Excited State Absorption of Doped and Undoped Polyanyline

Polyaniline is a conducting polymer with appealing electrical and optical properties, arising from the -conjugation along the polymer backbone. The understanding of its excited state absorption is of prime importance for designing and fabricating optical devices. Here, we report on the study of the excited state absorption of doped and undoped PANI by using femtosecond pulses in the spectral range from 450nm up to 850nm. For undoped PANI, we observed saturation of absorption as well as reverse saturable absorption, depending on the excitation wavelength. For doped PANI, however, only saturable absorption was observed.

A Multitechnique Study of Structure and Dynamics of Polyfluorene Cast Films and the Influence on Their Photoluminescence

This article describes the microstructure and dynamics in the solid state of polyfluorene-based polymers, poly(9,)-dioctylfluorenyl-2,7-diyl) (PFO), a semicrystalline polymer, and poly [(9,9-dioctyl- 2,7-divinylene-fluorenylene)-alt-co-{2-methoxy-5-(2-ethyl-hexyloxy)- 1,4-phenylene vinylene}, a copolymer with mesomorphic phase properties. These Structures were determined by wide-angle X-ray scattering (WAXS) measurements, Assuming a packing model for the copolymer structure, where the planes of the phenyl rings are stacked and separated by an average distance of similar to 4.5 angstrom and laterally spaced by about similar to 16 angstrom, we followed the evolution of these distances as a function of temperature using WAXS and associated the changes observed to the polymer relaxation processes identified by dynamical mechanical thermal analysis. Specific molecular motions were studied by solid-state nuclear magnetic resonance. The onset of the side-chain motion at about 213 K (beta-relaxation) produced a small increase in the lateral spacing and in the stacking distance of the phenyl rings in them aggregated Structures, Besides, at about 383 K (alpha-relaxation) there occurs a significant increase in the amplitude of the torsion motion in the backbone, producing a greater increase in the stacking distance of the phenyl rings. Similar results were observed in the semicrystalline phase of PFO, but in this case the presence of the crystalline structure affects considerably the overall dynamics, which tends to be more hindered. Put together, Our data explain many features of the temperature dependence of the photoluminescence of these two polymers.

The use of colloidal ferrofluid as building blocks for nanostructured layer-by-layer films fabrication

The electrostatic layer-by-layer technique has been exploited as an useful strategy for fabrication of nanostructured thin films, in which specific properties can be controlled at the molecular level. Ferrofluids consist of a colloidal suspension of magnetic grains (with only a few nanometers of diameter) with present interesting physical properties and applications, ranging from telecommunication to drug delivery systems. In this article, we developed a new strategy to manipulate ferrofluids upon their immobilization in nanostructured layered films in conjunction with conventional polyelectrolytes using the layer-by-layer technique. We investigated the morphological, optical, and magnetic properties of the immobilized ferrofluid as a function of number of bilayers presented in the films. Ferrofluid/polyelectrolyte multilayers homogeneously covered the substrates surface, and the magnetic and optical properties of films exhibited a linear dependence on the number of bilayers adsorbed.

Host-guest system of 4-nerolidylcatechol in 2-hydroxypropyl-beta-cyclodextrin: preparation, characterization and molecular modeling

The interaction of 4-nerolidylcatechol (4-NRC), a potent antioxidant agent, and 2-hydroxypropyl-beta-cyclodextrin (HP-beta-CD) was investigated by the solubility method using Fourier transform infrared (FTIR) methods in addition to UV-Vis, (1)H-nuclear magnetic resonance (NMR) spectroscopy and molecular modeling. The inclusion complexes were prepared using grinding, kneading and freeze-drying methods. According to phase solubility studies in water a B(S)-type diagram was found, displaying a stoichiometry complexation of 2:1 (drug:host) and stability constant of 6494 +/- A 837 M(-1). Stoichiometry was established by the UV spectrophotometer using Job`s plot method and, also confirmed by molecular modeling. Data from (1)H-NMR, and FTIR, experiments also provided formation evidence of an inclusion complex between 4-NRC and HP-beta-CD. 4-NRC complexation indeed led to higher drug solubility and stability which could probably be useful to improve its biological properties and make it available to oral administration and topical formulations.

Modelling water adsorption on Au(210) surfaces: II. Monte Carlo simulations

Canonical Monte Carlo simulations for the Au(210)/H(2)O interface, using a force field recently proposed by us, are reported. The results exhibit the main features normally observed in simulations of water molecules in contact with different noble metal surfaces. The calculations also assess the influence of the surface topography on the structural aspects of the adsorbed water and on the distribution of the water molecules in the direction normal to the metal surface plane. The adsorption process is preferential at sites in the first layer of the metal. The analysis of the density profiles and dipole moment distributions points to two predominant orientations. Most of the molecules are adsorbed with the molecular plane parallel to surface, while others adsorb with one of the O-H bonds parallel to the surface and the other bond pointing towards the bulk liquid phase. There is also evidence of hydrogen bond formation between the first and second solvent layers at the interface. (c) 2007 Elsevier B.V. All rights reserved.

