Ferroelectric and piezoelectric properties of nylon 11/poly(vinylidene fluoride) bilaminate films

The ferroelectric and piezoelectric properties of a new class of polymer ferroelectric and piezoelectric materials, nylon 11/polyvinylidene fluoride (PVF₂) bilaminate films, prepared by a co-melt-pressing method, is presented. The bilaminate films exhibit typical ferroelectric D-E hysteresis behavior with a remanent polarization, P_r, of about 75 mC/m², which is higher than the value of 52 mC/m² observed for PVF₂ or nylon 11 films measured under the same conditions. The coercive field, E_c, of the bilaminate films is ～ 78 MV/m, which is higher than that of either PVF₂ or nylon 11 films. Measurements of the temperature dependence of the piezoelectric strain coefficient, d₃₁, and the piezoelectric stress coefficient, e₃₁, were also carried out. The bilaminate films exhibit a piezoelectric strain coefficient, d₃₁, of 41 pC/N at room temperature, which is significantly higher than the PVF₂ films (25 pC/N) and the nylon 11 films (3.1 pC/N). When the temperature is increased to 110°C, d₃₁ of the bilaminate films reaches a maximum value of 63 pC/N, more than five times that of PVF₂ (11 pC/N) and more than four times that of nylon 11 (14 pC/N) at the same temperature. The piezoelectric stress coefficient, e₃₁, of the bilaminate films shows a value of 109 mC/m² at room temperature, almost twice that of the PVF₂ films (59 mC/m²) and about 18 times that of the nylon 11 films (6.2 mC/m²). Measurement of the temperature dependence of the hydrostatic piezoelectric coefficient, d_h, of the bilaminate films also shows an enhancement with respect to the individual components, PVF₂ and nylon 11. ©1995 John Wiley & Sons, Inc.     

Longitudinal piezoelectric strain measurements of poly(vinylidene fluoride) films

The longitudinal piezoelectric strain of poly(vinylidene fluoride) (PVF₂) films has been measured at room temperature using a high-sensitivity ac capacitance-type dilatometer. The dc bias field dependence of the piezoelectric strain coefficient d₃₃ has been determined. The polarization-related electrostrictive coefficient Q₃₃ obtained is several hundred times larger than the value in normal piezoelectric oxide crystals and is of opposite sign.     

Vibrational analysis of poly(vinylidene fluoride)

A vibrational analysis has been carried out for the two crystalline forms of poly(vinylidene fluoride) (PVF₂). The Raman spectrum of the planar form of PVF₂ is also reported. The band assignments are made on the basis of the spectral properties including the infrared dichroism and Raman intensities. A force field is derived based on a force constant refinement procedure utilizing the frequency data for both crystal forms.     

Raman scattering in nonplanar poly(vinylidene fluoride)

The Raman scattering of nonplanar (form 2) poly(vinylidene fluoride) (PVF₂) is described. Unique Raman bands not observed in the infrared spectra are found at 2973, 1437, 1327, 1198, and 1059 cm^?1. Band assignments are discussed by comparing infrared and Raman spectra of form 2 PVF₂.     

The morphology of poly(vinylidene fluoride) crystallized from blends of poly(vinylidene fluoride) and poly(ethyl acrylate)

