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By means of pyroelectrical measurements and dielectric spectroscopy as well as structural information from differential scanning calorimetry, it is shown that, in a poly(vinyl alcohol) with azobenzene-alkoxy side chains, pyroelctricity and dielectric hysteresis which are usually related to each other have different origins. The pyroelectric effect is explained with reversible dipole-density changes upon thermal expansion, whereas the dielectric hysteresis is proposed to result from a charge-carrier polarisation.
Electrets
(1999)
Dielectric spectra of a partially fluorinated chromophore / amorphous Teflon AF guest-host system
(1999)
Complete relaxation map of polyethylene : filler-induced chemical modifications as dielectric probes
(2001)
Coating of porous polytetrafluoroethylene films with other polymers for electret applications
(2001)
Relaxation behaviour of thermoplastic polyurethanes with covalently attached nitroaniline dipoles
(2002)
Ferroelectric polyamide 11 films were prepared by melt-quenching, cold-drawing and electrical poling. Their ferroelectricity was studied by means of dielectric-hysteresis measurements. A remnant polarisation of up to 35 mC/m(2) and a coercive field of 75 MV/m were obtained. The piezoelectric d(33) coefficient and the pyroelectric coefficient of the films are reduced by annealing just below the melting region, but remain at about 3 pC/N and 8 muC/(m(2)K), respectively, during further heat treatment. Differential scanning calorimetry (DSC), dielectric relaxation spectroscopy (DRS) and thermally stimulated depolarisation (TSD) were applied for investigating the conformational changes induced by melt-quenching, cold-drawing and annealing. The results indicate that the cold-drawn film mainly consists of a rigid amorphous phase which exhibits considerably lower conductivity, no glass transition and consequently no dielectric a relaxation. Instead, an a, relaxation is found, which is related to chain motions in regions of the rigid amorphous phase where the amide-group dipoles are not perfectly ordered. Annealing removes imperfectly ordered structures, but does not affect the ferroelectric polarisation. Therefore, it may be concluded that essentially the a, relaxation causes the thermally non-stable part of the piezo- and pyroelectricity in polyamide 11
Organic materials with non-centrosymmetric chromophores are known to be susceptible to a number of photochemical processes, including reversible isomerization reactions as well as irreversible photo-oxidation or photo- reduction reactions. Reversible isomerization is the basis for a variety of applications, such as photo-induced poling, optical data storage and optical grating formation. The irreversible processes that involve the destruction of the chromophores have been found useful for the fabrication of optical waveguides, but they also limit the life times of polymeric photonic devices. In this paper, it is demonstrated that dielectric measurements allow for an in-depth investigation of non-reversible chromophore degradation processes in a typical side-chain polymer. The time- and temperature-dependent dielectric function of the polymer at 1 kHz enables us to follow the chromophore-degradation kinetics and to monitor the bleaching depth as a function of time at room and elevated temperatures
The stability of space charge in electrets such as polytetrafluoroethylene (PTFE), polyethylene terephthalate (PETP) and polypropylene (PP) under ultraviolet irradiation has been investigated using photostimulated discharge spectroscopy. While only weak discharge currents were observed in PTFE coated with semitransparent gold electrodes, up to 15 pA/cm(2) were found in PETP around the UV absorption edge near 310 nm. Space charge profiles obtained with the piezoelectrically generated pressure step method indicate that near-surface charges were almost completely removed. In PP foam, recent findings of a UV-reduced d(33) coefficient were confirmed for exposure times of up to 3.5 h, and a discharge peak at 200 urn could be assigned to the charges stored on the surfaces of the voids. The unique morphology and the (quasi-) piezoelectric properties of cellular PP make it a role model for the future investigation of charge storage in electrets
Ferroelectrets : electrically charged polymer foams as quasi-piezoelectric transducer materials
(2004)
Voided space-charge electrets : piezoelectric transducer materials for electro-acoustic applications
(2004)
In cellular, electromechanically active polymer films, the so-called ferroelectrets, the cell size and shape distributions can be varied through a controlled inflation process. Up to now, high-pressure treatments were usually performed at elevated temperatures. There are, however, significant experimental limitations and complications if the pressure and temperature treatments are performed at the same time. Here, we demonstrate the controlled inflation of cellular polypropylene films by means of sepal-ate pressure and temperature treatments. Separate procedures are Much easier to implement. Excellent electromechanical properties were achieved with Such a two-step inflation process. The technique has significant potential for inflating large-area transducer films for electromechanical and electroacoustical applications