Electropolymerization studies of PAni/(poly)luminol over platinum electrodes

This work presents a cyclic voltammetry study of the polyaniline/polyluminol copolymer on platinum electrodes. The results show that under determined conditions it is possible to obtain the copolymer deposited on a metallic surface. The luminol presence clearly affects the oxidation of aniline in the nucleation process and, additionally, changes the cyclic voltammetric characteristics of the obtained material. In this aspect, the copolymer presents hybrid characteristics when compared to the polyaniline and polyluminol separately obtained and seems to present intermediary conductivity.

Agro-Based Biocomposites for Industrial Applications

Leaf fibers are fibers that run lengthwise through the leaves of most monocotyledonous plants such as pineapple, banana, etc. Pineapple (Ananas comosus) and Banana (Musa indica) are emerging fiber having a very large potential to be used for composite materials. Over 150,000 ha of pineapple and over 100,000 ha of banana plantations are available in Brazil for the fruit production and enormous amount of agricultural waste is produced. This residual waste represents one of the single largest sources of cellulose fibers available at almost no cost. The potential consumers for this fiber are pulp and paper, chemical feedstock, textiles and composites for the automotive, furniture and civil construction industry.

Pineapple Leaf Fibers for Composites and Cellulose

Pineapple leaf fiber (PALF) which is rich in cellulose, abundantly available, relatively inexpensive, low density, nonabrasive nature, high filling level possible, low energy consumption, high specific properties, biodegradability and has the potential for polymer reinforcement. The utilization of pineapple leaf fiber (PALF) as reinforcements in thermoplastic and thermosetting resins in micro and nano form for developing low cost and lightweight composites is an emerging field of research in polymer science and technology. In this paper we examines the industrial applicabiliy of PALF, mainly for production of composite materials and special papers, chemical feedstocks (bromelin enzyme) and fabrics.

Influence of Reaction Conditions on Synthesis of PAni/MnO(2) Composites

An investigation of the parameters as aniline: MnO(2) and temperature on synthesis of polyaniline/MnO(2) composites was performed. The composites were chemically prepared in H(2)SO(4) media using different aniline: MnO(2) ratios at 0 degrees C. After the ratio optimization, the syntheses were performed at 20 degrees C. The polyaniline/MnO(2) composites were characterized by scanning electron microscopy (SEM), ultraviolet-visible, near infrared and infrared spectroscopic techniques. Composites obtained with a uniform, homogeneous and thicker coating of polyaniline films under oxide was considered as the best condition for synthesis.

Thermodynamics and Lithium Intercalation in CeO(2)-TiO(2) Thin Film

The kinetics and the thermodynamics of electrochemical intercalation of lithium into CeO(2)-TiO(2) films prepared by the sol-gel process were studied by galvanostatic intermittent titration technique (GITT) as function of the depth of lithium intercalation. The open-circuit-potential versus x in Li(x)(CeO(2)-TiO(2)) curve consists of two straight lines with different slopes, one in the range of 0.03 <= x <= 0.09 and the other of 0.09 < x <= 0.15. The standard Gibbs energy for lithium intercalation Delta G(1)(0) was 6kJ/mol for x = 0.09 in Li(x)(CeO(2)-TiO(2)) at room temperature. The chemical diffusion coefficient value, D(Li+), of lithium intercalation into thin film oxide was 2.14.10(-11) cm(2)/s at x = 0.15, and the value of the component diffusion coefficient D(Li+),(k) was about one order of magnitude lower than the coefficient of chemical diffusion.

Electrochemical Behaviour of the AA2024 Aluminium Alloy Modified with Self-Assembled Monolayers/Polyaniline Double Films

The electrochemical characteristics of the AA2024 aluminium alloy modified with octadecyltrimethoxysilane (ODTMS) + polyaniline (PANi) and propiltrimethoxysilane (PTMS) + (PANi) were studied in the present work. The results show that the different protective coatings shift the values of corrosion and pit potentials to more positive values making the system nobler and indicate that the double film ODTMS + PANi present the best protection against corrosion characteristics, that is probably due to the two contributions: anodic protection associated with the barrier effect.

Defeitos pontuais nos compostos intermetálicos ZrNi e Zr/sub 2/Ni estudados por dinâmica molecular

