Dispersion of gamma-Alumina Nano-Sized Spherical Particles in a Calamitic Liquid Crystal. Study and Optimization of the Confinement Effects

We report an experimental study on confined systems formed by butyloxybenzylidene octylaniline liquid crystal (4O.8) + gamma-alumina nanoparticles. The effects of the confinement in the thermal and dielectric properties of the liquid crystal under different densities of nanoparticles is analyzed by means of high resolution Modulated Differential Scanning Calorimetry (MDSC) and broadband dielectric spectroscopy. First, a drastic depression of the N-I and SmA-N transition temperatures is observed with confinement, the more concentration of nanoparticles the deeper this depression is, driving the nematic range closer to the room temperature. An interesting experimental law is found for both transition temperatures. Second, the change in shape of the heat capacity peaks is quantified by means of the full width half maximum (FWHM). Third, the confinement does not noticeably affect the molecular dynamics. Finally, the combination of nanoparticles and the external applied electric field tends to favor the alignment of the molecules in metallic cells. All these results indicate that the confinement of liquid crystals by means of gamma-alumina nanoparticles could be optimum for liquid crystal-based electrooptic devices.

Micropartículas de quitosana estruturadas com aerosil®: estabilidade, adsorção, encapsulação e liberação de substâncias ativas

Biodegradable microspheres used as controlled release systems are important in pharmaceutics. Chitosan biopolymer represents an attractive biomaterial alternative because of its physicochemical and biological characteristics. Chitosan microspheres are expected to become promising carrier systems for drug and vaccine delivery, especially for non-invasive ways oral, mucosal and transdermal routes. Controlling the swelling rate and swelling capacity of the hydrogel and improving the fragile nature of microspheres under acidic conditions are the key challenges that need to be overcomed in order to enable the exploration of the full pharmaceutical potential use of these microparticles. Many studies have focused on the modification of chitosan microsphere structures with cross-linkers, various polymers blends and new organic-inorganic hybrid systems in order to obtain improved properties. In this work, microspheres made of chitosan and nanosized hydrophobic silica (Aerosil R972) were produced by a method consisting of two steps. First, a preparation of a macroscopically homogeneous chitosan-hydrophobic silica dispersion was prepared followed by spray drying. FTIR spectroscopy, X-ray powder diffraction, differential scanning calorimetry, thermal gravimetric analysis, scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (TEM) were used to characterize the microspheres. Also, the were conducted acid stability, moisture sorption capacity, release properties and biological assays. The chitosan-hydrophobic silica composite microspheres showed improved thermal degradation, lower water affinity, better acid stability and ability to retard rifampicin and propranolol hydrochloride (drug models) release under simulated physiological conditions. In vitro biocompatibility studies indicated low cytotoxicity and low capacity to activate cell production of the pro-inflammatory mediator nitric oxide. The results show here encourage further studies on the use of the new chitosan-hydrophobic silica composite microspheres as drug carrier systems via oral or nasal routes.

High specific surface area LaFeCo perovskites-Synthesis by nanocasting and catalytic behavior in the reduction of NO with CO

LaFe(1-x)CO(x)O(3) perovskites were conventionally or nanocasting synthesized. The nanocasting involved the preparation of a micro-mesoporous carbon mould using a Silica Aerosil 200 and a carbon source. Then, perovskites were carbon cast at 800 degrees C. The solids were characterized by XRD, N(2) sorption, FTIR, TGA/DTG, SEM and TEM. N(2) sorption evidenced that the nanocast perovskites did not show significant intraparticle porosity in despite of their enhanced (30-50 m(2)/g) specific surface area (SSA). Nevertheless, TEM images, XRD and Rietveld refinement data showed that the solids are constituted at least by 97 wt% of perovskite phase and by agglomerates smaller than 100 nm constituted by crystallites of about 6 nm. TGA/DTG results demonstrated carbon oxidation during the perovskite formation, thus eliminating the template effect and facilitating the occurrence of sintering, which limited the SSA increase. The nanocast perovskites were more active in the reduction of NO than the uncast ones, behavior that was attributed to the increase in their SSA that allows the exposure of a higher number of accessible active sites. However, the perovskite composition and the presence of impurities can reduce the effect of the improvement of the textural properties. The nanocast perovskites also showed high thermal and catalytic stability, corroborating their potential as catalysts for the studied reaction. (C) 2009 Elsevier B.V. All rights reserved.

