The polymorphism of poly(vinylidene fluoride) V. The effect of hydrostatic pressure on the melting behavior of copolymers of vinylidene fluoride

The high-pressure melting behavior of samples of vinylidene fluoride copolymerized with vinyl fluoride, trifluoroethylene, or tetrafluoroethylene indicate that the copolymers have a lower entropy of melting than the poly(vinylidene fluoride) homopolymers in the same phase. As the comonomer size increases, the entropy of melting decreases. High-pressure crystallization of copolymers of 91-9 mole% vinylidene fluoride-trifluoroethylene and 93-7 mole% vinylidene fluoride-tetrafluoroethylene results in a high-melting form of phase I (planar zig-zag).     

Structural phase transition in ferroelectric fluorine polymers: X-ray diffraction and infrared/Raman spectroscopic study

The structural phase transition has been investigated by X-ray diffraction and infrared and Raman spectroscopic measurements for ferroelectric fluorine polymers, including poly(vinylidene fluoride) and its copolymers with trifluoroethylene or tetrafluoroethylene. One of the most characteristic features of this ferroelectric transition is the large conformational change of the molecular chains between the trans and gauche rotational isomers, quite different from the structural change observed generally in the usual ionic ferroelectric materials. The crystallization and transition behaviors depend sensitively on the monomer composition in the copolymers as well as on the sample preparation conditions. The roles of the optic and acoustic phonons in the ferroelectric phase transition have been discussed based on the temperature dependences of the far-infrared spectra and the ultrasonic velocity.     

The polymorphism of poly(vinylidene fluoride) IV. The structure of high-pressure-crystallized poly(vinylidene fluoride)

A detailed study of high-pressure-crystallized poly(vinylidene fluoride) has indicated that a mixture of low-melting phase II and high-melting phase I is present, rather than a new crystalline phase (phase III) as originally suggested.

The relative amounts of phase I and phase II resulting from crystallization under pressure are a function of pressure and the degree of supercooling. Pressure crystallization at 285°C and 5500 atm results in samples which were pure phase I with an increased melting point of 187°C.     

The effect of hydrogen-fluorine defects on the conformational energy of polytrifluoroethylene chains

Conformational energy calculations were employed to determine the effect of hydrogen-fluorine defects on the conformation of the polytrifluoroethylene chain. It was determined that the 3₁ helix was energetically favored for all but the highly syndiotactic polymers, which favored the all-trans conformation. The incorporation of head-to-head linkages into the polymer chain increased the Conformational energy of the 3₁ helix while the Conformational energy of the all-trans form decreased. The energies of these two conformations did not equalize until the head-to-head concentration reached 20 to 30%, depending on the tacticity of the polymer. The trans, gauche, trans, gauche' conformation was also determined to be energetically favorable for the syndiotactic polymer, but both tacticity defects and head-to-head linkages caused a rapid increase in the Conformational energy. This was, therefore, concluded to be unlikely structure when chemical defects are incorporated into the polymer chain.     

Study of the combined carbonization of poly(vinylidene fluoride) by X-Ray photoelectron spectroscopy

The surface composition of two samples synthesized by the combined carbonization of poly(vinylidene fluoride) (PVDF) films is studied by X-ray photoelectron spectroscopy. One of them is successively exposed only to chemical and radiation impacts, and the treatment of the other includes chemical, heat, and radiation exposure. The chemical preparation of both samples is the same. It is shown that the magnitude and direction of the gradient of the residual fluorine concentration in the surface layer of PVDF carbonization products can be controlled. Since dehydrofluorination decreases the surface electrical resistance of the material, a combination of chemical, heat, and radiation treatments can be used to create a predetermined sequence of heterolayers with different fluorine concentration on a flexible and transparent polymer base and, therefore, with different conductivities.     