A combined optical and electron microscopical study has been carried out of the crystallization habits of poly(vinylidene fluoride) (PVF₂) when it is crystallized from blends with noncrystallizable poly(ethyl acrylate) (PEA). The PVF₂/PEA weight ratios were 0.5/99.5,5/95, and 15/85. Isothermal crystallization upon cooling the blends from the single-phase liquid region was carried out in the range 135–155°C, in which the polymer crystallizes in the α-orthorhombic unit cell form. The 0.5/99.5 blend yielded multilayered and planar lamellar crystals. The lamellae formed at low undercoolings were lozenge shaped and bounded laterally by {110} faces. This habit is prototypical of the dendritic lateral habits exhibited by the crystals grown from the same blend at high undercoolings as well as by the constituent lamellae in the incipient spherulitic aggregates and banded spherulites that formed from the 5/95 and the 15/85 blends, respectively. In contrast with the planar crystals grown from the 0.5/99.5 blend, the formation of the aggregates grown from the 5/95 blend is governed by a conformationally complex motif of dendritic lamellar growth and proliferation. The development of these aggregates is characterized by the twisting of the orientation of lamellae about their preferential b-axis direction of growth, coupled with a fan-like splaying or spreading of lamellae about that axis. The radial growth in the banded spherulites formed from the 15/85 blend is governed by a radially periodic repetition of a similar lamellar twisting/fan-like spreading growth motif whose recurrence corresponds to the extinction band spacing. This motif differs in its fan-like splaying component from banding due to just a helicoidal twisting of lamellae about the radial direction. © 1993 John Wiley & Sons, Inc.     

Ferroelectric properties of nylon 11 and poly(vinylidene fluoride) blends

Both poly(vinylidene fluoride) (PVF₂) and nylon 11 are ferroelectric polymers, and have been extensively studied over the past two decades. Blend films were made from mixed powders of these two polymers, which were then melt pressed and cold drawn. The ferroelectric properties of these blend films were investigated. The remnant polarization, P_r, was found to vary with composition, and to be 60% larger than that of either component at a 50/50 (by weight) composition where P_r exhibited a maximum of about 90 mC/m². The magnitude of the coercive field, E_c, also exhibited a maximum at this composition. Both P_r and E_c are also observed to change significantly with the draw ratio. The results are discussed based on a two-phase dielectric composite model. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3217–3225, 1999     

Melting and crystallization behavior of poly(vinylidene fluoride) produced isothermally in the intercrystalline spaces of poly(ethylene terephthalate) from its blends

The melting of isothermally crystallized poly(vinylidene fluoride) (PVF₂), produced in the intercrystalline spaces of poly(ethylene terephthalate) (PET) from its blends, showed a unique behavior: the melting temperature decreased with the increasing crystallinity of PVF₂ (i.e., with increasing crystallization time) for PVF₂ volume fractions of 0.64 and 0.51. The melting temperature of already crystallized PET also decreased as the PVF₂ crystallization progressed and the isothermal crystallization temperature of PVF₂ increased. Separate reasons were proposed to account for these behaviors. The equilibrium melting temperatures of PVF₂ in the blends, measured by the Hoffman–Weeks extrapolation procedure, were used to calculate the polymer–polymer interaction parameter (χ₂₁); only the noncrystallized portion of PET contributing to the mixed amorphous phase was considered. The χ₂₁value (−1.75) was lower than χ₁₂ (−0.14), calculated from the melting temperature depression of PET. However, when they were normalized to the unit volumes of the respective components, the two values were found to be the same. The crystallization rate of PVF₂ decreased with an increasing volume fraction of PET in the blend. The Avrami exponent increased for the volume fraction of PVF₂ (0.77) and then progressively decreased with an increasing volume fraction of PET. A gradual change in the nature of the regime transition from regime II/regime I to regime III/regime II with increasing PET concentration was observed. The value of the chain-extension factor of PVF₂ significantly increased with an increase in the PET concentration in the blends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2215–2227, 2004     

Melting studies of poly(vinylidene fluoride) and its blends with poly(methyl methacrylate)

Blends of poly(vinylidene fluoride) (PVF₂) and poly(methyl methacrylate) exhibit complex melting behavior when crystallized at low undercoolings. Three crystals comprised of two different PVF₂ forms grow. Hoffman-Weeks plots of the observed melting points T_m of these crystals versus crystallization temperatures are constructed. The lowest-melting-point species, the α form, shows a change in slope which is attributed to fewer head-to-head PVF₂ units trapped in the crystal at higher temperatures. Defect energies in the crystal due to these units are calculated to be from 6.3 to 10.3 kJ/mol. Estimating lamellar thicknesses from the slopes of the two regions gives much more reasonable values when the high-temperature data are used. Removal of kinetic effects that lower the observed T_m by extrapolating the data to obtain T permits the thermodynamic interaction energy density B between the two polymers to be obtained. The low-temperature α-form data give B = ?8.83 × 10⁶ J/m³. The high-temperature α-form data and the T of the γ-form crystals both show B to vary from ?5.40 × 10⁶ to ?2.96 × 10⁷ J/m³ as the blend composition goes from 40.1 vol % to pure PVF₂.     

