35 resultados para Fluorine containing polymers

em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"


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The temperature dependence of photoinduced birefringence was investigated for mixed Langmuir-Blodgett (LB) films from the homopolymer poly[4'-[[2-(methacryloyloxy)ethyl]ethyl-amino]-2-chloro-4-nitroazobenzene] (HPDR13) and cadmium stearate (Cdst) and from the copolymer 4-[N-ethyl-N-(2-hydroxyethyl)]amino-2'-chloro-4'-nitroazobenzene (MMA-DR13) and CdSt. Birefringence was achieved by impinging a linearly polarized light on the LB films. The maximum birefringence achieved decreased with temperature as thermal relaxation of the chromophores was facilitated. The buildup curves for birefringence were fitted with biexponential functions representing distinctly different mechanisms with time constants. The first, fast process is thermally activated and may be represented by an Arrhenius process. The decay of birefringence after switching off the laser source was described by a Kohlraush-Williams-Watts (KWW) function, consistent with a distribution of relaxation times for the polymer system. Activation energies were obtained from Arrhenius plots of the rate constant of the exponential functions and KWW function, which showed that the buildup of birefringence was very similar for the two polymer systems. The decay, however, was slower for the LB film from MMA-DR13/CdSt. (C) 2002 Published by Elsevier B.V. Ltd.

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The photoinduced birefringence is analyzed in a guest-host azobenzene-containing polymer in the temperature range from 20 to 330 K. An anomalous behavior arises in the low-temperature range, suggesting strong influence from the free volume for the chromophores in the polymer. This influence is so strong that quenched samples have a photoinduced signal ca. 5 times greater than the annealed ones at room temperature. An extended free volume model is presented based on two assumptions about thermal fluctuations in the cavities and their size distribution. This model, which is an extension of the model by Mita et al., can explain the main features of the photoinduced birefringence as a function of time, temperature, and initial free volume state. To account for the influence of free volume on the photoorientation, the detailed reorientation model by Sekkat's was used. We show that Sekkat's model leads to an exponential behavior at small orientation regimes, which simplifies the mathematical treatment and allows the mean free volume to be obtained from the data fitting.

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The nucleation and growth model, which is usually applied to switching phenomena, is adapted for explaining surface potential measurements on the P(VDF-TrFE) (polyvinylidene fluoride-trifluoroethylene) copolymer obtained in a constant current corona triode. It is shown that the growth is one-dimensional and that the nucleation rate is unimportant, probably because surface potential measurements take much longer than the switching ones. The surface potential data can therefore be accounted for by a growth model in which the velocity of growth varies exponentially with the electric field. Since hysteresis loops can be obtained from surface potential measurements, it is suggested that similar mechanisms can be used when treating switching and hysteresis phenomena, provided that account is taken of the difference in the time scale of the measurements.

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Differential scanning calorimetry (DSC) studies were performed for 60/40 P(VDF-TrFE). The results not only confirm the importance of thermal history but also show that the samples with various configurations in terms of ferroelectric phases can be obtained via thermal treatment.

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The thermal behavior of blends of poly(vinylidene fluoride), or PVDF, and poly(o-methoxyaniline) doped with toluene sulfonic acid was studied by thermogravimetic analysis, electrical conductivity measurements, differential scanning calorimetry, X-ray diffraction and scanning electron microscopy. Blends with thermal and electrical conductivity stabler than the conductive polymer alone were obtained. Nevertheless, degradation occurs after a long period of time (500 h) at high temperatures. The possible association of the conductivity decay with dopant loss, degradation and structural and morphological changes of the blend is discussed. (C) 2000 Elsevier Science Ltd.

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This work reports on the effects from thermal treatment in poly(vinylidene fluoride), PVDF, obtained with differential scanning calorimetry (DSC) and dynamic thermal analysis (DMA) measurements. It is shown that in successive DMA measurements performed with one sample the α relaxation peak almost disappears while the γ′ peak appears. The α relaxation peak, at ∼100°C in DMA measurements, is attributed to the preferential orientation of chains in the amorphous phase while the γ′ relaxation peak, at ∼50°C, is related to the thermal treatment to which the sample was submitted.