Piezo-, pyro- and ferroelectricity in poly (vinylidene fluoride-hexafluoropropylene) copolymer films
(2004)
Thin films of poly(vinylidene fluoride-hexafluoropropylene) P(VDF-HFP) show significant electroactive properties, such as piezoelectricity, pyroelectricity and electrostriction. Suitable polar P(VDF-HFP) copolymer films can be prepared by melt-pressing or solution-casting. Dipolar orientation causes the macroscopic polarization and thus also the symmetry breaking necessary for electroactive properties. We discuss the polarization build-up in thin, stretched and non-stretched, films of P(VDF-HFP) copolymer with a HFP content of 15%. Poling currents measured in-situ during electric poling are analyzed and the polarization is calculated. Suitable electric poling leads to hysteresis phenomena of the polarization as a function of the electric field as well as to significant polarization during switching experiments. Our results indicate dipolar orientation also in non-stretched P(VDF-HFP) films
When exposed to sufficiently high electric fields, polymer-foam electret materials with closed cells exhibit ferroelectric-like behavior and may therefore be called ferroelectrets. In cellular ferroelectrets, the influence of the cell size and shape distributions on the application-relevant properties is not yet understood. Therefore, controlled inflation experiments were carried out on cellular polypropylene films, and the resulting elastical and electromechanical parameters were determined. The elastic modulus in the thickness direction shows a minimum with a corresponding maximum in the electromechanical transducer coefficient. The resonance frequency shifts as a function of the elastic modulus and the relative density of the inflated cellular films. Therefore, the transducer properties of cellular ferroelectrets can be optimized by means of controlled inflation. (C) 2004 American Institute of Physics
We present calculations on the deformation of two- and three-layer electret systems. The electrical field is coupled with the stress-strain equations by means of the Maxwell stress tensor. In the simulations, two-phase systems are considered, and intrinsic relative dielectric permittivity and Young's modulus of the phases are altered. The numerically calculated electro-mechanical activity is compared to an analytical expression. Simulations are performed on two- and three-layer systems. Various parameters in the model are systematically varied and their influence on the resulting piezoelectricity is estimated. In three-layer systems with bipolar charge, the piezoelectric coefficients exhibit a strong dependence on the elastic moduli of the phases. However, with mono-polar charge, there is no significant piezoelectric effect. A two-dimensional simulation illustrated that higher piezoelectric coefficients can be obtained for non-uniform surface charges and low Poisson's ratio of phases. Irregular structures considered exhibit low piezoelectric activity compared to two-layer structures. (C) 2004 Elsevier B.V. All rights reserved
Cellular polypropylene (PP) films were treated with sulfur hexafluoride (SF6) gas in order to study the SF6 penetration behaviour and optimize the electric charging conditions. There were differences in the penetration of SF6 for different cellular PP materials, depending on the microscopic properties, which manifest themselves in the voided structure as well as in the mechanical stiffnesses of the cellular films. The penetration of SF6 after long-term pressure treatment is confirmed in strongly inflated cellular PP films with a low mechanical stiffness of about 1 MPa. No SF6 penetration occurs for slightly inflated cellular PP films with smaller void sizes and higher mechanical stiffnesses of around 5.8 MPa. The observed thickness variations, the higher charging fields during corona charging because of SF6 penetration and the SF6 environment, as well as the resulting electromechanical properties are discussed
Space-charge depth profiles in various electret polymers have been measured in both the time and the frequency domain using thermal pulses and waves, respectively. A comparison of the two techniques on corona-charged polytetrafluoroethylene showed that the thermal-pulse method yielded similar results as the thermal-wave technique, but approximately 20-50 times faster. The article discusses sensitivity limitations as well as possible applications, including the real-time monitoring of space-charge decay under UV irradiation. (C) 2005 American Institute of Physics
High-resolution, large-area three-dimensional mapping of polarization profiles in electret polymers was carried out by means of a fast thermal pulse technique with a focused laser beam. A lateral resolution of 38 mu m and a near- surface depth resolution of less than 0.5 mu m was achieved. At larger depths, fast thermal diffusion in the metal electrode rather than the laser spot size becomes the limiting factor for the lateral resolution. (c) 2005 American Institute of Physics