A spectroscopic study to interpret the increased piezoelectric effect at high temperature in poly(vinylidene fluoride)

Spectroscopic experiments were carried out to directly measure the electric-field-induced microstructural changes in PVF₂ at high temperature (65°C). We found, in comparison with roomtemperature measurements, that the reduction of the coercive field is directly related to faster dipolar orientation at this temperature. Furthermore, the α to β or δ phase transformation can take place at a much faster rate and lower field strength than has been previously reported either theoretically experimentally.     

Crystallization and morphology of melt-solidified poly(vinylidene fluoride)

Crystallization of poly(vinylidene fluoride) (PVF₂) from the melt yields two types of spherulites. The first consists of large, highly birefringent, and tightly banded spherulites of the α-form, which are seen at all temperatures. The second type, termed mixed, crystallizes with a newly reported unit cell which appears to be the correct one for γ-PVF₂, but may contain inclusions of a different form (probably α-PVF₂); it is seen only at relatively high temperatures and frequently exhibits irregular or disorganized birefringent and morphological features. In thin films, some mixed spherulites contain regions of single-crystal-like aggregates which are grown parallel to the substrate and appear essentially nonbirefringent between crossed polars. Mixed spherulites frequently undergo transformations at their growth fronts leading to initiation of α-growth. These transformations are associated with the generally higher growth rate of α-spherulites which may exceed that of their mixed counterparts by almost seven times. However, with increasing temperature this difference in growth rates is progressively reduced and ultimately reversed.     

Brillouin scattering studies of poly(vinylidene fluoride) films subject to uniaxial stretching

Brillouin scattering spectra of poly(vinylidene fluoride) films subject to stretching have been studied as a function of draw (stretch) ratios. The longitudinal sound velocity is found to be isotropic for the unoriented film, but as the film is stretched, the velocity along the direction of stretch becomes higher than that perpendicular to it. The increase in the sound velocity is due to the induced orientation of the chains in the amorphous and the crystalline regions. The Hermans orientation parameter has been determined as a function of stretch from the velocity data. The result indicates the occurrence of recrystallization and reorganization as a result of transformation to form I crystallites from the amorphous phase as the film is stretched.     

Multiscale Porosity from Thermoreversible Poly(vinylidene fluoride) Gels in Diethyl Azelate

Poly(vinylidene fluoride) (PVF₂) produces thermoreversible gels in a series of diesters. The polymer-solvent complexation occurred for intermittent number of carbon atoms n ⩾ 2 and the enthalpy of complexation increased with increasing n. The gels were dried by replacing the diesters with low boiling solvent like cyclohexane (bp. 80 °C) and methylcyclohexane (bp. 99 °C). The porosity of the dried gels was measured using Poremaster-60. For PVF₂-DEAZ gel meso and macro porosity have been observed. The former pore dimensions have been attributed for polymer-solvent complexation while the macroporosity has been attributed for caging of solvent between the PVF₂ fibrils The porosity measured from nitrogen adsorption isotherms using BJH method indicate presence of minimum pore diameter of 3.8 nm for the 10% dried gel of PVF₂.     

