α to β Phase Transformation and Microestructural Changes of PVDF Films Induced by Uniaxial Stretch

The phase transformation from α to β poly(vinylidene fluoride) (PVDF) through a stretching process at different temperatures was investigated. Samples of originally α-PVDF were stretched uniaxially at different temperatures at draw ratios from 1 to 5. The stretched samples were studied and characterized by infrared spectroscopy, scanning electron microscopy, and differential scanning calorimetry. The maximum β-phase content was achieved at 80°C and a stretch ratio of 5, but the samples still showed 20% of the original α-phase. Accompanying the phase transformation, an orientation of the polymer chains was observed. The stretching process also influenced the degree of crystallinity of the polymer. Poling of the samples also improves the α- to β-phase transformation.     

Relaxation processes and structural transitions in stretched films of polyvinylidene fluoride and its copolymer with hexafluoropropylene

Relaxation processes and structural transitions in nonstretched and uniaxially stretched films of poly(vinylidene fluoride-hexafluoropropylene) (P(VDF-HFP)) and its homopolymer polyvinylidene fluoride (PVDF) for comparison were investigated with the aim of understanding the electromechanical properties of this lower-modulus ferroelectric copolymer. The mechanical and the dielectric response at the glass transition (?? _a relaxation) exhibit similar temperature dependence of the relaxation time, whereas mechanical and dielectric processes above the glass transition are not related. They represent a continuous softening process within the amorphous phase and the dielectric ?? _c relaxation, respectively. The latter is attributed to conformational changes of VDF segments in lamellae of spherulites constituting the nonpolar crystalline ?? phase. Furthermore, there is a contribution from melting of secondary crystallites formed in the amorphous phase during annealing or storage. Mechanically, this transition appears in nonstretched and stretched films as an accelerated decrease of the elastic modulus that terminates the rubber plateau. Dielectrically, this transition becomes visible as a frequency-independent loss peak only in stretched films, because stretching removes the ?? _c relaxation, which superimposes the transition in nonstretched films. Melting of secondary crystallites is shown to appear in the homopolymer, too, though less pronounced because of more complete primary crystallisation. Stretching increases the modulus above the glass transition only slightly, and it does not significantly influence the softening process. On the other hand, stretching causes a spontaneous polarisation and introduces order within the amorphous phase, rendering it more polar. Melting of secondary crystallites provides an additional contribution to the polarisation. These findings may explain the relatively high electromechanical activity of P(VDF-HFP) but also its relatively low thermal stability. Moreover, they may be important for correct procedure and analysis of temperature-dependent dielectric measurements on partially crystalline polymers, in particular on those with less favourable sterical conditions for primary crystallisation.     

Relaxation phenomena of poly-γ-benzyl-L-glutamate,poly-γ-methyl-L-glutamate,and copoly(γ-methyl-L-glutamate, γ-benzyl-L-glutamate)

Relaxation phenomena of poly-α-amino acids in the solid state have been investigated using poly-γ-benzyl-L-glutamate (PBLG), poly-γ-methyl-L-glutamate (PMLG), and copoly (γ-methyl-L-glutamate, γ-benzyl-L-glutamate) (PMBG) by means of dielectric, dynamic mechanical, NMR, dilatometric, and X-ray diffraction measurements at temperatures between ?196 and 180°C.

Each of the samples exhibits two relaxation regions, one at room temperature (β-relaxation) and the other in the range from ?150 to ?100°C (γ-relaxation). The γ-relaxation is attributed to motion of the side chains with small amplitude. The β-relaxation is due to large-scale motion of the side chain. It has been found that the β-relaxation is well described by the WLF-equation.

The intensity of the X-ray diffraction peak at 2θ = 7° for PBLG increases with increasing temperature, which is similar to results obtained in small-angle X-ray scattering for polymer crystals consisting of two phases, amorphous and crystalline. A break point is observed at 18°C where the specific volumetemperature curve also shows a break point.

It is concluded that the side chains of these polymers are almost amorphous, and that they undergo a glass-like transition while the backbones keep an α-helical conformation.     

