Institut für Physik und Astronomie
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- P(VDF-TrFE-CFE) terpolymer (3)
- Curie transition (2)
- dielectric relaxation spectroscopy (2)
- relaxor-ferroelectric polymer (2)
- dielectric polarisation (1)
- differential scanning calorimetry (1)
- electrical polarization hysteresis (1)
- ferroelectric and paraelectric phases (1)
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- relaxor-ferroelectric polymers (1)
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- thermally stimulated depolarization current (1)
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The influence of chemical composition and crystallisation conditions on the ferroelectric and paraelectric phases and the resulting morphology in Poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) terpolymer films with 55.4/37.2/7.3 mol% or with 62.2/29.4/8.4 mol% of VDF/TrFE/CFE was studied. Poly(vinylidene fluoride trifluoroethylene) (P(VDF-TrFE)) with 75/25 mol% VDF/TrFE was employed as reference material. Fourier-Transform Infrared Spectroscopy (FTIR) was used to determine the fractions of the relevant terpolymer phases, and X-Ray Diffraction (XRD) was employed to assess the crystalline morphology. The FTIR results show an increase of the fraction of paraelectric phases after annealing. On the other hand, XRD results indicate a more stable paraelectric phase in the terpolymer with higher CFE content.
Dielectric relaxation processes and structural transitions in Poly(vinylidenefluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) terpolymer films with two different monomer compositions were investigated in comparison with Poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) copolymer films as reference material. Differential Scanning Calorimetry was employed to assess annealing effects on phase transitions and crystalline structure, while relaxation processes were investigated by means of Dielectric Relaxation Spectroscopy, the results of which indicate the existence of two separate dispersion regions, denoted as processes A and B, respectively. Process A appears at a certain temperature independent of frequency, but is strongly influenced by the crystallisation temperature and the CFE content, while peak B shows typical features of a relaxation process and is less influenced by crystallisation temperature and CFE content. Furthermore, peak B is related to the glass transition which is more pronounced in the terpolymer than in P(VDF-TrFE). A closer analysis indicates that the addition of CFE and thermal annealing gradually shift the ferro-to-paraelectric transition in P(VDF-TrFE) to lower temperatures, while the phase transition is transformed more and more into a relaxation.
Dielectric Relaxation Spectroscopy (DRS) and Thermally Stimulated Depolarization Current (TSDC) measurements were employed to study dielectric-relaxation processes, structural transitions and electric-polarization phenomena in poly(vinylidenefluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) terpolymer films. Results from DRS confirm the existence of two separate dispersion regions related to a para-to-ferroelectric phase transition and to the glass transition. The dipolar TSDC peak correlates with the loss peak of the ? relaxation that represents the glass transition. The electric polarization calculated from the dipolar TSDC peak (glass transition) shows a non-linear electric-field dependence and saturates at high electric poling fields. As the observed behaviour is essentially the same as that of the electric polarization obtained from direct polarization-versus-electric-field hysteresis measurements, TSDC experiments are also suitable for studying the polarization in relaxor-ferroelectric polymers. A saturation polarization of 44 mC m(?2) was found for an electric field of 190 MV m(?1).
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.
Dielectric measurements have been carried out on all-organic metal-insulator-semiconductor structures with the ferroelectric polymer poly(vinylidenefluoride-trifluoroethylene) as the gate insulator. It is shown that the polarization states remain stable after poling with accumulation and depletion voltage. However, negative charge trapped at the semiconductor-insulator interface during the depletion cycle masks the negative shift in flatband voltage expected during the sweep to accumulation voltages.
Thin films of ferroelectric beta-phase poly(vinylidene fluoride) (PVDF) were spin-coated from a solution that contained small amounts of the ionic liquid (IL) 1-ethyl-3-methylimidazolium nitrate. A remanent polarization of 60 mC/m(2) and a quasi-static pyroelectric coefficient of 19 mu C/m(2)K at 30 degrees C were observed in the films. It is suggested that the IL promotes the formation of the beta phase through dipolar interactions between PVDF chain-molecules and the IL. The dipolar interactions are identified as Coulomb attraction between hydrogen atoms in PVDF chains and anions in IL. The strong crystallinity increase is probably caused by the same dipolar interaction as well.
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 ( 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 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 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.
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.