Annealing effects of phase I poly(vinylidene fluoride)

The effects of annealing temperatures on stretched poly(vinylidene fluoride) film were systematically studied from the “as-received” condition up to the melting range (180°C). X-ray diffraction studies indicate that the annealing process brings about better chain packing and increased crystallite perfection. The elastic modulus and piezoelectric strain and stress constants, d₃, and e₃₁, decrease as the annealing temperature T_a increases up to 160°C, while the remanent polarization P_r remains almost constant. Some of these characteritics may be interpreted in terms of a morphological transformation of microfibrils. The values of P_r, d₃₁, and e₃₁ increase dramatically as T_a increases from 160 to 180°C; P_r increases from 56 to 85 mC/m², d₃₁ from 20.2 to 27.7 pC/N, and e₃₁ from 51.4 to 65.2 mC/m². As a result, the values of P_r and d₃₁ were the largest recorded from any of the samples used in the present study. e₃₁ showed a value close to the largest one; this usually occurs in unannealed samples. Samples annealed in the melting range also exhibit significantly improved ageing characteristics. The large value of P_r and the small relaxation strength of both the dielectric constant and elastic modulus indicates that the largest crystallinity obtained is approximately 70%.     

Heat capacity of poly(vinylidene fluoride) and polytetrafluoroethylene between 5 and 200°K

Heat capacities of poly(vinylidene fluoride) (PVF₂) and polytetrafluoroethylene (PTFE) have been measured between 5 and 100°K with an accuracy of (1–5)% by adiabatic calorimetry. Calculations based on contributions from known optical lines and the Tarasov continuum model are in good agreement with experimental results down to 30°K for PVF₂ and 10°K for PTFE, and yield characteristic temperatures θ₁ and θ₃ which are consistent with previous values determined from high-temperature (100—350°K) data. At lower temperature the measured heat capacity is significantly higher [(30–100)%] than the model prediction, and can be satisfactorily accounted for by the introduction of localized vibrators at a concentration of about 1% as compared to acoustical oscillators and at a characteristic temperature of about 20°K. Using established data on polyethylene for comparison, the principle of additivity for heat capacities is found to be valid down to at least 20°K, convering the region (<60°K) where interchain vibrations contribute significantly to the heat capacity. Possible reasons for this unexpected behavior are discussed.     

Solid-state 13C-NMR studies of the aging of poly(vinylidene fluoride)/poly(methyl methacrylate) blends

Solid state ¹³C-NMR was used to investigate the miscibility and subsequent separation of solution-cast blends of poly(vinylidene fluoride) (PVF₂) and poly(methyl methacrylate) (PMMA) with aging for a range of compositions. It was found that one amorphous phase and intimate mixing of the polymer chains in this phase existed for all compositions of the blends, even after 2 months of aging at room temperature as determined by the proton spin lattice relaxation time T_1ρH in the rotating frame, and the time constant T_CH for transfer of magnetization. The T_1ρH is sensitive to the spatial homogeneity of the blend via spin diffusion and would indicate the presence of phases or domains in the amorphous component of the blend larger than approximately 19 Å. The T_CH is proportional to the inverse sixth power of the interatomic distances needed for transfer of magnetization from proton to carbon and would be sensitive to a separation of polymer chains in the amorphous phase with aging on the order of 4–5 Å. There was an increase of the T_1ρH and T_CH values with aging, indicating that a subtle separation between unlike chains in the amorphous phase was occurring although a single amorphous phase was present.     

Kink motion in poly(vinylidene fluoride) form I

The diffuse-streak x-ray scattering intensity from poly(vinylidene fluoride) form I, which is caused by kink bands with GT_n? (n odd) conformation contained in the crystallite, decreases with increasing temperature, while the intensity of the 001 reflection does not change. This is attributed to the disappearance of the kink bands in the crystallite, not to partial melting of crystallites containing kink bands. The disappearance of the kink bands suggests that kink motion takes place in the crystallite. Plots of the intensity of diffuse-streak scattering, estimated from the asymmetric part of the 001 reflection, against 1/T roughly give ΔH_v = ?4.6 kcal/mol. This suggests that the kink band is energetically more stable than the regular structure of form I.     