Nuclear spin relaxation and molecular motions in sebacate polyesters

In this study, pulsed NMR techniques were used to probe the molecular motions occurring in poly(hexamethylenesebacate) (HMS), and its amorphous isomer poly(2-methyl-2-ethyl-1,3-propylenesebacate (MEPS), and in particular, to examine the perturbations in the molecular motions of HMS and MEPS that arise as a result of block copolymerization. The results show a low-temperature β-relaxation due to local motion of the methylenes of the chain backbone, an α-relaxation associated with the glass transition, and an α_c-relaxation due to the melting of the crystalline phase. Both α-and β-relaxations in the block copolymer are only slightly perturbed, and this suggests that the blocks are incompatible. The β-relaxation of HMS is confined to the amorphous regions of the polymer. Although sample preparation had little effect on the degree of crystallinity, large differences in the relaxation behavior were observed when the sample preparation was varied.     

Effects of CNT inclusions on structure and dielectric properties of PVDF/CNT nanocomposites

ABSTRACT

The effects of multiwall carbon nanotube (CNT) inclusions on the crystalline structure of poly(vinylidene fluoride) (PVDF), and on the dielectric properties of PVDF/CNT nanocomposites (NCs), prepared by melt mixing, were investigated by employing X-ray diffraction, differential scanning calorimetry, and dielectric spectroscopy techniques. Our results imply that, in the NCs, the formation of β-phase crystals depends on specific compression treatment in the melt and fast cooling. Dielectric measurements on NCs, with CNT concentrations below the electrical percolation threshold, reveal that the dielectric strength of the two relaxation processes in the amorphous phase and dielectric permittivity, ?′, measured within the broad temperature range from ?150 °C to 60 °C, increase strongly with increasing CNT concentration. This enhancement of amorphous PVDF polarizability has been attributed to the increase of the local electric field, due to local polarization generated at the surface of conductive inclusions/CNT clusters.     

Phase Behavior of Rapidly Quenched PVDF/PMMA Blends as Characterized by Raman Spectroscopy,X‐Ray Diffraction and Thermal Techniques

Although PVDF/PMMA blends have been studied extensively, the phase behavior as a function of melt quenching conditions has not been examined in detail in the past. In this paper we report our results on the isotropic blends of PVDF/PMMA quenched into ice water as well as on a casting roll set at 30°C in all composition ranges. The results confirm the miscibility of this blend for all composition ranges, although at high PVDF (～85%) concentration micro heterogeneities were evidenced through thermal analysis. Though pure PVDF is observed to be mostly in the α crystalline form, the addition of PMMA favors the β crystal structure in composition range 85/15–60/40. Ice water quenching yields amorphous blends containing more than 40% PMMA and these films are deemed good candidates for rubbery state processes (between T _g and T _cc), including tenter frame biaxial stretching, where they can be oriented significantly at these low temperatures while undergoing strain induced crystallization.     

Dielectric relaxation and dc conductivity on the PVOH-CF3COONH4 polymer system

In the present paper, the ionic conductivity and the dielectric relaxation properties on the poly(vinyl alcohol)-CF₃COONH₄ polymer system have been investigated by means of impedance spectroscopy measurements over wide ranges of frequencies and temperatures. The electrolyte samples were prepared by solution casting technique. The temperature dependence of the sample’s conductivity was modeled by Arrhenius and Vogel-Tammann-Fulcher (VTF) equations. The highest conductivity of the electrolyte of 3.41×10^− 3 (Ωcm)^− 1 was obtained at 423 K. For these polymer system two relaxation processes are revealed in the frequency range and temperature interval of the measurements. One is the glass transition relaxation (α-relaxation) of the amorphous region at about 353 K and the other is the relaxation associated with the crystalline region at about 423 K. Dielectric relaxation has been studied using the complex electric modulus formalism. It has been observed that the conductivity relaxation in this polymer system is highly non-exponential. From the electric modulus formalism, it is concluded that the electrical relaxation mechanism is independent of temperature for the two relaxation processes, but is dependent on composition.     

Multiple relaxation in α- and γ-loss bands of polyethylene

Dielectric and NMR behavior of linear polyethylene was observed in the α-and γ-loss bands in order to investigate the nature of the multiple loss patterns of these loss bands. The results obtained are compared with those of mechanical measurements. In the dielectric behavior of oxidized linear polyethylene, three relaxations are found in the γ-loss band, while only one relaxation is found in the α-loss band. The β-relaxation is found as a plateau region between the α-and γ-loss bands. The loss pattern of the α-loss band is different from that for the mechanical case which is composed of three relaxations. The effects of difference in morphology, addition of diluent, and heat treatment on the multiple loss patterns are examined. The results suggest that there are two noncrystalline regions in the exterior part of lamellae, including lamellar surfaces, and the two modes of molecular motion in each of these regions are responsible for each pair of relaxations; of the three relaxations found in the γ-loss band the γ₂-relaxation is related to the dielectric α-relaxation, while the γ₁-relaxation is related to the β-relaxation. The relation between the two relaxations in each pair is similar to that between the primary relaxation due to micro-Brownian motion and the local mode relaxation of amorphous polymers which are caused by the two modes of motion of the same molecules. The γ₃-relaxation seems to be caused by some different mechanism.     

