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Термоактивационная спектроскопия композитных полимерных пленок на основе ударопрочного полистирола
(2019)
С помощью метода токов термостимулированной деполяризации (ТСД) исследованы релаксационные процессы в пленках ударопрочного полистирола (УПС) без наполнителя и с различным содержанием диоксида титана TiO2 (2, 4, 6 об.%). На кривых тока ТСД, полученных для композитных пленок, обнаружено три пика. Первый (α-релаксация) возникает при температуре около 93 °C и соответствует переходу вещества из стеклообразного состояния в высокоэластическое. Второй (ρ-пик) появляется как высокотемпературное плечо α-пика и соответствует процессу высвобождения и движения избыточных носителей заряда. Наличие третьего пика при температуре около 150 ºС характерно только для композитных пленок УПС. Разделение перекрывающихся α- и ρ-пиков проведено методом частичной термоочистки. Последующее применение регуляризующих алгоритмов Тихонова позволило определить энергию активации второго процесcа и сравнить полученное значение с результатом, полученным методом диэлектрической спектроскопии.
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.
Relaxation processes at the glass transition in polyamide 11 : From rigidity to viscoelasticity
(2006)
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
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