On the gelation rate of thermoreversible poly(vinylidene fluoride) gels in glyceryl tributyrate

The gelation rate of poly(vinylidene fluoride) (PVF₂)/glyceryl tributyrate (GTB) system has been measured. It has been analysed with the help of an equation which contains φⁿ and f(T) term where φ is a reduced overlapping concentration and n is analogous to the percolation exponent β in a three-dimensional lattice. f(T) is related to the temperature function of the coil-to-helix transition. Analysis of the gelation rates supports that the three-dimensional percolation is a suitable mechanism in this gelation process and it also indicates that the gelation is caused by coil-to-helix transition followed by their association.     

An equilibrium study on the distribution of structural defects between the lamellar and amorphous portions of poly(vinylidene fluoride) and (vinylidene fluoride‐tetra fluoro ethylene) copolymer crystals

Samples of poly(vinylidene fluoride) (PVF₂) and (vinylidene fluoride‐tetra fluoroethylene) (VF₂‐VF₄) copolymer were etched with a chromium‐based etching reagent. The etching rate was lower for the VF₂‐VF₄ copolymer samples than for the PVF₂ samples. The melting point and enthalpy of fusion increased with increased etching time of the etched specimen. This was also true for the melt‐quenched (etched) samples, whose values were always lower than those obtained from the direct run of the etched samples. The scanning electron micrographs of specimens etched for 24 h indicated that only the amorphous portion was etched without affecting the crystalline lamella. The sequence distribution of the PVF₂ and VF₂‐VF₄ copolymer crystals were determined by ¹⁹F NMR measurements of the samples and their etched species. The observed probabilities (P_obs), calculated from the integrated area of the NMR peaks, indicated that the crystalline lamella had a more oriented chain structure than that of the amorphous overlayer portion. The head‐to‐head defects calculated from the aforementioned sequence analysis indicated a greater propensity in the amorphous portion than in the crystalline lamella. The equilibrium constant (K) for the distribution of defects between the lamella and amorphous portion of the crystal varied from 0.7 to 0.9. It was higher at a higher quenching rate of the crystallization, and in the isothermal crystallization, it also had a substantially high value, indicating the equilibrium inclusion of defects in the crystal. The distribution constant increased with an increase in the defect content in the chain and decreased with an increase in the defect size. The sequence distribution data, analyzed through a suitable melting‐point depression equation, indicated a defect energy of 2.25 kcal/mol for the α‐phase PVF₂ crystals and 0.68 kcal/mol for the β‐phase VF₂‐VF₄ copolymer. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 297–308, 2000     

Thermal expansion of poly(vinylidene fluoride)

The thermal expansion behavior of oriented poly(vinylidene fluoride) films has been studied over the temperature range ?75 to +20°C. Representative high draw, low draw, and voided samples have been examined. For all samples at low temperatures the transverse thermal expansion coefficients, both in the plane of the sheet and perpendicular to it, are similar and have positive values of about 10^?4 K^?1. In the draw direction the thermal expansion coefficients are much smaller in magnitude and can be either positive or negative, the room temperature values varying in the range +4 × 10^?6 K^?1 for low draw samples to ?14 × 10^?6 K^?;1 for high draw samples. As the temperature is raised the coefficients also increase but, above the glass transition temperature, the value in the draw direction, α₁, shows a rapid fall in value. It is shown that this effect can be related quantitatively to the presence of an internal shrinkage stress. Differences between samples can then be primarily related to differences in the magnitude of this internal stress and to differences in the temperature dependence of the modulus of the sample.     

Characteristic ratio of the mean-square end-to-end distance of poly(vinylidene fluoride) with microstructural defects

The segment length distribution of isoregic head-to-head and tail-to-tail sequences in poly-(vinylidene fluoride) (PVF₂)

1 System. name: poly(1,1-difluoroethylene).

chains is calculated from ¹⁹F NMR literature data. It is found that the average length of inverse segments is very close to one unit; therefore almost all head-to-head defects are immediately repaired by an adjacent tail-to-tail addition. The role of microstructure on the characteristic ratio of the end-to-end distance is then investigated. Results obtained by two different methods indicate that, in agreement with previous Monte Carlo calculations, defects play a minor role for the conformational characteristics of PVF₂. However, a slight contraction of about 4% is expected for very defective chains.