Dielectric relaxation investigations of 100 MeV Ag-ion-irradiated polyetherimide using thermally stimulated discharge current techniques

The thermally stimulated discharge current technique (TSDC) has been used to elucidate various dielectric relaxation processes in 100 MeV Ag-ion-irradiated polyetherimide (PEI). The irradiated PEI samples (85 μm thickness, area 0.12 cm²) were polarized at different temperatures ranging from 50–200 °C under various biasing fields (50–300 kV/cm). TSDC spectra, in general, consist of four current maxima namely γ, β, α and ρ in ascending order of temperature, appearing around 40, 110, 200 and 230 °C, respectively. The origin of γ - and β -peaks has been attributed to the dipolar nature of ether linkages and carbonyl groups, respectively, whereas α- and ρ-maxima have been attributed to the space charge polarization process. The absence of γ-peak in irradiated samples is attributed to the significant loss in ether linkages due to irradiation. The free radical formation, demerization of carbonyl groups and cross-linking of imide groups due to ion irradiation in PEI have been held to be responsible for the behavior of these relaxation processes. In the vicinity of the β-relaxation, a new relaxation process, termed δ-relaxation, is also observed.     

Effect of the ceramic grain size and concentration on?the?dynamical mechanical and dielectric behavior of?poly(vinilidene fluoride) Pb(Zr0.53Ti0.47)O3 composites

In this work, poly(vinilidene fluoride)/Pb(Zr_0.53Ti_0.47)O₃([PVDF]_1−x /[PZT] _x ) composites of volumetric fractions x and (0–3) type connectivity were prepared in the form of thin films. PZT powder of crystallite size of 0.84, 1.68, and 2.35 μm in different amounts of PZT (10, 20, 30, and 40%) was mixed with the polymeric matrix. The crystalline phase of the polymeric matrix was the nonpolar α-phase and the polar β-phase. Dielectric and dynamic mechanical (DMA) measurements were performed to these composites in order to evaluate the influence of particle size and the amount of PZT filler with respect to the PVDF matrix. The inclusion of ceramic particles in the PVDF polymer matrix increases the complex dielectric constant and dynamical mechanical response of the composites. A similar behavior is observed for the α- or β-phase of the polymeric matrix indicating that the PVDF polymer matrix is not particularly relevant for the composite behavior. On the other hand, ceramic size and especially content play the major role in the increase of the dielectric response and the room temperature storage modulus. In particular, the storage modulus increases with increasing PZT concentration, but this increase is more pronounced, in terms of maximum value, for the sample with 2.35 μm particle size; DMA reveals two main relaxations in the analyzed samples. A low-temperature process maximum at ca. −40°C, usually labeled by β or α _a associated to the T _g of the polymer and the α-relaxation at temperatures above 30°C. The β-relaxation is also observed in the dielectric measurements. The models used to asses the dielectric behavior of the samples with increasing PZT concentration indicate that the particle–matrix interaction plays a relevant role, as well as the particle asymmetry and relative orientation, being the Yamada model the most appropriate to describe the composite behavior. An erratum to this article can be found at     

Investigation on crystalline structure and dielectric relaxation behaviors of hot pressed poly(vinylidene fluoride) film

The dielectric relaxation behaviors of hot pressed poly(vinylidene fluoride) (PVDF) film have been studied using dielectric spectroscopy in the frequency domain from 20 Hz to 5 MHz at temperatures between 20 °C and 200 °C. Crystalline/amorphous interphase is suggested with methods of FTIR, XRD, and DSC. Frequency and temperature dependence of dielectric spectroscopy reveals the relaxation behavior and structural dynamics of the samples, and three types of relaxation processes are suggested, α_Ac relaxation process contributed by the hopping transport process near the periphery of conduction band or valence zones at Fermi energy, α_c relaxation process related to the structure change of crystal lattice trapped dipoles in crystalline regions, and α_a relaxation process arising from segmental dipole rearrangement of interphases in amorphous regions. Cole-Cole and Havriliak-Negami experimental equations were utilized to analyze these relaxation processes, and differences of Arrhenius parameters for α_Ac and α_c relaxation processes obtained from Cole-Cole and Havriliak-Negami equations were discussed in detail. Activity energy of different relaxation processes obtained from Arrhenius equation and VFT equation indicates non-single thermal activation mechanism for hot pressed PVDF film.     