Ferroelectric properties of vinylidene fluoride copolymers

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% vinylidene fluoride at temperatures from 70 to 140°C. The transition accompanies cooperative dipole motions associated with elementary trans-gauche transformations. Changes in various properties as well as in structures in the vicinity of the Curie point are consistent with an order-disorder transition of first order. Detailed characteristics specifying their ferroelectricity are summarized and discussed in relation to the molecular, crystalline, and higher-order structures inherent to ferroelectric polymers.     

Emission of negative and positive ions at rupture of polymers

The emission of negative and positive ions at rupture of polymers has been recorded under high vacuum. The time characteristics of the emission have been investigated with a time resolution up to 1 μs by varying the sizes and the tension rate of poly(ethylene terephthalate), poly(caprolactam), poly(vinylidene fluoride), polyimide, and poly(tetrafluoroethylene) specimens. The kinetics of emission at the last stages of the tension is associated with the specific features of the intergrowth of the main crack in polymers of different types. Possible mechanisms of ion emission have been discussed.     

Study on the Nonisothermal Crystallization Kinetics of Poly(Vinylidene Fluoride)/Tributyl Citrate Blends Via Thermally Induced Phase Separation

The nonisothermal crystallization kinetics of poly (vinylidene fluoride) (PVDF) in PVDF/tributyl citrate (TBC) blends having undergone thermally induced phase separation were investigated through differential scanning calorimetry measurements. Ozawa theory, Mo's method and Kissinger model were used to analyze the kinetics of the nonisothermal crystallization process. The Ozawa theory failed to describe the crystallization behavior of PVDF in the PVDF/TBC blends, whereas the Mo model was able to describe the nonisothermal crystallization process fairly well. The crystallization activation energy was determined by the Kissinger method, and was in the range of 90–165 kJ/mol.     

聚偏氟乙烯分子链旋转时势能的变化

计算了聚偏氟乙烯分子链旋转时势能的变化.结果显示,当中心分子链旋转而其它链静止不动时,计算得到的势能曲线有4个很高的势垒,这些势垒来源于中心分子链和最近邻分子链中的氟原子对的“空间位阻”效应.这一结果与“六阱势”模型预言的势能变化存在准六度对称性相矛盾.计算结果表明,如果中心分子链和周围分子链同步旋转,势垒高度将极大地降低.另外,极化反转时晶格常数发生变化.最后得到的势垒高度约为7.5kJ/mol.与室温下的分子势运动的能量（约2.5kJ/mol）相比,这样的“浅”势阱不足以锁定分子偶极矩形成稳定的自发极 关键词：     

Effect of PMMA on crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate) blend prepared in semi-dilute solutions

Films of poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blend were derived from a special procedure of casting semi-dilute solutions. Hydrophilic character and crystallization of PVDF were optimized by variation of PMMA concentration in PVDF/PMMA blends. It was found that a PVDF/PMMA blend containing 70 wt% PMMA has a good performance for the potential application of hydrophilic membranes via thermally induced phase separation. The films presented β crystalline phase regardless of PMMA content existed in the blends. Thermal analysis of the blends showed a promotion of crystallization of PVDF with small addition of PMMA which induced larger lamellar thickness of PVDF, leading to the largest spherulitic crystal of PVDF (10 wt% PMMA) is about 8 μm. SEM micrographs illustrated no phase separation occurred in blends, due to the high compatibility between PVDF and PMMA.     

Surface ferroelectric phase transition in multilayer polymer Langmuir films

The ferroelectric phase transition on the free surface of a polymer ferroelectric Langmuir-Blodgett film was studied by the optical second harmonic generation (SHG) technique. A hysteresis in the temperature dependence of the SHG intensity observed for a multilayer film of a poly(vinylidene fluoride)-trifluoroethylene copolymer in the vicinity of T≈15°C is a manifestation of the first-order ferroelectric phase transition in the topmost surface monolayer of the film.     