Empregamos a técnica de Dinâmica Molecular para estudar propriedades de defeitos pontuais nos compostos intermetálicos ZrNi e Zr2Ni. Descrevemos as configurações estáveis de defeitos e mecanismos de migração, assim como as energias envolvidas. Os potenciais interatômicos foram derivados do Embedded Atom Model. No intuito de levar em conta a variação de estequiometria causada pela presença de alguns tipos de defeitos em intermetálicos, apresentamos um método numérico que fornece a energia efetiva de formação de defeitos e aplicamos o método ao ZrNi e Zr2Ni. Os resultados mostraram que vacâncias são mais estáveis na sub—rede do Ni, com energia de formação de 0,83 e-0,61 eV em ZrNi e Zr2Ni, respectivamente. Vacâncias de Zr são instáveis em ambos compostos; elas decaem espontaneamente em pares anti—sítio e vacância de Ni. Configurações e energias de formação de intersticiais também foram calculadas e mostraram comportamentos similares. Em ZrNi, a migração de vacâncias ocorre preferencialmente nas direções [025] e [100], com as respectivas energias de migração 0,67 e 0,73 eV, e é um processo essencialmente bidimensional no plano (001). Em Zr,Ni, a migração de vacâncias é unidimensional, ocorrendo na direção [001], com energia de migração de 0,67 eV. Em ambos compostos a presença de defeitos de anti—sítio de Ni diminui a energia de migração da vacância de Ni em até 3 vezes e facilita a movimentação em três dimensões. Mecanismos de anel não são energeticamente eficientes em comparação com saltos diretos. As configurações estáveis de intersticiais em ambos compostos consistem em um átomo de Ni sobre o plano (001) entre dois vizinhos de Zr fora do plano. Intersticiais de Zr são instáveis e tendem a deslocar um átomo de Ni, ocupando seu sítio. Energias de deslocamento foram estudadas através de simulações de irradiação de ambos compostos. Durante o processo de colisão binária, um potencial universal ZBL foi usado para colisões a curta distância. Para distâncias intermediárias usamos um potencial de união arbitrário. Zr mostrou—se mais difícil de ser arrancado de seu sítio do que Ni. Encontramos valores de energia de deslocamento no intervalo de aproximadamente 29 eV até 546 eV. Alguns resultados experimentais são mostrados e apresentam boa concordância com os cálculos.

Influência de parâmetros moleculares em funções de correlação temporal na dinâmica de solvatação mecânica

No presente trabalho descrevemos nossos resultados relativos à investigação da dinâmica de solvatação mecânica por meio de simulações por dinâmica molecular, respeitando o regime da resposta linear, em sistemas-modelo de argônio líquido com um soluto monoatômico ou diatômico dissolvido. Estudamos sistematicamente a influência dos parâmetros moleculares dos solutos (tamanho, polarizabilidade) e da densidade frente a vários modelos de solvatação. Funções de Correlação Temporal da Energia de Solvatação foram calculadas com relação à correlações de n-corpos (n = 2; 3) distinguindo interações repulsivas e atrativas para ambos os sistemas líquidos. Também obtivemos segundas derivadas temporais dessas funções referindo-se à parcelas translacionais, rotacionais e roto-translacionais na solução do diatômico. Encontramos que funções de correlação temporal coletivas podem ser razoavelmente bem aproximadas por correlações binárias a densidades baixas e, a densidades altas, correlações ternárias tornam-se mais importantes produzindo um descorrelacionamento mais rápido das funções coletivas devido a efeitos de cancelamento parciais. As funções de correlação para interações repulsivas e atrativas exibem comportamentos dinâmicos independentes do modelo de solvatação devido a fatores de escalonamento linear que afetam apenas as amplitudes das dessas funções de correlação temporal. Em geral, os sistemas com grau de liberdade rotacional apresentam tempos de correlação mais curtos para a dinâmica coletiva e tempos de correlação mais longos para as funções binárias e ternárias. Finalmente, esse estudo mostra que os sistemas contendo o diatômico relaxam-se predominantemente por mecanismos translacionais binários em modelos de solvatação envolvendo alterações apenas na polarizabilidade do soluto, e por mecanismos rotacionais atrativos binários em modelos envolvendo alterações no comprimento de ligação.

Natural fibers based composites - Technical and social issues

Brazil is the only country in South America to have an automotive supplier sector based on natural fibers. New opportunities are arising due to an increase demand by the car makers in applying natural fibers in their parts. Several crop fibers have been developed in Brazil. Among them can be listed caroa, piacava, pupunha, mutum and others of regional application. For the automotive industry, which requires large quantities with uniform quality, the alternatives are sisal (170,000 ton/yr), curaua (150 ton/yr in 2003), malva, 200 ton/yr; Brazil is the single largest producer country of sisal, and commercially, the only one in curaua. For South America, the alternatives are fique in Colombia, abaca in equator, flax in Argentina and curaua in Venezuela. It must be understood by the target countries of drugs, is that crop fiber can be an economic alternative to coca in the Andes region, therefore an instrument of land reform and drug reduction plantations. Several companies have a strong program of apply natural fibers based components in their products: Volkswagen do Brazil, DaimlerChrysler, General Motors do Brazil. Among their suppliers can be listed companies such Pematec (curaua), Toro (sisal, coir and jute), Incomer (sisal and jute), Ober (jute, curaua), Indaru (jute and sisal), Antolin (imported kenaf,) Tapetes Sao Carlos (sisal), Poematec (coir) and Art-Gore, with Woodstock'' wood and natural fibers). Figures about production and demand are discussed in the paper.

Host-guest system of 4-nerolidylcatechol in 2-hydroxypropyl-beta-cyclodextrin: preparation, characterization and molecular modeling

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)