive shock phenomenon, shock-induced polarization. 

The preparation and properties of a novel, commercially viable Li-ion battery based on a gel electrolyte has recently been disclosed by Bellcore (USA) [124]. The technology has, to date, been licensed to six companies and full commercial production is imminent. The polymer membrane is a copolymer based on PVdF copolymerized with hexafluoropropylene (HFP). HFP helps to decrease the crystallinity of the PVdF component, enhancing its ability to absorb liquid. Optimizing the liquid absorption ability, mechanical strength, and processability requires optimized amorphous/crystalline-phase distribution. The PVdF-HFP membrane can absorb plasticizer up to 200 percent of its original volume, especially when a pore former (fumed silica) is added. The liquid electrolyte is typically a solution of LiPF6 in 2 1 ethylene carbonate dimethyl car-... 

A phase transition can be induced also by a high electric field. This is, for instance, the case of the conversion of the non polar a form (form II) of PVDF to the polar 8 form (form lip) [31] (see Sect. 2.3). 

In particular, blends of PVDF with a series of different polymers (polymethylmethacrylate [100-102], polyethylmethacrylate [101], polyvinyl acetate [101]), for suitable compositions, if quenched from the melt and then annealed above the glass transition temperature, yield the piezoelectric [3 form, rather than the normally obtained a form. The change in the location of the glass transition temperature due to the blending, which would produce changes in the nucleation rates, has been suggested as responsible for this behavior. A second factor which was identified as controlling this behavior is the increase of local /rans-planar conformations in the mixed amorphous phase, due to specific interactions between the polymers [102]. 

According to Tarascon and co-workers, the swelling of PVdF—HFP by liquid electrolytes was never complete due to the semicrystalline nature of the copolymer, which tends to microphase-separate after the activation by electrolyte. On the other hand, it is those crystalline domains in the gelled PVdF—HFP that provide mechanical integrity for the resultant GPE. Thus, a dual phase structure was proposed for the Bellcore GPE by some authors, wherein the amorphous domain swollen by a liquid electrolyte serves as the ion conduction phase, while tiny crystallites act as dimensional stabilizer. 

These types of separators consist of a solid matrix and a liquid phase, which is retained in the microporous structure by capillary forces. To be effective for batteries, the liquid in the microporous separator, which generally contains an organic phase, must be insoluble in the electrolyte, chemically stable, and still provide adequate ionic conductivity. Several types of polymers, such as polypropylene, polysulfone, poly(tetrafluoroethylene), and cellulose acetate, have been used for porous substrates for supported-liquid membranes. The PVdF coated polyolefin-based microporous membranes used in gel—polymer lithium-ion battery fall into this category. Gel polymer... 

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. 

In the P phase of polyvinylene fluoride (PVDF), the CF2 groups in a polymer chain are all pointing in the same direction (Figure 9.20), so that a dipole moment... 

In addition to quantitative estimates of material properties, molecular modeling can offer valuable qualitative insights into the dynamical properties of materials, without resorting to direct simulation (e.g., molecular dynamics), where the rigorous treatment of all the dynamics at the atomic scale would be prohibitively time-consuming. To illustrate this point, the second part of this chapter describes recent studies of the relaxation in the crystalline a-phase of PVDF. Molecular modeling provides a way to characterize the mechanism of... 

The unique piezoelectric and pyroelectric properties of semicrystalline films of PVDF arise from changes in the polarization imparted to the overall film by the crystalline P-phase. The polar nature of the P-phase is, in turn, a direct result of the parallel alignment of the dipole moment of the repeat units in the unit cell (Figure 11.1). The crystal polarization is defined as the dipole moment density of the crystal ... 

From Eq, (1) it is clear that a model of crystal polarization that is adequate for the description of the piezoelectric and pyroelectric properties of the P-phase of PVDF must include an accurate description of both the dipole moment of the repeat unit and the unit cell volume as functions of temperature and applied mechanical stress or strain. The dipole moment of the repeat unit includes contributions from the intrinsic polarity of chemical bonds (primarily carbon-fluorine) owing to differences in electron affinity, induced dipole moments owing to atomic and electronic polarizability, and attenuation owing to the thermal oscillations of the dipole. Previous modeling efforts have emphasized the importance of one more of these effects electronic polarizability based on continuum dielectric theory" or Lorentz field sums of dipole lattices" static, atomic level modeling of the intrinsic bond polarity" atomic level modeling of bond polarity and electronic and atomic polarizability in the absence of thermal motion. " The unit cell volume is responsive to the effects of temperature and stress and therefore requires a model based on an expression of the free energy of the crystal. 

For the P-phase of PVDF the fc-axis is a principal axis of the polarizability tensor of the repeat unit in the absence of an applied field, only the component of parallel to the (>-axis is nonzero. Equation (3) may thus be expressed in scalar form, where Ap is also directed along the b-axis. 

In the case of polar crystals such as the P-phase of PVDF, the elastic and dielectric properties are strongly coupled. This coupling, described formally in... 

The high-frequency dielectric constant is determined by the effects of electronic polarization. An accurate estimate of this property lends confidence to the modeling of the electronic polarization contribution in the piezoelectric and pyroelectric responses. The constant strain dielectric constants (k, dimensionless) are computed from the normal modes of the crystal (see Table 11.1). Comparison of the zero- and high-frequency dielectric constants indicates that electronic polarization accounts for 94% of the total dielectric response. Our calculated value for k (experimental value of 1.85 estimated from the index of refraction of the P-phase of PVDF. ... 

Table 11.1. Calculated Properties of the P-phase of PVDF at Several Temperatures...

The material properties appearing in Eqs. (6)-(9) are defined by the partial derivatives of the dependent variables (P, c, e) with respect to the independent variables. At this point, to maintain consistency with the literature on the P-phase of PVDF, we label c as the 1 axis, a as the 2 axis, and, b as the 3 axis. In evaluating the piezoelectric and pyroelectric responses we consider changes in polarization along the 3 axis only polarization along the 1 and 2 axes remains zero, by symmetry, for all the cases considered here. The direct piezoelectric strain 03 , pC/N) and stress (gaj, C/iiE) coefficients are defined in Eqs. (10) and (11),... 

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