The electronic delocalization in para-substituted beta-nitrostyrenes probed by resonance Raman spectroscopy and quantum-chemical calculations

The electronic (UV-vis) and resonance Raman (RR) spectra of a series of para-substituted trans-beta-nitrostyrenes were investigated to determine the influence of the electron donating properties of the substituent (X = H, NO2, COOH, Cl, OCH3, OH, N(CH3)(2), and O-) on the extent of the charge transfer to the electron-withdrawing NO2 group directly linked to the ethylenic (C=C) unit. The Raman spectra and quantum chemical calculations show clearly the correlation of the electron donating power of the X group with the wavenumbers of the nu(s)(NO2) and nu (C=C)(sty) normal modes. In conditions of resonance with the lowest excited electronic state, one observes for X = OH and N(CH3)2 that the symmetric stretching of the NO2. nu(s)(NO2), is the most substantially enhanced mode, whereas for X = O-, the chromophore is extended over the whole molecule, with substantial enhancement of several carbon backbone modes. Copyright (c) 2008 John Wiley & Sons, Ltd.

Automotive engineering metal foam structures: fabrication, characterisation, testing and simulation

The contrubution of this thesis is to generate fundamental research and design information on the impact and bending behaviours of metal foams and foam-filled tubes

Particular solution for anomalous diffusion equation with source term

In literature the phenomenon of diffusion has been widely studied, however for nonextensive systems which are governed by a nonlinear stochastic dynamic, there are a few soluble models. The purpose of this study is to present the solution of the nonlinear Fokker-Planck equation for a model of potential with barrier considering a term of absorption. Systems of this nature can be observed in various chemical or biological processes and their solution enriches the studies of existing nonextensive systems.

Microemulsões biocompatíveis de anfotericina B para administração oral: estudo estrutural, liberação in vitro e farmacocinética pré-clínica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Modelagem e simulação de ciclos a gás com resfriamento de ar na entrada

The optimization of energy generation systems has become a key issue for technological and social development, mainly in developing countries, where the electricity consumption rises sharply. Gas turbine cycle is an electricity generating system, which studies have demonstrated that inlet air cooling increases net power and thermal efficiency. Thus, this study intends to quantify these parameters for environments with different ambient temperature and relative humidity. Two types of air cooling were used: evaporative and absorption systems. The configuration parameters only with the gas turbine cycle were compared to those whose configuration allowed cooling. First, it was analyzed only evaporative cooling. Next, the absorption system was used for analysis. The last configuration mixed these two methods, dividing equally its flow. The results showed that thermal efficiency and net power increase in any case of cooling, with absorption system more advantageous in terms of generated energy, where an increase between 1 and 2 MW was observed, depending on the ambient conditions . When the two methods were working together at low relative humidity, it showed a thermal efficiency increase compared to absorption system, up to 2.4%. Evaporative cooling was less effective, but it is a good and cheap possibility to increase the cycle parameters at high temperature and low relative humidity

Modelagem e simulação de ciclos a gás com resfriamento de ar na entrada

The optimization of energy generation systems has become a key issue for technological and social development, mainly in developing countries, where the electricity consumption rises sharply. Gas turbine cycle is an electricity generating system, which studies have demonstrated that inlet air cooling increases net power and thermal efficiency. Thus, this study intends to quantify these parameters for environments with different ambient temperature and relative humidity. Two types of air cooling were used: evaporative and absorption systems. The configuration parameters only with the gas turbine cycle were compared to those whose configuration allowed cooling. First, it was analyzed only evaporative cooling. Next, the absorption system was used for analysis. The last configuration mixed these two methods, dividing equally its flow. The results showed that thermal efficiency and net power increase in any case of cooling, with absorption system more advantageous in terms of generated energy, where an increase between 1 and 2 MW was observed, depending on the ambient conditions . When the two methods were working together at low relative humidity, it showed a thermal efficiency increase compared to absorption system, up to 2.4%. Evaporative cooling was less effective, but it is a good and cheap possibility to increase the cycle parameters at high temperature and low relative humidity

