A general all-atom force field for atomistic simulation of common organic molecules, inorganic small molecules, and polymers was developed using state-of-the-art ab initio and empirical parametrization techniques. The valence parameters and atomic partial charges were derived by fitting to ab initio data, and the van der Waals (vdW) parameters were derived by conducting MD simulations of molecular liquids and fitting the simulated cohesive energies and equilibrium densities to experimental data. The combined parametrization procedure significantly improves the quality of a general force field. Validation studies based on large number of isolated molecules, molecular liquids and molecular crystals, representing 28 molecular classes, show that the present force field enables accurate and simultaneous prediction of structural, conformational, vibrational, and thermophysical properties for a broad range of molecules in isolation and in condensed phases. Detailed results of the parametrization and validation f...

COMPASS: An ab Initio Force-Field Optimized for Condensed-Phase ApplicationsOverview with Details on Alkane and Benzene Compounds

Ferroelectric properties of copolymers of vinylidene fluoride with trifluoroethylene and tetrafluoroethylene are described with special interest in their polarization reversal and phase transition behavior. The ferroelectric phase consists of all-trans molecules packed in a parallel fashion while molecules adopt irregular TT, TG, T[Gbar] conformations in the paraelectric phase. In the ferroelectric phase, polarization reversal occurs at very high fields (> 100 MV/m) as a result of eventual 180° rotations of individual chain molecules around their axes. The switching time ranges from sec to nsec depending upon the strength of the applied field according to an exponential law with a particularly large activation field (∼ 1 GV/m). The value of the observed remnant polarization is consistent with prediction from a simple dipole sum implying a minor contribution from the Coulomb interaction. The ferroelectric-to-paraelectric transition appears most clearly for copolymers containing 50-80 mol% vinylide...

Ferroelectric properties of vinylidene fluoride copolymers

Poly(vinylidene fluoride) (PVDF) has been widely utilized in scientific research and the manufacturing industry for its unique piezoelectric properties. In the past few decades, the vibrational spectra of PVDF polymorphic polymers via FTIR (Fourier transform infrared spectroscopy) have been extensively investigated and documented. However, reports on the analysis of α, β and γ phases often have conflicting views based on measured data. In this work, we analyze the FTIR vibrational bands of PVDF materials fabricated by different processes with detailed XRD (X-ray diffraction) characterization to identify the structural α, β and γ phases. By examining the results in this work and extensively reviewing published research reports in the literature, a universal phase identification procedure using only the FTIR results is proposed and validated. Specifically, this procedure can differentiate the three phases by checking the bands around 763 and/or 614, 1275, and 1234 cm−1 for the α, β and γ phases, respectively. The rule for assignment of the 840* and 510* cm−1 bands is provided for the first time and an integrated quantification methodology for individual β and γ phase in mixed systems is also demonstrated.

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A critical analysis of the α, β and γ phases in poly(vinylidene fluoride) using FTIR

The crystal structures of three forms of poly(vinylidene fluoride) were studied by X-ray diffraction method. Although the structure of form I has been determined to be a fully extended planar zigzag by Lando, et al. [orthorhombic; a=8.58 A, b=4.91 A, and c(fiber axis)=2.56 A; space group Cm2m(C2v14)], an alternately-deflected molecular structure was postulated in order to release the steric hindrance between the fluorine atoms along the chain. A satistically disordered packing of such deflected chains satisfies the observed fiber period and improves appreciably the structure factor agreement. Form II is monoclinic [pseudo-orthorhombic; a=4.96 A, b=9.64 A, c(fiber axis)=4.62 A, and β=90°; space group P21/c(C2h5)], and its cell contains two molecular chains. The molecular conformation is essentially the TGTG type (internal rotation angles, 179° and 45°), and the glide plane of the molecular chain coincides with the c glide plane of the lattice. It is suggested that form III is monoclinic [a=8.66 A, b=4.93 A, c(fiber axis)=2.58 A, and β=97°; space group C121(C23)], and the structural features similar to that of form I.