Piezoelectric cellular polypropylene films, so-called ferroelectrets, are assembled in a stack with two active transducer layers. The stack is characterized with respect to its linear and quadratic response in a frequency range from 1 kHz to 80 kHz. A relatively smooth frequency response in the sound-pressure level is found for the individual layers as well as for both layers driven in phase. The piezoelectric response of the two-layer stack is twice the response of an individual layer over a rather broad frequency range. Furthermore, the influence of the preparation conditions on the resonance frequency and the effect of the quadratic distortion on the radiated sound are investigated both for the individual transducer films in the stack and for the stack system as a whole
In this paper, a recently developed numerical method to analyze dielectric-spectroscopy data is applied to alpha-phase polyvinylidene fluoride (PVDF). The numerical procedure is non-parametric and does not contain any of the extensively used empirical formulas mentioned in the literature. The method basically recovers the unknown distribution of relaxation times of the generalized dielectric function representation by simultaneous application of the Monte Carlo integration method and of the constrained least-squares optimization. The relaxation map constructed after the numerical analysis is compared to a-phase PVDF data presented in the literature and results of the parametric analysis with a well- known empirical formula. (c) 2005 Elsevier B.V. All rights reserved
The conductivity of alpha-polyvinylidene fluoride is obtained from dielectric measurements performed in the frequency domain at several temperatures. At temperatures above the glass-transition, the conductivity can be interpreted as an ionic conductivity, which confirms earlier results reported in the literature. Our investigation shows that the observed ionic conductivity is closely related to the amorphous phase of the polymer. (C) 2005 American Institute of Physics
The acetone extracts of the root bark and stem bark of Erythrina sacleuxii showed antiplasmodial activities against the chloroquine-sensitive (D6) and chloroquine-resistant (W2) strains of Plasmodium falciparum. Chromatographic separation of the acetone extract of the root bark afforded a new isoflavone, 7-hydroxy-4 -methoxy-3'- prenylisoflavone (trivial name 5-deoxy-3' - prenylbiochanin A) along with known isoflavonoids as the antiplasmodial principles. Flavonoids and isoflavonoids isolated from the stem bark of E. sucleuxii were also tested and showed antiplasmodial activities. The structures were determined on the basis of spectroscopic evidence.
Ferroelectrets are thin films of polymer foams, exhibiting piezoelectric properties after electrical charging. Ferroelectret foams usually consist of a cellular polymer structure filled with air. Polymer-air composites are elastically soft due to their high air content as well as due to the size and shape of the polymer walls. Their elastically soft composite structure is one essential key for the working principle of ferroelectrets, besides the permanent trapping of electric charges inside the polymer voids. The elastic properties allow large deformations of the electrically charged voids. However, the composite structure can also possibly limit the stability and consequently the range of applications because of, e. g., penetration of gas and liquids accompanied by discharge phenomena or because of a mechanical pre-load which may be required during the application. Here, we discuss various stability aspects related to the piezoelectric properties of polypropylene ferroelectrets. Near and below room temperature, the piezoelectric effect and the stability of the trapped charges are practically independent from humidity during long-time storage in a humid atmosphere or water, or from operating conditions, such as continuous mechanical excitation. Thermal treatment of cellular polypropylene above -10 degrees C leads to a softening of the voided structure which is apparent from the decreasing values of the elastic modulus. This decrease results in an increase of the piezoelectric activity. Heating above 60 degrees C, however, leads to a decrease in piezoelectricity
We report measurements on the synchronization properties of organ pipes. First, we investigate influence of an external acoustical signal from a loudspeaker on the sound of an organ pipe. Second, the mutual influence of two pipes with different pitch is analyzed. In analogy to the externally driven, or mutually coupled self-sustained oscillators, one observes a frequency locking, which can be explained by synchronization theory. Further, we measure the dependence of the frequency of the signals emitted by two mutually detuned pipes with varying distance between the pipes. The spectrum shows a broad '' hump '' structure, not found for coupled oscillators. This indicates a complex coupling of the two organ pipes leading to nonlinear beat phenomena.