Simultaneous treatment of polymer surface by EUV radiation and ionized nitrogen

In this paper chemical modification of a poly(vinylidene fluoride) surface by extreme ultraviolet (EUV) irradiation in a presence of ionized nitrogen was demonstrated for the first time. Nitrogen gas, injected into an interaction region, was ionized and excited by the EUV radiation from a laser-plasma source. The ionization degree and excited states of nitrogen were investigated using EUV spectrometry and the corresponding spectra are presented. Chemical modification of polymer after combined EUV and ionized nitrogen treatment was investigated using X-ray photoelectron spectroscopy. A?significant contribution of nitrogen atoms in near-surface layer of the polymer after the treatment was demonstrated.     

Enhanced dielectric permittivity in poly (vinylidene) fluoride/multiwalled carbon nanotubes nanocomposite thin films fabricated by pulsed laser deposition

The fabrication of high quality thin films of poly (vinylidene fluoride) embedded with multiwalled carbon nanotubes using pulsed laser deposition technique is reported. The prepared films were characterized for structural, morphology and dielectric properties. The morphology analysis revealed uniform dispersion of multiwalled carbon nanotubes throughout the polymer matrix. X-ray diffraction results suggested that the poly (vinylidene fluoride) film is in amorphous phase while addition of multiwalled carbon nanotubes showed presence of crystalline peaks in the nanocomposites films. It was interesting to note that the nanocomposite films exhibits significant enhancement of the ferroelectric β-phase as evidenced by the X-ray diffraction and Fourier transform infrared spectroscopy results. The dielectric analysis shows a remarkable enhancement in the dielectric permittivity of nanocomposites with lower loss and conductivity level. The results can be attributed to the formation of minicapacitor network and relatively higher percolation threshold in the nanocomposites.     

The microwave spectrum of α-fluoropropionic acid

The rotational absorption lines in the microwave spectrum of α-fluoropropionic acid were shown to originate from two different molecular conformations. The rough geometries of the two conformations could be determined from the observed dipole moments and the substitution coordinates of the carboxylic hydrogen atom. In both conformations the fluorine atom is near the plane of the carboxyl group; in the conformation with the fluorine atom trans with respect to the hydroxyl group the carboxyl group has the usual geometry, while in the cis conformation the molecule is stabilized by an internal OH?F hydrogen bond. By measuring the relative intensities of the absorption lines it was found that the cis conformer is 0.5 ± 0.2 kJ mole^?1 lower in energy than the trans conformer. The barrier to internal rotation of the methyl group in the trans conformation was determined from A-E line splittings in the second excited vibrational state V₃ = 13.5 ± 0.3 kJ mole^?1.     

Conformational studies of poly(methacrylic acid). I. Conformational energy calculations on lsotactic and syndiotactic poly(methacrylic acid)

The conformational energies of isotactic and syndiotactic poly (methacrytic acid) were calculated for isolated chains in order to determine the most probable helical conformations. It was concluded that the most probable backbone conformation of the isotactic polymer is either a 5₂ or 8₃ helix, where the internal rotations of the two helices are nearly equal. The left-handed and right-handed conformations were also essentially equienergy conformations. Two lowenergy helical conformations were found for the syndiotactic polymer. One of these conformations had backbone internal rotations nearly identical to those of the 5₂ and 8₃ helices of isotactic poly(methacry1ic acid). The second conformation was a nearly planar structure containing two monomer units in the axial repeat unit, with backbone rotation angles nearly identical to those of the 5₂ and 8₃ helices or their negatives.

Deformation of the backbone C─C─C bond angles was considered in the conformational energy calculations. The optimum bond angles for both isotactic and syndiotactic polymer chains were considerably larger than the normal tetrahedral bond angle. The relative energies calculated for helical conformations were influenced by the backbone bond angles. It was demonstrated that the failure to consider backbone bond-angle deformation may lead to erroneous conformational assignments in disubstituted vinyl polymers.     