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Crystal Structures of Three Crystalline Forms of Poly(vinylidene fluoride)

After an introduction reporting the properties and the applications of fluoropolymers, a first part deals with i) the main routes to produce vinylidene fluoride (VDF) monomer, ii) its homopolymerization, and iii) the advantages and uses of polyvinylidene fluoride (PVDF). In a second section, this review, illustrated by numerous examples, extensively reports the synthesis, properties and applications of the copolymers based on VDF with non-halogenated, fluorinated, commercially available or synthesized comonomers. These comonomers exhibit XYC=CZ-Sp-R structures where X, Y, and Z represent H, F, and CF3 groups, Sp a spacer and R a function such as OH, OAc, SAc, CO2R' (R' being a H atom or an alkyl group), CN, P(O)(OR')2 and SO3H. According to the nature and to the amount of the comonomer, the copolymers can be thermoplastic, elastomeric or thermoplastic elastomers. Introducing reactive R side groups brings complementary properties such as hydrophily, ionic exchange or surface properties, or further crosslinking of the resulting copolymers. Then, the kinetics of radical copolymerization of VDF with M comonomers led to the assessment of the reactivity ratios which are compared. Hence, a reactivity series of these M comonomers with respect to a macroradical terminated by VDF is proposed. Usually, these copolymers exhibit random structures but only three comonomers produced alternating copolymers with VDF: hexafluoroisobutylene, F2C=CFCO2CH3, and H2C=C(CF3)CO2R. The controlled radical copolymerizations of VDF with other comonomers (such as chlorotrifluoroethylene, 3,3,3-trifluoropropene, hexafluoropropylene, perfluoromethyl vinyl ether or-trifluoromethacrylic acid) either in the presence of xanthates, borinates or iodo-compounds are also reported. In addition, new VDF-containing copolymers exhibit well-defined architectures, such as block and graft copolymers. They can be synthesized either by conventional techniques or by controlled radical copolymerization. Chemical modifications of PVDF and poly(VDF-co-monomer) copolymers are also presented. Several properties and applications (such as surfactants, dielectrical polymers, thermoplastic elastomers, fuel cell and ultrafiltration membranes, or polycondensates, the fluorinated segments of which bringing softness and thermal stability) of these VDF-containing copolymers will illustrate this review.

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From vinylidene fluoride (VDF) to the applications of VDF-containing polymers and copolymers: recent developments and future trends.

The formation of three crystalline forms of poly(vinylidene fluoride) was studied in detail by using an apparatus for heat treatments under high pressure up to 5000 atm. Form II consisting of TGTG-type molecular chains was the most stable under atmospheric pressure, and form I, composed of planar zigzag-type chains, was formed under special conditions, such as tension, high pressure, etc. Form III may be an intermediate modification between I and II. Based upon these experimental facts, as well as the potential energy calculations of the intra- and intermolecular interactions in the crystal lattices due to the van der Waals and electrostatic forces, the relation between the conditions of formation of the three forms and their structures was examined. The planar zigzag-type conformation (in forms I and III) is considered to be less stable than the TGTG type (form II) because of the steric hindrances and electrostatic dipole interactions. In spite of the difference in the intramolecular potential energy between these two molecular conformations, the stabilities of the three crystalline forms are not so very different because of the more favorable intermolecular interaction in form I.

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Molecular Conformation and Packing of Poly(vinylidene fluoride). Stability of Three Crystalline Forms and the Effect of High Pressure

A convenient pressure apparatus was designed for crystallization of high polymers under hydrostatic pressure up to 5000 atm. Melt crystallization as well as heat treatment under various temperatures and pressures was carried out on several polymers, and the effects of pressure on the molecular and crystal structures of the samples are discussed. Heat treatment of syndiotactic polypropylene under high pressure yields a new crystal modification rather than the previously known helix and planar zigzag modifications. Of the three modifications of poly(vinylidene fluoride), modification III was found as a high-pressure phase for specimens in the unoriented state, while modification I was obtained as the most stable one on heat treatment of oriented specimens under high pressure. Heat treatment under high pressure converts ordinary isotactic poly-4-methylpentene-1 with a lower density than the noncrystalline value, to a new crystal modification with higher density. As is reasonable, the dense modification is stable in a high-pressure range. For these three cases, the orientation of specimens was found to remain unchanged during the transitions, which must therefore occur in the solid state.

Ryozo Hasegawa

Papers

Crystal Structures of Three Crystalline Forms of Poly(vinylidene fluoride)

Molecular Conformation and Packing of Poly(vinylidene fluoride). Stability of Three Crystalline Forms and the Effect of High Pressure

Structural studies of pressure-crystallized polymers. I. Heat treatment of oriented polymers under high pressure