Polyvinylidene fluoride was dissolved together with solid sodium hydroxide as catalyst in a dimethylsulfoxide/ acetone mixture and moderately dehydrofluorinated. The dehydrofluorination leads to a partial degradation of the fluorohydrocarbons, and in particular to main-chain scission and to formation of carbon double or triple bonds. This enhances the absorption at UV-vis frequencies. The degradation process also generates a large amount of excess charges in the polymer, which influence the electrical polarization behavior of the dehydrofluorinated polymer. Uniaxial stretching of moderately dehydrofluorinated polyvinylidene fluoride leads to films in a polar phase. Dipole polarization in the degraded and stretched films is demonstrated by means of switching experiments
In this paper, a measuring technique is presented for the detection of radial oscillations of tube walls excited by changes in internal air pressure. On organ pipes, the oscillations were investigated by means of piezoelectric polymer films slightly tensioned around the pipe bodies. Employing sensors with patterned electrodes, the well-known elliptical oscillation of the cross section as well as an additional monopole breathing of the organ-pipe body were detected. For the monopole breathing, a close relationship between the pressure distribution of the air-column resonances inside the pipe and the circumference variations along the pipe was observed
Relaxation processes at the glass transition in polyamide 11 : From rigidity to viscoelasticity
(2006)
Elastic properties and electromechanical coupling factor of inflated polypropylene ferroelectrets
(2006)
New ferroelectrets were developed on the basis of foams from cyclo-olefin polymers and copolymers. The results obtained on the cyclo-olefin polymer foam demonstrate a significant improvement of the service temperature for ferroelectret transducer materials. Suitable compounding and preparation led to cyclo-olefin ferroelectrets with an electromechanical activity of around 15 pC/N, which is thermally stable at least up to 110 degrees C. The properties in sensor and actuator applications are strongly dependent on the processing parameters related to film-making, sensor and actuator preparation, gas content and electric charging. The processing window for the film stretching was very narrow compared to the earlier developed polypropylene ferroelectrets. The film porosity, softness and thus the electromechanical activity are adjusted by gas-diffusion expansion. The activity of the electromechanically operating sensors and actuators was increased by stacking several layers of cellular cyclo-olefin film. For applications such as flat loudspeakers, the foamed films are tuned by tensioning them on a support frame. Correct tensioning was essential also for reducing the distortion levels.
Relaxation processes at the glass transition in polyamide 11: From rigidity to viscoelasticity
(2006)
Relaxation processes associated with the glass transition in nonferroelectric and ferroelectric polyamide (PA) 11 are investigated by means of differential scanning calorimetry, dynamic mechanical analysis, and dielectric relaxation spectroscopy (DRS) in order to obtain information about the molecular mobility within the amorphous phase. In particular, the effects of melt quenching, cold drawing, and annealing just below the melting region are studied with respect to potential possibilities and limitations for improving the piezoelectric and pyroelectric properties of PA 11. A relaxation map is obtained from DRS that shows especially the crossover region where the cooperative alpha relaxation and the local beta relaxation merge into a single high-temperature process. No fundamental difference between quenched, cold-drawn, and annealed films is found, though in the cold-drawn (ferroelectric) film the alpha relaxation is suppressed and slowed down, but it is at least partly recovered by subsequent annealing. It is concluded that there exists an amorphous phase in all structures, even in the cold-drawn film. The amorphous phase can be more rigid or more viscoelastic depending on preparation. Cold drawing not only leads to crystallization in a ferroelectric form but also to higher rigidity of the remaining amorphous phase. Annealing just below the melting region after cold drawing causes a stronger phase separation between the crystalline phase and a more viscoelastic amorphous phase.