Análisis del acoplamiento vibro-acústico en resonadores de membrana

El presente Trabajo Fin de Máster pretende llevar a cabo el análisis del comportamiento vibratorio de resonadores de membrana, consistentes en un panel delgado y ligero montado a cierta distancia de un elemento constructivo rígido y pesado. Este tipo de sistemas resonantes son empleados habitualmente como absorbentes de media-baja frecuencia en aplicaciones de acondicionamiento acústico de salas. El análisis hará especial hincapié en la influencia del acoplamiento mecánico-acústico entre la placa vibrante (estructura) y el colchón de aire (fluido) encerrado entre la misma y la pared rígida. En primer lugar, realizaremos el análisis modal experimental del resonador objeto de ensayo a partir de las mediciones de su respuesta vibratoria, con el fin de caracterizar su comportamiento en base a sus primeros modos propios acoplados de flexión. El análisis de las señales vibratorias en el dominio de la frecuencia para la identificación de dicho modos se realizará en el entorno de programación MATLAB, haciendo uso de una herramienta propia que implementa los métodos de cálculo y los algoritmos necesarios para tal fin. Asimismo, simularemos el comportamiento del resonador mediante el método de elementos finitos (FEM), utilizando las aplicaciones ANSYS y SYSNOISE, considerando diferentes condiciones frontera en el modelo generado. Los resultados aquí obtenidos serán de utilidad para complementar aquellos obtenidos de forma experimental a la hora de extraer conclusiones prácticas del análisis realizado. SUMMARY. This Master's Thesis intends to carry out the analysis of the vibratory behaviour of resonance absorbers, consisting of a thin and lightweight panel mounted at a distance from a rigid wall. Such systems are commonly used as sound absorption systems for mid-low frequency in room acoustics applications. The analysis will emphasize the influence of mechanical-acoustic coupling between the vibrating plate (structure) and the air cushion (acoustic element) enclosed behind it. First of all, we are performing the experimental modal analysis of the resonance absorber under test from the vibrational response measurements, in order to characterize its behaviour based on its first bending coupled-modes. The analysis of vibration signals in the frequency domain for the identification of such modes will be made in MATLAB programming environment, using a proprietary tool that implements the calculation methods and algorithms needed for this purpose. Furthermore, we are simulating the behaviour of the resonance absorber applying the Finite Element Method (FEM) – using ANSYS and SYSNOISE applications - considering different boundary conditions in the model created. The results from the simulation will be useful to complement those obtained experimentally when drawing practical conclusions from this analysis.

Some examples of modeling in chemical engineering: thermal treatment of polymers, phase equilibrium calculations and process design

Presentation submitted to PSE Seminar, Chemical Engineering Department, Center for Advanced Process Design-making (CAPD), Carnegie Mellon University, Pittsburgh (USA), October 2012.

Intergalactic H II regions discovered in SINGG

A number of very small isolated H II regions have been discovered at projected distances up to 30 kpc from their nearest galaxy. These H II regions appear as tiny emission-line objects in narrowband images obtained by the NOAO Survey for Ionization in Neutral Gas Galaxies (SINGG). We present spectroscopic confirmation of four isolated H II regions in two systems; both systems have tidal H I features. The results are consistent with stars forming in interactive debris as a result of cloud-cloud collisions. The Halpha luminosities of the isolated H II regions are equivalent to the ionizing flux of only a few O stars each. They are most likely ionized by stars formed in situ and represent atypical star formation in the low-density environment of the outer parts of galaxies. A small but finite intergalactic star formation rate will enrich and ionize the surrounding medium. In one system, NGC 1533, we calculate a star formation rate of 1.5 x 10(-3) M-. yr(-1), resulting in a metal enrichment of similar to 1 x 10(-3) solar for the continuous formation of stars. Such systems may have been more common in the past and a similar enrichment level is measured for the metallicity floor'' in damped Lyalpha absorption systems.

Long-term flow rates and biomat zone hydrology in soil columns receiving septic tank effluent

Soil absorption systems (SAS) are used commonly to treat and disperse septic tank effluent (STE). SAS can hydraulically fail as a result of the low permeable biomat zone that develops on the infiltrative surface. The objectives of this experiment were to compare the hydraulic properties of biomats grown in soils of different textures, to investigate the long-term acceptance rates (LTAR) from prolonged application of STE, and to assess if soils were of major importance in determining LTAR. The STE was applied to repacked sand, Oxisol and Vertisol soil columns over a period of 16 months, at equivalent hydraulic loading rates of 50, 35 and 8 L/m(2)/d, respectively Infiltration rates, soil matric potentials, and biomat hydraulic properties were measured either directly from the soil columns or calculated using established soil physics theory. Biomats 1 to 2 cm thick developed in all soils columns with hydraulic resistances of 27 to 39 d. These biomats reduced a 4 order of magnitude variation in saturated hydraulic conductivity (K.) between the soils to a one order of magnitude variation in LTAR. A relationship between biomat resistance and organic loading rate was observed in all soils. Saturated hydraulic conductivity influenced the rate and extent of biomat development. However, once the biomat was established, the LTAR was governed by the resistance of the biomat and the sub-biomat soil unsaturated flow regime induced by the biomat. Results show that whilst initial soil K. is likely to be important in the establishment of the biomat zone in a trench, LTAR is determined by the biomat resistance and the unsaturated soil hydraulic conductivity, not the K, of a soil. The results call into question the commonly used approach of basing the LTAR, and ultimately trench length in SAS, on the initial K, of soils. (c) 2006 Elsevier Ltd. All rights reserved.