Crystallinity and dielectric relaxations in semi-crystalline poly(ether ether ketone)

The Maxwell-Wagner-Sillars (MWS) relaxation is studied for semi-crystalline polymers poly (ether ether ketone) (PEEK), in the range 20 Hz-1 MHz and temperature varying from 80 to 330 °C. The parameter is the crystallization condition in the case of PEEK, which is a semi-crystalline polymer considered as a particulate composite. The relaxation found in the semi-crystalline polymers above the α relaxation of the PEEK is ascribed to the trapping of conductive carriers at the interface between crystalline lamellae and the amorphous matrix. The study of PEEK microstructure is based on differential calorimetry and X-rays diffraction. Two lamellae populations have been detected, that depends on the crystallization temperature and its duration. The crystallinity rate is increasing with crystallization temperature and duration. In dielectric studies, the use of the electric modulus instead of permittivity allows us to minimize the ionic conduction and then leads to the appearance of the interfacial relaxation. According to our measurements, the crystallinity rate is not the main factor of the interfacial relaxation intensity, which also depends on the nature and degree of perfection of the lamellae.     

Crystalline and relaxation properties of ethylene copolymer films inserted between two steel sheets

The relaxation and crystalline properties of ethylene vinyl acetate (EVA) co-polymers inserted in steel/polymer/steel assemblies were studied. To investigate the properties of the interfacial region, polymers of different thickness inserted in the assemblies were analyzed. The studied EVA copolymers are semicrystalline polymers. The relaxation properties of the amorphous phase were investigated by dynamic mechanical measurements performed on the steel/polymer/steel assemblies, and the crystalline properties were studied by differential scanning calorimetry (DSC). The results indicate that, for low polymer thicknesses, the mobility of the amorphous phase is significantly reduced. Significant changes in the crystalline organization also were observed when the polymer thickness decreased, with the presence of more numerous disorganized crystals for thin EVA layers. These crystals can act as physical ties that reduce the mobility of the neighboring amorphous chains. These results indicate the formation of an interphase layer of reduced mobility.     

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.     

Effect of Radiation from an Infrared Laser and <Emphasis Type="Italic">γ</Emphasis>-Rays from <Superscript>60</Superscript>Co on the Molecular–Topological Structure of Polyvinylidene Fluoride

We investigate the molecular–topological structure of polyvinylidene fluoride (PVDF) irradiated with γ-rays from ⁶⁰Co and IR radiation from a carbon dioxide laser by the thermomechanical spectroscopy method. The initial PVDF has a topological three-block network structure containing the low- and high-temperature amorphous blocks and crystalline fragments. Both types of irradiation can initiate interblock mass transfer of the macromolecular fragments from the amorphous to the crystalline form. As a result, unlike the predominantly amorphous structure of the native polymer, which is 7% crystalline, the weight fraction of the crystalline modification of the PVDF due to irradiation by an IR laser increases to 72%. Comparative analysis leads to the conclusion that the PVDF has a greater resistance to γ-irradiation than to IR laser irradiation. After IR laser irradiation, the pseudo-network structure of PVDF undergoes noticeable changes. The quantitative content of the crystalline fragments of macromolecules increases by almost an order of magnitude; the mobility of chains is reduced, and the rigidity of the chains is increased. However, the molecular flow of the polymer irradiated by the laser and γ-rays begins in the same temperature range (437 – 441 K) near where the native polymer is flowing (438 K).     

RELATIONSHIPS BETWEEN MECHANICAL TENSILE BEHAVIOR AND MICRO-MECHANISMS IN POLY(VINYLIDENE FLUORIDE) AT HIGH TEMPERATURES: INFLUENCE OF THE MOLECULAR WEIGHT DISTRIBUTION

Polyvinylidene fluoride (PVDF) is a crystalline polymer known for its multiple crystalline phases. When elongated at room temperature before necking, the nucleation and growth of micro-voids is a major process. No phase transition was observed. In this paper, micromechanisms of deformation are studied and linked to the macroscopic mechanical tensile behavior at temperatures higher than 100°C and after necking. Cavitation, crystalline phase transitions and orientation process are investigated by small and wide angle x-ray experiments. Two PVDF with different molecular weight distributions are considered. These microstructure differences mainly affect cavitation.     