Fast, three-dimensional polarization mapping in piezoelectric sensor cables was performed by means of the novel thermal-pulse tomography (TPT) technique with a lateral resolution of 200 mum. The active piezoelectric cable material (a copolymer of polyvinylidene fluoride with trifluoroethylene) was electrically poled with a point-to-cable corona discharge. A focused laser was employed to heat the opaque outer electrode, and the short-circuit current generated by the thermal pulse was used to obtain 3D polarization maps via the scale transformation method. The article describes the TPT technique as a fast non-destructive option for studying cylindrical geometries.
Spectroscopic study of dielectric barrier discharges in cellular polypropylene ferroelectrets
(2007)
The transient light emission from the dielectric barrier discharges (DBDs) in cellular polypropylene ferroelectrets subjected to high electric poling fields was spectroscopically measured. The spectrum shows strong emission from the second positive system of molecular nitrogen, N-2(C (3)Pi(u))-> N-2(B (3)Pi(g)), and the first negative system of N-2(+), N-2(+)(B (2)Sigma(+)(u))-> N-2(+)(X (2)Sigma(+)(g)), consistent with a DBD in air. When a dc voltage is applied stepwise to the ferroelectret film, light emission starts above a threshold, coinciding with the threshold voltage in obtaining piezoelectricity. From selected vibronic band strength ratios, the electric field in the discharge was determined and found to agree with Townsend breakdown.
Zerstörungsfreie Tomographie von Raumladungs- und Polarisationsverteilungen mittles Wärmepulsen
(2007)
Non-destructive, three-dimensional imaging of space-charge and polarization distributions in electret materials has been implemented by means of laser-induced thermal pulses. In pyroelectric films of poled poly(vinylidene fluoride), images of up to 45 x 45 pixels with a depth resolution of less than 0.5 mu m and a lateral resolution of 40 mu m were recorded, the latter being limited by fast thermal diffusion in the absorbing metallic front electrode. Initial applications include the analysis of polarization distributions in corona-poled piezoelectric sensor cables and the detection of patterned space-charge distributions in polytetrafluoroethylene films.
Charging properties and time-temperature stability of innovative polymeric cellular ferroelectrets
(2007)
After appropriate mechanical and electrical treatments, some cellular polymers become able to retain space charge for a long time, i.e. they acquire electret behavior. The electrical treatment consists of charging under high levels of DC electric field. The mechanical treatment, based on the application of stretching forces to cellular polymer slabs that were before expanded under pressurized gas, affects the cavity size and shape, and therefore also the effectiveness of the charging process itself. An investigation of charging mechanisms, as well as of mechanical treatment, is therefore fundamental for optimizing the ferro- and piezo-electret properties. The aim of this paper is to discuss the effect of the physical dimension of the cavities on the charging behavior of cellular ferroelectrets and to focus on the time-temperature stability for two families of polymeric cellular ferroelectrets based on polypropylene (PP) and on a cyclo-olefin copolymer (COC). Emphasis will be given to the stretching process and in particular to the expansion rate applied during the manufacturing process (which affects the radial dimension and the height of the cavities, respectively). Space-charge and partial-discharge measurements as a function of time and temperature are the main tools to infer the influence of the cavity size on charging and stability characteristics.
Cork is a natural cellular and electrically insulating material which may have the capacity to store electric charges on or in its cell walls. Since natural cork has many voids, it is difficult to obtain uniform samples with the required dimensions. Therefore, a more uniform material, namely commercial cork agglomerate, usually used for floor and wall coverings, is employed in the present study. Since we know from our previous work that the electrical properties of cork are drastically affected by absorbed and adsorbed water, samples were protected by means of different polymer coatings (applied by spin-coating or soaking). Corona charging and isothermal charging and discharging currents were used to study the electrical trapping and detrapping capabilities of the samples. A comparison of the results leads to the conclusion that the most promising method for storing electric charges in this cellular material consists of drying and coating or soaking with a hydrophobic, electrically insulating polymer such as polytetraflouroethylene (Teflon (R)). (c) 2007 Elsevier B.V. All rights reserved.
