Hybrid organic-inorganic ionic conductors, also called ormolytes (organically modified electrolytes), were obtained by dissolution of LiClO 4 in siloxane-poly(propylene glycol) matrixes. The dynamic features of these nanocomposites were studied and correlated to their electrical properties. Solid-state nuclear magnetic resonance (NMR) spectroscopy was used to probe the effects of the temperature and nanocomposite composition on the dynamic behaviors of both the ionic species ( 7 Li) and the polymer chains ( 13 C). NMR, dc ionic conductivity, and DSC results demonstrate that the Li + mobility is strongly assisted by the segmental motion of the polymer chain above its glass transition temperature. The ac ionic conductivity in such composites is explained by use of the random free energy barrier (RFEB) model, which is in agreement with their disordered and heterogeneous structures. These solid ormolytes are transparent and flexible, and they exhibit good ionic conductivity at room temperature (up to 10 -4 S/cm). Consequently, they are very promising candidates for use in several applications such as batteries, sensors, and electrochromic and photoelectrochemical devices.
The ac complex conductivity σ*(f) of polyaniline (PAN) films at different doping levels and different temperatures, in the 1–100 KHz frequency range, are reported. The results are typical of a disordered medium where the real component of ac conductivity is frequency independent at low frequencies, rising for higher values of frequencies. In order to interpret both the real and the imaginary components of σ*(f), we developed a model which considers the doped PAN as a disordered insulating matrix, sprinkled with conductive islands generated by doping, as indicated by energy dispersed x-ray microanalysis. The conduction through the insulating matrix obeys the random free energy barrier model, while in the conductive islands a metallic frequency-independent conductivity is considered. From the fittings we obtained the activation energy value of the maximum energy barrier of the doping mechanism and estimated the concentration of hopping sites.
In this work, the effect of gamma radiation on the optical properties of poly[2-methoxy-5-(2′-ethylhexyloxy)-p-phenylenevinylene] (MEH-PPV) is studied. The samples were irradiated at room temperature with different doses from 0Gyto152Gy using a Co60 gamma ray source. For thin films, significant changes in the UV-visible spectra were only observed at high doses (>1kGy). In solution, shifts in absorption peaks are observed at low doses (<10Gy), linearly dependent on dose. The shifts are explained by conjugation reduction, and possible causes are discussed. Our results indicate that MEH-PPV solution can be used as a dosimeter adequate for medical applications.
Poly(p‐phenylenevinylene) (PPV) and its derivatives exhibit strong luminescence, being serious candidates to be used as active layers in organic light‐emitting diodes. However, the structural degradation caused by photo‐oxidation is an obstacle for commercial applications of such materials. Here, we show that spectroscopy ellipsometry is a useful technique to investigate the photo‐oxidation of poly[(2‐methoxy‐5‐hexyloxy)‐p‐phenylenevinylene] (MH‐PPV), a PPV derivative, which emits a red color light. Spectroscopy ellipsometry enables determination of the complex dielectric function—ϵ*(E)—of MH‐PPV thin‐layer films exposed to air, in the 2.1–4.2 eV energy range, as a function of the light exposure time (te). By using the Lorentz model to fit the experimental ϵ*(E) curves, it was inferred that the interactions among polymeric chains increase with te. From ϵ*(E), it is also possible to obtain the complex refractive index, N*(E) = n + ik. At higher energies (where k ≪ n), n increases from 1.32 to 1.40 with the photo‐oxidation progress. The behavior of n was investigated by using the Lorenz–Lorentz equation, taking into account the contribution for n by the chromophores of MH‐PPV. The effect of photo‐oxidation, mainly due to the replacement of vinyl CC by the ketone CO bonds, is confirmed by Fourier transform infrared measurements, an effect that reduces the average effective polymer conjugation length. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1033–1041, 2004
Optical absorption and fluorescence measurements have been done on poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene]/[aluminum-tris(8-hydroxyquinoline)] solutions. The authors show that there is a visible response that covers the electronic absorption of bilirubin (350-500 nm), and hence, this material is applicable for managing the radiation doses planning before treatment of jaundice of neonates, which is one of the most common reasons of hospital readmission of newborns infants. The results show that the material presents a gradation of color from orange to yellow clearly, while its peak position emission shifts from orange-red (lambda(max) = 571 nm) to green (lambda(max) = 540 nm) with the radiation exposure time. The rate of these changes can be altered by manipulations of organic solution concentration and they are usually slow (from 2 to 8 h), suggesting these color and emission changes can be used to design an easy to make, easy to read, easy to operate, low cost (< US $0.50) and accuracy for individual monitoring indicator dosimeter in order to represent easily the radiation exposure time usually used in management of neonatal jaundice.
Complex impedance measurements were used to analyze the influence of ultraviolet and ozone gas on the electronic behaviour of ZnO films grown by rf magnetron sputtering. The data show that UV exposure strongly increases the ac conductivity of the film at very low frequencies, and that after ozone exposure it recovers the original value. At high frequencies, however, UV-light exposure it does not change the conductivity but the ozone acts in the sense to decrease it. Two distinct mechanisms, related to two relaxation time distributions are clearly observed: they are superimposed in the virgin sample, but they split forming two semicircles in the z 00 (f) À z 0 (f) diagrams when the samples are treated with UV and/or ozone gas. A combination of the bruggeman effective medium approximation (BEMA) with the random free energy barrier model is used to fit the data and to explain the ac conductivity variation phenomena observed.
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