Photoluminescence study of new lanthanide complexes with benzeneseleninic acids

New lanthanide complexes with benzeneseleninic (ABSe) and 4-chloro-benzeneseleninic (ABSeCl) acids have been synthesized and characterized by elemental analysis, infrared and UV-visible spectroscopies. The emission spectra of the trivalent europium complexes presented the typical electronic (5)D(0) -> (7)F(j) transitions of the ion (J = 0-4). The ground-state geometries of the europium complexes have been calculated by using the Sparkle/AM1 model. From these results, the 4f-4f intensity parameters and energies of the ligand singlet and triplet excited states have been obtained. The lower emission quantum yield for the [Eu(ABSe)(3)(H(2)O)(2)](H(2)O)(2) compound, as compared to the [Eu(Al(3)SeCl)(3)(H(2)O)(2)] one, can be associated to the higher numbers of water molecules, in the first and second coordination spheres, that contribute to the luminescence quenching. The [Eu(Al(3)Se)(3)(H(2)O)(2)](H(2)O)(2) complex presents an intermediate state whose energy difference with respect to the first excited singlet state is resonant with three phonons from the water molecules, favouring a multiphonon relaxation process from the singlet state followed by a fast internal conversion process; this effect is less pronounced in the complex with the ABSeCl ligand. The luminescence decay curves of the gadolinium complexes indicate that the level responsible for the intramolecular energy transfer process has a triplet character for both compounds. The nephelauxetic effect in these compounds was investigated under the light of a recently proposed covalency scale based on the concept of overlap polarizability of the chemical bond. (C) 2009 Elsevier B.V. All rights reserved.

Excited-state dynamics of polyfluorene derivatives in solution

The excited-state dynamics of two polyfluorene copolymers, one fully conjugated containing phenylene vinylene units alternated with 9,9`-dihexylfluorenyl groups and the other segmented by -(CH2)(8)- spacer, were studied in dilute solution of different solvents using a picosecond single-photon timing technique. The excited-state dynamics of the segmented copolymer follows the Forster resonant energy-transfer model which describes intrachain energy-transfer kinetics among random oriented chromophores. Energy transfer is confirmed by analysis of fluorescence anisotropy relaxation with the measurement of a short decay component of about 60 ps. The fluorescence decay surface of the fully conjugated copolymer is biexponential with decay times of about 470 and 900 ps, ascribed to deactivation of chain moieties containing trans and cis isomers already in a photostationary condition. Thus, energy transfer is very fast due to the conjugated nature and rigid-rod-like structure of this copolymer chain.

Influência das espécies ativas na absorção de intersticiais durante a carbonitretação a plasma do TI

Physical-chemical properties of Ti are sensible to the presence of interstitial elements. In the case of thermochemical treatments plasma assisted, the influence of different active species is not still understood. In order to contribute for such knowledge, this work purposes a study of the role played by the active species atmosphere into the Ar N2 CH4 carbonitriding plasma. It was carried out a plasma diagnostic by OES (Optical Emission Spectroscopy) in the z Ar y N2 x CH4 plasma mixture, in which z, y and x indexes represent gas flow variable from 0 to 4 sccm (cm3/min). The diagnostic presents abrupt variations of emission intensities associated to the species in determined conditions. Therefore, they were selected in order to carry out the chemical treatment and then to investigate their influences. Commercial pure Ti disks were submitted to plasma carbonitriding process using pre-established conditions from the OES measurements while some parameters such as pressure and temperature were maintained constant. The concentration profiles of interstitial elements (C and N atoms) were determined by Resonant Nuclear Reaction Analysis (NRA) resulting in a depth profile plots. The reactions used were 15N(ρ,αγ)12C and 12C(α,α)12C. GIXRD (Grazing Incidence X-Ray Diffraction) analysis was used in order to identify the presence of phases on the surface. Micro-Raman spectroscopy was used in order to qualitatively study the carbon into the TiCxN1 structure. It has been verified which the density species effectively influences more the diffusion of particles into the Ti lattice and characteristics of the layer formed than the gas concentration. High intensity of N2 + (391,4 nm) and CH (387,1 nm) species promotes more diffusion of C and N. It was observed that Hα (656,3 nm) species acts like a catalyzer allowing a deeper diffusion of nitrogen and carbon into the titanium lattice.