Polymer foams with electrically charged cellular voids, the so-called ferroelectrets, are soft piezoelectric transducer materials. Several polymers such as polyethylene terephthalate or cyclo-olefin copolymers are under investigation with respect to their suitability as ferroelectrets. Here, the authors report an additional ferroelectret polymer, cellular polyethylene-naphthalate (PEN), which was prepared from commercial uniform polymer films by means of foaming in supercritical carbon dioxide, inflation, biaxial stretching, electrical charging, and metallization. Piezoelectric d(33) coefficients of up to 140 pC/N demonstrate the suitability of such cellular PEN films for transducer applications. Their piezoelectricity is partially stable at elevated temperatures as high as 100 degrees C.
Electrically charged cellular polymer films can exhibit very high piezoelectric activity and are therefore more and more often employed in advanced electromechanical and electro-acoustical transducers. In this paper, we report an optimized sequence of steps for preparing such ferroelectrets from commercial nonvoided ploy(ethylene terephthalate) (PETP) films by means of foaming with CO2 biaxial mechanical stretching, controlled void inflation, and bipolar electric charging. The nonvoid PETP films foamed with supercritical CO2 at a suitably high pressure and subsequently annealed for stabilization. The cellular foam structure was further optimized by means of well controlled biaxial stretching in a commercial stretcher and sometimes subsequent inflamation in a pressure chamber. Bipolar electric charging of the internal voids was achieved through the application of high electric fields in an SF0 atmosphere. The new optimized PETP ferroelectric exhibit quite large piezoelectric coefficients up to almost 500 pCN(-1), for which unusually low elastic stiffness of only around 0.3 MPa are essential. The PETP foam ferroelectrics posses unclamped thickenss-extension resonance frequences between approximately 120 and 250 kHz, and are thus highly suitable for several established as well as novel ultrasonic-transductant applications.
We describe the concept, the fabrication, and the most relevant properties of a piezoelectric-polymer system: Two fluoroethylenepropylene (FEP) films with good electret properties are laminated around a specifically designed and prepared polytetrafluoroethylene (PTFE) template at 300 degrees C. After removing the PTFE template, a two-layer FEP film with open tubular channels is obtained. For electric charging, the two-layer FEP system is subjected to a high electric field. The resulting dielectric barrier discharges inside the tubular channels yield a ferroelectret with high piezoelectricity. d(33) coefficients of up to 160 pC/N have already been achieved on the ferroelectret films. After charging at suitable elevated temperatures, the piezoelectricity is stable at temperatures of at least 130 degrees C. Advantages of the transducer films include ease of fabrication at laboratory or industrial scales, a wide range of possible geometrical and processing parameters, straightforward control of the uniformity of the polymer system, flexibility, and versatility of the soft ferroelectrets, and a large potential for device applications e.g., in the areas of biomedicine, communications, production engineering, sensor systems, environmental monitoring, etc.
In this paper, two non-destructive thermal methods are used in order to determine, with a high degree of accuracy, three-dimensional polarization distributions in thin films (12 mu m) of poly(vinylidenefluoride- trifluoroethylene) (PVDF-TrFE). The techniques are the frequency-domain Focused Laser Intensity Modulation Method (FLIMM) and time-domain Thermal-Pulse Tomography (TPT). Samples were first metalized with grid-shaped electrode and poled. 3D polarization mapping yielded profiles which reproduce the electrode-grid shape. The polarization is not uniform across the sample thickness. Significant polarization values are found only at depths beyond 0.5 mu m from the sample surface. Both methods provide similar results, TPT method being faster, whereas the FLIMM technique has a better lateral resolution.
The zeta potential of the motile spores of the green alga (seaweed) Ulva linza was quantified by video microscopy in combination with optical tweezers and determined to be -19.3ñ1.1 mV. The electrostatic component involved in the settlement and adhesion of spores was studied using electret surfaces consisting of PTFE and bearing different net charges. As the surface chemistry remains the same for differently charged surfaces, the experimental results isolate the influence of surface charge and thus electrostatic interactions. Ulva spores were demonstrated to have a reduced tendency to settle on negatively charged surfaces and when they did settle the adhesion strength of settled spores was lower than with neutral or positively charged surfaces. These observations can be ascribed to electrostatic interactions.