Estudo da blenda PBAT/PLA com cargas.

Neste trabalho compósitos foram obtidos a partir da blenda comercial 100% biodegradável Ecovio® C2224 da BASF, uma blenda formada por 55% em massa de um copoliéster biodegradável, o Ecoflex® (poli[(adipato de butileno)-co-(tereftalato de butileno)]) e 45% em massa de PLA poli(ácido láctico). Como carga, utilizaram-se dois tipos de argilas comerciais do grupo das esmectitas, ambas predominantemente montmorilonitas: Cloisite Sódica® e Cloisite 30B®. Também foi utilizado como carga a sílica coloidal comercial Aerosil 200®, com área superficial de 200 m2/g e diâmetro médio de partícula 12nm. Os compósitos estudados, ambos contendo 5% e 10% em massa de cargas, foram preparados em uma extrusora de rosca dupla, acoplada a um reômetro de torque. O estudo foi dividido em três etapas: 1ª) etapa: Obtenção e caracterização dos compósitos de Ecovio®/ argila e Ecovio® / sílica; 2ª) etapa: Avaliação da fotodegradação do Ecovio® puro e dos compósitos obtidos; 3ª) etapa: Avaliação da biodegradabilidade do Ecovio® puro e dos compósitos após exposição em câmara de UV. As propriedades mecânicas dos compósitos antes e depois de serem submetidos à exposição em câmara de UV foram avaliadas por ensaios de resistência à tração e resistência ao impacto Izod. Os resultados obtidos na 1ª etapa deste trabalho indicaram aumento nos valores de módulo de elasticidade de todos os compósitos, em relação à blenda pura. Destacam-se as composições com 5% e 10% em massa de sílica coloidal, que apresentaram aumentos de até 115% nos valores de módulo de elasticidade, sem perdas significativas em resistência à tração, alongamento e resistência ao impacto, quando comparadas à fase matriz. Na 2ª etapa, a partir de 20 dias de exposição, todas as composições (blendas e compósitos) apresentam redução nas propriedades mecânicas em função do aumento do tempo de exposição à radiação UV. Na 3ª etapa, independente do tipo ou teor de carga presente na blenda, todas as composições apresentaram índices de biodegradabilidade, depois de 120 dias, de 40 a 60%, devido à prévia exposição à radiação UV.

Structural study of composites of aerosil fumed silica and tetraethoxysilane-derived sonogels

Composites of aerosil fumed silica and tetraethoxysilane-derived sonogel were prepared by changing the aerosil content between 0 and 30wt% with respect to the silica content in the original tetraethoxysilane (TEOS). The structural characteristics were studied by density and Vickers microhardness measurements and analyzed by means of small-angle X-ray scattering (SAXS). The structure of the composite aerosil/TEOS-derived sonogel can be described as inclusions of the aerosil particles embedded in the matrix of the TEOS-derived sonogel, forming an aerosil/matrix interfacial surface inside the composite. The weakening of the bonding of aerosil/matrix interface, as suggested by the reported decrease in microhardness, increases the fracture toughness of the composite. The additive effect of the aerosil particles on the structure of the sonogel accounts for the increase of the bulk density and reduction of the specific surface of the composite. Some internal structure associated with the microclusters making up the sonogels is apparent from systematic deviations from Porod's law found in the system with small aerosil contents. (c) 2005 Elsevier B.V. All rights reserved.

Desenvolvimento de cerâmicas de mulita a partir de alumina, ácido silícico e aerosil

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The strength and failure of silica optical fibers

The mechanical strength and failure behavior of conventional and microstructured silica optical fibers was investigated using a tensile test and fracture mechanics and numerical analyses. The effect of polymer coating on failure behavior was also studied. The results indicate that all these fibers fail in a brittle manner and failure normally starts from fiber surfaces. The failure loads observed in coated fibers are higher than those in bare fibers. The introduction of air holes reduces fiber strength and their geometrical arrangements have a remarkable effect on stress distribution in the longitudinal direction. These results are potentially useful for the design, fabrication and evaluation of optical fibers for a wide range of applications.