Conversor CC/CA de alta freqüência baseado em inversores ressonantes com comutação seqüencial para excitação de uma tocha indutiva a plasma térmico

This work describes the study, the analysis, the project methodology and the constructive details of a high frequency DC/AC resonant series converter using sequential commutation techniques for the excitation of an inductive coupled thermal plasma torch. The aim of this thesis is to show the new modulation technique potentialities and to present a technological option for the high-frequency electronic power converters development. The resonant converter operates at 50 kW output power under a 400 kHz frequency and it is constituted by inverter cells using ultra-fast IGBT devices. In order to minimize the turn-off losses, the inverter cells operates in a ZVS mode referred by a modified PLL loop that maintains this condition stable, despite the load variations. The sequential pulse gating command strategy used it allows to operate the IGBT devices on its maximum power limits using the derating and destressing current scheme, as well as it propitiates a frequency multiplication of the inverters set. The output converter is connected to a series resonant circuit constituted by the applicator ICTP torch, a compensation capacitor and an impedance matching RF transformer. At the final, are presented the experimental results and the many tests achieved in laboratory as form to validate the proposed new technique

Desenvolvimento de antenas de microfita com Patch em anel utilizando materiais ferrimagnéticos e metamateriais

In general, the materials used as substrates in the project of microstrip antennas are: isotropic, anisotropic dielectrics and ferrimagnetic materials (magnetic anisotropy). The use of ferrimagnetic materials as substrates in microstrip patch antennas has been concentrated on the analysis of antennas with circular and rectangular patches. However, a new class of materials, called metamaterials, has been currently the focus of a great deal of interest. These materials exhibit bianisotropic characteristics, with permittivity and permeability tensors. The main objective of this work is to develop a theoretical and numerical analysis for the radiation characteristics of annular ring microstrip antennas, using ferrites and metamaterials as substrates. The full wave analysis is performed in the Hankel transform domain through the application of the Hertz vector potentials. Considering the definition of the Hertz potentials and imposing the boundary conditions, the dyadic Green s function components are obtained relating the surface current density components at the plane of the patch to the electric field tangential components. Then, Galerkin s method is used to obtain a system of matrix equations, whose solution gives the antenna resonant frequency. From this modeling, it is possible to obtain numerical results for the resonant frequency, radiation pattern, return loss, and antenna bandwidth as a function of the annular ring physical parameters, for different configurations and substrates. The theoretical analysis was developed for annular ring microstrip antennas on a double ferrimagnetic/isotropic dielectric substrate or metamaterial/isotropic dielectric substrate. Also, the analysis for annular ring microstrip antennas on a single ferrimagnetic or metamaterial layer and for suspended antennas can be performed as particular cases

Análise neurocomputacional de Antenas de microfita multibanda para sistemas de comunicação sem fio

This work presents a study of implementation procedures for multiband microstrip patch antennas characterization, using on wireless communication systems. An artificial neural network multilayer perceptron is used to locate the bands of operational frequencies of the antenna for different geometrics configurations. The antenna is projected, simulated and tested in laboratory. The results obtained are compared in order to validate the performance of archetypes that resulted in a good one agreement in metric terms. The neurocomputationals procedures developed can be extended to other electromagnetic structures of wireless communications systems