Emergence and Fate of Siloxanes in Waste Streams: Release Mechanisms, Partitioning and Persistence in Three Environmental Compartments

Siloxanes are widely used in personal care and industrial products due to their low surface tension, thermal stability, antimicrobial and hydrophobic properties, among other characteristics. Volatile methyl siloxanes (VMS) have been detected both in landfill gas and biogas from anaerobic digesters at wastewater treatment plants. As a result, they are released to gas phase during waste decomposition and wastewater treatment. During transformation processes of digester or landfill gas to energy, siloxanes are converted to silicon oxides, leaving abrasive deposits on engine components. These deposits cause increased maintenance costs and in some cases complete engine overhauls become necessary. The objectives of this study were to compare the VMS types and levels present in biogas generated in the anaerobic digesters and landfills and evaluate the energetics of siloxane transformations under anaerobic conditions. Siloxane emissions, resulting from disposal of silicone-based materials, are expected to increase by 29% within the next 10 years. Estimated concentrations and the risk factors of exposure to siloxanes were evaluated based on the initial concentrations, partitioning characteristics and persistence. It was determined that D4 has the highest risk factor associated to bioaccumulation in liquid and solid phase, whereas D5 was highest in gas phase. Additionally, as siloxanes are combusted, the particle size range causes them to be potentially hazardous to human health. When inhaled, they may affix onto the alveoli of the lungs and may lead to development of silicosis. Siloxane-based COD-loading was evaluated and determined to be an insignificant factor concerning COD limits in wastewater. Removal of siloxane compounds is recommended prior to land application of biosolids or combustion of biogas. A comparison of estimated costs was made between maintenance practices for removal of siloxane deposits and installation/operation of fixed-bed carbon absorption systems. In the majority of cases, the installation of fixed-bed adsorption systems would not be a feasible option for the sole purpose of siloxane removal. However they may be utilized to remove additional compounds simultaneously.

Emergence and fate of siloxanes in waste streams: Release mechanisms, partitioning and persistence in three environmental compartments

Siloxanes are widely used in personal care and industrial products due to their low surface tension, thermal stability, antimicrobial and hydrophobic properties, among other characteristics. Volatile methyl siloxanes (VMS) have been detected both in landfill gas and biogas from anaerobic digesters at wastewater treatment plants. As a result, they are released to gas phase during waste decomposition and wastewater treatment. During transformation processes of digester or landfill gas to energy, siloxanes are converted to silicon oxides, leaving abrasive deposits on engine components. These deposits cause increased maintenance costs and in some cases complete engine overhauls become necessary. ^ The objectives of this study were to compare the VMS types and levels present in biogas generated in the anaerobic digesters and landfills and evaluate the energetics of siloxane transformations under anaerobic conditions. Siloxane emissions, resulting from disposal of silicone-based materials, are expected to increase by 29% within the next 10 years. Estimated concentrations and the risk factors of exposure to siloxanes were evaluated based on the initial concentrations, partitioning characteristics and persistence. It was determined that D4 has the highest risk factor associated to bioaccumulation in liquid and solid phase, whereas D5 was highest in gas phase. Additionally, as siloxanes are combusted, the particle size range causes them to be potentially hazardous to human health. When inhaled, they may affix onto the alveoli of the lungs and may lead to development of silicosis. Siloxane-based COD-loading was evaluated and determined to be an insignificant factor concerning COD limits in wastewater. ^ Removal of siloxane compounds is recommended prior to land application of biosolids or combustion of biogas. A comparison of estimated costs was made between maintenance practices for removal of siloxane deposits and installation/operation of fixed-bed carbon absorption systems. In the majority of cases, the installation of fixed-bed adsorption systems would not be a feasible option for the sole purpose of siloxane removal. However they may be utilized to remove additional compounds simultaneously.^

Quantum Flows as Markovian Limit of Emission, Absorption and Scattering Interactions

Gough, John, (2004) 'Quantum Flows as Markovian Limit of Emission, Absorption and Scattering Interactions', Communications in Mathematical Physics 254 pp.498-512 RAE2008

LIII absorption edge studies of mixed valent cerium intermetallics and related systems

LIII absorption edge measurements clearly delineate 3+ and 4+ states of Ce. Absorption edges of 3+ compounds show a single peak, while those of 4+ compounds show two peaks, both appearing at higher energies than the characteristic peaks of 3+ compounds. In systems where there is interconfigurational fluctuation, features due to both 3+ and 4+ states are distinctly seen.

Steric effects on the ultraviolet absorption of 1,2-enedioic and related systems

1,2-Enedioic systems, being sterically perturbed from planarity do not show the effect of the extended conjugation expected of a (formal) trienic entity. In the absence of a model which approximates to a uniplanar situation, the strategy of replacing an ester group in the enedioates by a cyano (for which less stringent steric demand may be presumed) and noting the correction concomitant to this replacement was adopted to arrive at a notional figure for the position of maximal absorption in the planar enedioates. From this the conclusion, subject to substantiation by molecular mechanical or quantum chemical calculations, was drawn that even the E-isomeric and comparatively less substituted enedioates are highly sterically perturbed. An alternative to an earlier explanation of the bathochromic shift of absorption maxima encountered in the 5-cyclic ene-ester and ene-nitrile, relative to the 6-cyclic analogues (observed also with the enedioates and cyanovinyl ester systems), seen later to have been based on unwarranted premises, has been advanced. A comment on the absorption characteristics of enedioic anhydrides has been appended.