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Significant efforts are devoted to developing new ferroelectrets with well-controlled void distributions or uniform voids and with good long-term and thermal stability of the piezoelectricity. Here, we describe the concept, the fabrication, and the most relevant properties of fluoropolymer ferroelectret systems with three separate films of fluoroethylenepropylene (FEP), alternating with two polytetrafluoroethylene (PTFE) templates. The FEP films are selectively fused by means of a lamination process. Two practically identical PTFE templates are used, which have parallel rectangular openings (1.5×30 mm 2) separated by PTFE ridges of 1.5 mm width. After removing the PTFE templates, a three-layer FEP-film sandwich with tubular channels is obtained. We demonstrate that such FEP-film systems exhibit significant and stable piezoelectricity after charging under a high DC voltage. The resulting piezoelectric effect may be further improved by carefully assembling and arranging the PTFE templates during preparation. ©2010 IEEE.

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Two different cationic polymers of the same chemical type and with very similar chemical structures were reacted with a natural bentonite over a wide range of polymer/clay ratios. This study involved the synthesis of cationic aliphatic ammonium polyionenes, specifically 3,6-ionene and 3,6-dodecylionene. Ionenes are ion-containing polymers that contain quaternary nitrogen atoms in the main macromolecular chain as opposed to a pendant chain. The CHN content, basal spacing, and elemental composition of each of the polymer-clay complexes were analyzed by X-ray diffraction, X-ray fluorescence, and thermogravimetry. All the polycations reacted to form interlayer complexes with clay, which displaced more Na+ and little Ca2+. Sodium and calcium were both present as interlayer cations in the clay and its complexes. The TG/DTG curves show that both polymers underwent thermal degradation in more than one stage. Specifically, 3,6-ionene was found to undergo two stages of decomposition and 3,6-dodecylionene undergo three stages. The behavior of the TG/DTG curves and the activation energy values suggest that 3,6-dodecylionene (E = 174,85 kJ mol-1) complexes have greater thermal stability than 3,6-ionene (E = 115,52 kJ mol-1) complexes. The mechanism of degradation suggests a direct interaction with the dodecyl chain containing 12 carbons, which are present in 3,6-dodecylionene but not in 3,6-ionene. © 2012 Akadémiai Kiadó, Budapest, Hungary.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Electrostatic interactions govern most properties of polyelectrolyte films, as in the photoinduced bire-fringence of azo-containing polymers. In this paper we report a systematic investigation of optical storage characteristics of cast and layer-by-layer (LbL) films of poly[1 -[4-(3-carboxy-4 hydroxypheny-lazo) benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO). Birefringence was photoinduced faster in PAZO cast films prepared at high pHs, with the characteristic writing times decreasing almost linearly with the pH in the range between 4 and 9. This was attributed to an increased free volume for the azochromophores with the enhanced electrostatic repulsion in PAZO charged to a greater extent. In contrast, in LbL films of PAZO alternated with poly(allylamine hydrochloride) (PAH), the electrostatic interactions between the oppositely charged polymers hampered photoisomerization and molecular rearrangement, thus leading to a slower writing kinetics for highly charged PAH or PAZO.

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The effects of ion irradiation on fluorinated plasma polymer films are investigated using profilometry, surface contact-angle measurements, infrared reflection absorption spectroscopy (IRRAS) and X-ray photoelectron spectroscopy (XPS). Remarkably, helium plasma immersion ion implantation (PIII) of several amorphous hydrogenated fluorinated plasma polymers deposited from C(2)H(2)-SF(6), C(6)H(6)-SF(6) or C(6)F(6) produces film compactions of up to 40%, and modifies the surface energy in the 35 to 65 dyn cm(-1) range. As revealed by IRRAS and XPS, the films contain C-H, C-C, C=C, C=O, O-H and C-F groups. XPS spectra confirm the presence of N (typically similar to 5%). The films produced from SF(6)-containing plasmas also contain S. For irradiation times of 80 min, the film carbon content is increased, and the fluorine content is greatly reduced, by factors of about 3 to 15, depending on the initial film composition. (C) 2010 Elsevier B.V. All rights reserved.

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Mixtures of C6H6 and SF6 were polymerized in an r.f. discharge. Actinometry (quantitative optical emission spectroscopy) was used to determine trends in the plasma concentrations of the species F, H and CH as a function of the proportion of SF6 in the feed. Infrared spectroscopy and electron spectroscopy for chemical analysis were employed to characterize the deposited material. Increasing proportions of SF6 in the feed produced increased fragmentation of the benzene molecules and greater fluorination of the deposited material. The deposition rate, as determined by optical interferometry, was found to be enhanced about 4 times by the presence of 10-20% SF6 in the feed. At 50% SF6 in the feed, deposition rates were greater than in pure C6H6 plasmas despite the (probably large) etching effect of atomic fluorine from the discharge. Relationships between the plasma composition, electron density and temperature, film composition and growth rate are discussed. © 1992.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)