Long-lived excited state of spiroanthroxazine after its matrix isolation in halogenated polyolefins by supercritical fluid impregnation

Supercritical fluid impregnation was used to perform matrix isolation of spiroanthroxazine (SAO) photochromic molecules in halogenated polymer films (polyvinylchloride and tetrafluoroethylene copolymer with vinylidene fluoride). An excited (colored) SAO form not relaxing to the ground (colorless) state was stabilized in polymers. Such a long-lived excited SAO form could exist as an isomer of the B form (B₅₃₅ with an absorption band at λ_max = 535 nm) in the fluorinated polymer matrix, for which the absorption maximum was shifted by more than 75 nm to the blue, and as the B form with a small admixture of the B₅₃₅-form (in polyvinylchloride).     

Role of the polymer matrix in determining the chemical–physical and electrochemical properties of gel polymer electrolytes for lithium batteries

Gel polymer polymer membranes, prepared by immobilizing lithium-conducting solutions in a polymer matrix, are promising electrolyte materials for promoting the advancement of the lithium battery technology. However, so far, not much attention has been devoted to the definition of the role of the constituents in determining the properties of these electrolytes. In this work we have examined the characteristics of three common examples of polymer electrolytes based on a poly(vinylidene fluoride)-fluoropropylene, poly(vinyilidene fluoride)–hexa-fluoropropylene copolymer matrix. The three selected electrolytes differed from the nature of their polymer matrix. The results, based on X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and conductivity tests, show that, indeed, the type of the polymer matrix may influence the properties of the electrolytes, especially in terms of conductivity.     

Solid-state F NMR investigation of poly(vinylidene fluoride) with high-power proton decoupling

The use of high-power proton decoupling has enabled highly-resolved spectra of fluorine polymers to be recorded, as is exemplified herein for semicrystalline poly(vinylidene fluoride) (PVDF). By means of high MAS speeds (up to 17 kHz), the spinning sidebands are removed from the whole of the relevant chemical shift range. For spectra of the crystalline regions of the polymer, the high-power decoupling is necessary, though its effect is not large. Various relaxation techniques have been used to examine the semicrystallinity and the polymorphism of PVDF, with special pulse sequences used to discriminate between the various domains. Different chemical shifts have been observed for the signals of the amorphous and crystalline phases. Those of the more immobile parts cover a substantial range.     

Preparation of Poly(vinylidene fluoride)/Poly(methyl methacrylate) Blend Microporous Membranes via the Thermally Induced Phase Separation Process

The thermally induced phase separation (TIPS) process was employed to prepare poly(vinylidene fluoride)/poly(methyl methacrylate) (PVDF/PMMA) blend microporous membranes. The effect of PMMA content on the dynamic crystallization temperature of the PVDF/PMMA/sulfolane system was analyzed. The effects of PMMA weight fraction and cooling rate on the cross-sectional morphology, crystallinity, crystal structure, thermal stability, and porous structure of the resulting membranes were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and a mercury porosimeter, respectively. The mechanical properties of the membranes were evaluated by tensile tests. It was found that solid–liquid phase separation occurred in the PVDF/PMMA/sulfolane system. Scanning electron microscopy revealed that either increasing PMMA weight fraction or decreasing cooling rate will lead to a macroscopical phase separation between PVDF and PMMA. PMMA weight fraction and cooling rate had some influence on the crystallinity, porous structure, and mechanical properties, but no influence on the polymer crystal structure of the membranes. PMMA weight fraction influenced thermal stability of the final membranes but cooling rate did not.     

The influence of structural and electrical parameters of the pyroelectric phase on the pyroelectric properties of a polymer-pyroelectric ceramic composite

The influence of structural and electrical parameters of the pyroelectric phase on the pyroelectric properties of composites based on poly(vinylidene fluoride), vinylidene fluoride-tetrafluoroethylene copolymer (F-42), and pyroelectric ceramics of the lead zirconate titanate family with different structures is investigated. It is revealed that the pyroelectric coefficient of the composite is determined by the reorientation polarization and the mobility of domains in the pyroelectric ceramic phase, which depend on the homogeneous parameter of the spontaneous strain of the perovskite cell.