Polymer-dispersed liquid crystals (PDLCs) are prepared from poly(vinylidene fluoride-trifluoroethylene) (P(VDF- TrFE)) and a nematic liquid-crystal (LC). The anchoring effect was studied using dielectric relaxation spectroscopy. Two dispersion regions are observed in the dielectric spectra of the pure P(VDF-TrFE) film. They are related to the glass transition and to a space-charge relaxation. In PDLC films containing 10 wt% of LC, an additional, bias field-dependent relaxation peak is found that can be attributed to the motion of LC molecules. Due to the hindered movement of the LC molecules, this relaxation process is considerably slowed down, compared with the related process in the pure LC.
beta-phase poly(vinylidene fluoride-hexafluoropropylene) (P(VDF-HFP)) copolymer films were prepared by uniaxially stretching solution-cast or melt-quenched samples. Different preparation routes lead to different amounts of the crystalline alpha and beta phases in the films, as detected by means of Fourier-transform infrared spectroscopy and X-ray diffractometry. The beta phase is significantly enhanced in melt-quenched and stretched films in comparison to solution-cast and stretched films. This is particularly true for copolymer samples with higher HFP content. The beta- phase enhancement is also observed in ferroelectric-hysteresis experiments where a rather high polarization of 58 mC/ m(2) was found on melt-quenched and stretched samples after poling at electric fields of 140 MV/m. After poling at 160 MV/m, one of these samples exhibited a piezoelectric d(33) coefficient as high as 21 pC/N. An electric-field-induced partial transition from the alpha to the beta phase was also observed on the melt-quenched and stretched samples. This effect leads to a further increase in the applications-relevant dipole polarization. Uniaxially stretched ferroelectric- polymer films are highly anisotropic. Dielectric resonance spectroscopy reveals a strong increase of the transverse piezoelectric d(32) coefficient and a strong decrease of the transverse elastic modulus c(32) upon heating from 20 to 50 degrees C.
The influence of the solvent-evaporation rate on the formation of of. and P crystalline phases in solution-cast poly(vinylidene fluoride) (PVDF) films was systematically investigated. Films were crystallized from PVDF/N,N- dimethylformamide solutions with concentrations of 2.5, 5.0, 10, and 20 wt % at different temperatures. During crystallization, the solvent evaporation rate was monitored in situ by means of a semianalytic balance. With this system, it was possible to determine the evaporation rate for different concentrations and temperatures of the solution under specific ambient conditions (pressure, temperature, and humidity). Fourier-Transform InfraRed spectroscopy with Attenuated Total Reflectance revealed the P-phase content in the PVDF films and its dependence on previous evaporation rates. Based on the relation between the evaporation rate and the PVDF phase composition, a consistent explanation for the different amounts of P phase observed at the upper and lower sample surfaces is achieved. Furthermore, the role of the sample thickness has also been studied. The experimental results show that not only the temperature but also the evaporation rate have to be controlled to obtain the desired crystalline phases in solution-cast PVDF films.
A new arrangement of the optical elements in a Thermal-Pulse-Tomography (TPT) setup allows to scan micrometer structures in composite and heterogeneous samples such as polymer-dispersed liquid crystals (PDLCs). The non-destructive TPT technique allows the determination of three-dimensional profiles of polarization and space charge in dielectrics. The samples under study were 12 mu m thick films of a copolymer of vinylidene fluoride with trifluoroethylene P(VDF- TrFE) (65/35) with embedded liquid-crystal droplets. The poling process was performed in direct contact well above the coercive field of the copolymer. The 3D map obtained from scanning with a 10 mu m wide spot shows elliptically shaped areas with liquid-crystal droplets. Considering the droplets as oblate spheroids, their major axis lies in the x-y plane, while their minor axis in the z direction measures 0.5 mu m or more. This result is in good agreement with scanning electron micrographs. It is believed that the major axis is overestimated due to imaging of liquid-crystal clusters.