Spectroscopic, morphological and electrochromic characterization of layer-by-layer hybrid films of polyaniline and hexaniobate nanoscrolls

The combination of semiconducting oxides and polyaniline in the nanoscale range may result in hybrid materials having enhanced properties, such as electrochromism and charge capacity. This paper reports the spectroscopic, morphological and electrochromic characterization of hybrid films made up of hexaniobate one-dimensional (1D) nanoscrolls and polyaniline prepared by the layer-by-layer assembly technique (LbL). Secondary electron imaging and backscattered electron imaging techniques performed using a scanning electron microscope showed that polyaniline is adsorbed on the hexaniobate nanoscrolls, which confirms the combination of the components in the nanoscale domain. UV-VIS-NIR electronic spectra of the LbL hybrid films showed the absorption tail in the NIR region, assigned to delocalized polarons of the polyaniline. Resonance Raman spectra in the 1000-1700 cm(-1) range indicated that hybrid films present a higher relative intensity of polaron bands at 1337 and 1508 cm(-1) than pristine polyaniline in the emeraldine salt form. These results suggest that hexaniobate nanoscrolls induce a secondary doping of polyaniline. The cyclic voltammetry (CV) data for the hybrid film showed a specific capacity of 870 C cm(-3). According to CV results, the synergistic effect on charge storage properties of the hybrid material is attributed to the enhanced electroactivity of the hexaniobate component in the LbL film. Spectroelectrochemical experiments showed that the electrochromic efficiencies at 420 nm are ca. -41 and 24 cm(2) C-1 as the potential changes from 0.8 to -0.9 V and from -0.9 to -1.8 V, respectively, whereas at 800 nm the efficiencies are ca. -55 and 8 cm(2) C-1 for the same potential ranges. The electrochromic efficiencies and multi-colour character of the LbL film of hexaniobate nanoscrolls and polyaniline indicate that this novel hybrid material is an interesting modified electrode for electrochromic devices.

Viscosidade cinemática de pastas cimentícias com incorporadores de ar avaliadas em diferentes temperaturas

A presença de aditivos incorporadores de ar (AIA) em suspensões cimentícias torna esses materiais sensíveis às etapas de processamento e às condições ambientais de preparo das composições. Diversos estudos têm sido reportados em literatura avaliando o efeito de incorporadores de ar nas propriedades de materiais cimentícios, sobretudo no estado endurecido. Porém o efeito da temperatura na incorporação de ar e nas propriedades reológicas dessas composições tem sido menos investigado, sendo este o objetivo do presente trabalho. Para tanto, foram avaliadas as características de pastas cimentícias, compostas por cimentos CPIIF ou CPIIE e dois tipos de AIA, em função da variação da temperatura. O conceito de viscosidade cinemática foi adotado na análise dos resultados para compensar diferenças de inércia das pastas com densidades distintas. Os resultados mostraram que o tipo de cimento, a presença do aditivo e a temperatura influenciaram significativamente na incorporação de ar e nas propriedades reológicas.

Gold ion implantation into alumina using an “inverted ion source” configuration.

We describe an approach to ion implantation in which the plasma and its electronics are held at ground potential and the ion beam is injected into a space held at high negative potential, allowing considerable savings both economically and technologically. We used an “inverted ion implanter” of this kind to carry out implantation of gold into alumina, with Au ion energy 40 keV and dose (3–9) × 1016 cm−2. Resistivity was measured in situ as a function of dose and compared with predictions of a model based on percolation theory, in which electron transport in the composite is explained by conduction through a random resistor network formed by Au nanoparticles. Excellent agreement is found between the experimental results and the theory.

Electron Interactions with Disulfide Bridges

Because of its electronic properties, sulfur plays a major role in a variety of metabolic processes and, more in general, in the chemistry of life. In particular, S-S bridges between cysteines are present in the amino acid backbone of proteins. Protein disulfur radical anions may decay following different paths through competing intra and intermolecular routes, including bond cleavage, disproportionation, protein-protein cross linking, and electron transfer. Indeed, mass spectrometry ECD (electron capture dissociation massspectroscopy) studies have shown that capture of low-energy (<0.2 eV) electrons by multiply protonated proteins is followed by dissociation of S-S bonds holding two peptide chains together. In view of the importance of organic sulfur chemistry, we report on electron interactions with disulphide bridges. To study these interactions we used as prototypes the molecules dimethyl sulfide [(CH3)2S] and dimethyl disulfide [(H3C)S2(CH3)]. We seek to better understand the electron-induced cleavage of the disulfide bond. To explore dissociative processes we performed electron scattering calculations with the Schwinger Multichannel Method with pseudopotentials (SMCPP), recently parallelized with OpenMP directives and optimized with subroutines for linear algebra (BLAS) and LAPACK routines. Elastic cross sections obtained for different S-S bond lengths indicate stabilization of the anion formed by electron attachment to a σ*SS antibonding orbital, such that dissociation would be expected.

Fe valence fluctuations and magnetoelastic coupling in Pb-based multiferroics perovskites

Lead-based multiferroics perovskites with nominal compositions Pb(Fe1/2Nb1/2)O3 and Pb(Fe2/3W1/3)O3 were synthesized following a two-stage method. Magnetic proprieties were investigated and correlated to anelastic proprieties, measured by the conventional pulse-echo method. The discussions are focused in the region around 250 K, where magnetoelectroelastic instabilities have been observed. X-ray absorption nearedge structure (XANES) study further indicates that the edge position varies with temperature revealing a fluctuation on the valence of iron ions with the temperature, which can be related to a variation in anelastic and magnetic proprieties.

PVC orientado-avaliação de processo de orientação e das propriedades mecânicas em função da razão de estiramento

Este artigo avalia o efeito da "orientação molecular" nas propriedades mecânicas do PVC Rígido. Introduz-se o tema associando-o à aplicação do PVC Orientado em sistemas de tubulações, considerando a importância do nível de gelificação na qualidade desses produtos. É descrito e testado um método experimental de orientação mono-axial em um extrudado e materiais com diferentes razões de estiramento são produzidos para avaliação de propriedades mecânicas. Aumentando a razão de estiramento, há ganhos principalmente no limite de resistência à tração, além do módulo elástico sob tração e tenacidade. Por outro lado, a deformação na ruptura é reduzida.