Dielectric relaxation of poly(ethylenglycol)- b-poly(propylenglycol)-b-poly(ethylenglycol) copolymers above the glass transition temperature

The complex dielectric permittivity has been measured for three poly(ethylenglycol)-b-poly(propylenglycol)-b-poly(ethylenglycol) copolymers with different content of poly(ethylenglycol) (15%, 33% and 80%), and increasing degree of crystallinity (0%, 10% and 20%, respectively). Only the non-crystalline sample shows the normal mode relaxation together with the segmental (α-relaxation) and the Johari-Goldstein (β-relaxation) modes. The crystalline samples show also polarization contributions due to the existence of interfaces between the crystallites and the amorphous phase. The relaxation times of the (α and normal modes can be described by a VFT equation with the same value of T₀. There is a slowing-down of the segmental mode due to the presence of crystallites. The temperature dependence of the α and β relaxations in the copolymers is very similar to that found in pure PPG, while there are significant differences in the case of the normal mode of the non-crystalline sample. The size of the cooperatively rearranging regions CRR, and the width of the glass transition region increase slightly with the degree of crystallinity. The temperature dependence of the size of CRRs is compatible with the prediction of fluctuation theory. No systematic effect of the degree of crystallinity on the β-relaxation has been found. Near T _g the β-relaxation time is close to the primitive time of the coupling model. Received: 31 May 2000     

Dielectric relaxation in polyvinylidenefluoride–polysulfone blends

Dielectric properties of polymer blend of polyvinylidenefluoride (PVDF) and polysulfone (PSF) of different wt. % have been studied to understand the molecular motion and their relaxation behavior in the frequency range of 100 Hz to 10 kHz at different temperatures between 30 and 190 °C. The dielectric constant of the blend decreased with frequency and increased with the increasing temperature and PSF content in the blend. The magnitude of dielectric loss also increased with increase in temperature and PSF content. The observed characteristic has been consistently explained in terms of dipolar motions and the plasticization effect brought about by blending of PSF with PVDF. At constant frequency and temperature, the blend follows a linear relationship between logarithm of their dielectric constant and different ratios of blend. The appearance of a peak for each concentration in dielectric loss suggests the presence of relaxing dipoles in the blend. In addition of PSF with PVDF, the peak shifts toward higher frequency side suggesting the speed up the relaxation process. AC dielectric data is also combined with thermally stimulated depolarization current (TSDC) data which is generally studied for low-frequency dielectric properties of polymers blends so as to produce the results in a wide frequency range. The glass transition temperature (T_g) of the blend was studied by differential scanning calorimetric technique (DSC), the T_g was compared and correlated with TSDC peak. The blend samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) to study the formation of blend and micro structural properties of the materials. The shifting of peak toward lower diffraction angle side confirms the reduction in particle size with increasing amorphous content in the blend.     

Local variation of the dielectric properties of poly(vinylidene fluoride) during the α- to β-phase transformation

The phase transformation from the non-polar α-phase to the polar electroactive β-phase of polyvinylidene fluoride (PVDF) has been investigated using the fluorescence from Nile red. Films of α-PVDF doped with Nile red were stretched at controlled rates at a temperature of 80 °C to produce the α- to β-phase transition. The thermo/mechanical dependent changes in the crystalline structure are related to the physical rotation of the polar (CH₂-CF₂) group, which can be monitored by steady state fluorescence techniques. The degree of phase transformation is related to variation in the fluorescence, which in turn is linked to local dielectric constant of the polymer. The variation of the refractive index is more associated to the alignment of the polymeric chains than to the phase transformation. Thus, fluorescence is a suitable technique to monitor phase transitions coupled to a variation in the polarity of the dielectric medium.     

Investigation of MWS Relaxation in Nylon 1010 using Dielectric Relaxation Spectroscopy

Maxwell–Wagner–Sillars (MWS) relaxation in nylon 1010, arising from charge carriers accumulated at the interphase between amorphous and crystalline regions, has been investigated by means of dielectric relaxation spectra. In the frequency spectra of nylon 1010, dielectric permittivity showed high values at low frequencies originating from charge carrier movement. For the MWS relaxation, the dielectric strength was independent of temperature. The results revealed that there is a transition temperature, located between 110 and 120°C, resulting in the separation of two different charge carrier movement mechanisms. Below and above this transition temperature, the temperature dependence of the MWS relaxation time follows the Vogel–Tammann–Fulcher type, showing that the charge carrier transport is governed by the motion of the polymer chains. The change of charge carrier movement mechanisms is due to the onset of polymer chain motion in the interphase.