Antenas de microfita com patch quase-fractal para aplicações em Redes WPAN/WLAN

The microstrip antennas are in constant evidence in current researches due to several advantages that it presents. Fractal geometry coupled with good performance and convenience of the planar structures are an excellent combination for design and analysis of structures with ever smaller features and multi-resonant and broadband. This geometry has been applied in such patch microstrip antennas to reduce its size and highlight its multi-band behavior. Compared with the conventional microstrip antennas, the quasifractal patch antennas have lower frequencies of resonance, enabling the manufacture of more compact antennas. The aim of this work is the design of quasi-fractal patch antennas through the use of Koch and Minkowski fractal curves applied to radiating and nonradiating antenna s edges of conventional rectangular patch fed by microstrip inset-fed line, initially designed for the frequency of 2.45 GHz. The inset-fed technique is investigated for the impedance matching of fractal antennas, which are fed through lines of microstrip. The efficiency of this technique is investigated experimentally and compared with simulations carried out by commercial software Ansoft Designer used for precise analysis of the electromagnetic behavior of antennas by the method of moments and the neural model proposed. In this dissertation a study of literature on theory of microstrip antennas is done, the same study is performed on the fractal geometry, giving more emphasis to its various forms, techniques for generation of fractals and its applicability. This work also presents a study on artificial neural networks, showing the types/architecture of networks used and their characteristics as well as the training algorithms that were used for their implementation. The equations of settings of the parameters for networks used in this study were derived from the gradient method. It will also be carried out research with emphasis on miniaturization of the proposed new structures, showing how an antenna designed with contours fractals is capable of a miniaturized antenna conventional rectangular patch. The study also consists of a modeling through artificial neural networks of the various parameters of the electromagnetic near-fractal antennas. The presented results demonstrate the excellent capacity of modeling techniques for neural microstrip antennas and all algorithms used in this work in achieving the proposed models were implemented in commercial software simulation of Matlab 7. In order to validate the results, several prototypes of antennas were built, measured on a vector network analyzer and simulated in software for comparison

Análise e projeto de superfícies seletivas de frequência com elementos pré-fractais para aplicações em comunicações indoor

In this thesis, a frequency selective surface (FSS) consists of a two-dimensional periodic structure mounted on a dielectric substrate, which is capable of selecting signals in one or more frequency bands of interest. In search of better performance, more compact dimensions, low cost manufacturing, among other characteristics, these periodic structures have been continually optimized over time. Due to its spectral characteristics, which are similar to band-stop or band-pass filters, the FSSs have been studied and used in several applications for more than four decades. The design of an FSS with a periodic structure composed by pre-fractal elements facilitates the tuning of these spatial filters and the adjustment of its electromagnetic parameters, enabling a compact design which generally has a stable frequency response and superior performance relative to its euclidean counterpart. The unique properties of geometric fractals have shown to be useful, mainly in the production of antennas and frequency selective surfaces, enabling innovative solutions and commercial applications in microwave range. In recent applications, the FSSs modify the indoor propagation environments (emerging concept called wireless building ). In this context, the use of pre-fractal elements has also shown promising results, allowing a more effective filtering of more than one frequency band with a single-layer structure. This thesis approaches the design of FSSs using pre-fractal elements based on Vicsek, Peano and teragons geometries, which act as band-stop spatial filters. The transmission properties of the periodic surfaces are analyzed to design compact and efficient devices with stable frequency responses, applicable to microwave frequency range and suitable for use in indoor communications. The results are discussed in terms of the electromagnetic effect resulting from the variation of parameters such as: fractal iteration number (or fractal level), scale factor, fractal dimension and periodicity of FSS, according the pre-fractal element applied on the surface. The analysis of the fractal dimension s influence on the resonant properties of a FSS is a new contribution in relation to researches about microwave devices that use fractal geometry. Due to its own characteristics and the geometric shape of the Peano pre-fractal elements, the reconfiguration possibility of these structures is also investigated and discussed. This thesis also approaches, the construction of efficient selective filters with new configurations of teragons pre-fractal patches, proposed to control the WLAN coverage in indoor environments by rejecting the signals in the bands of 2.4~2.5 GHz (IEEE 802.11 b) and 5.0~6.0 GHz (IEEE 802.11a). The FSSs are initially analyzed through simulations performed by commercial software s: Ansoft DesignerTM and HFSSTM. The fractal design methodology is validated by experimental characterization of the built prototypes, using alternatively, different measurement setups, with commercial horn antennas and microstrip monopoles fabricated for low cost measurements

Desenvolvimento de um ressoador retangular de fenda com múltiplas camadas de substrato e com utilização de material PBG para sistema de comunicação sem fio

In the globalized world modern telecommunications have assumed key role within the company, causing a large increase in demand for the wireless technology of communication, which has been happening in recent years have greatly increased the number of applications using this technology. Due to this demand, new materials are developed to enable new control mechanisms and propagation of electromagnetic waves. The research to develop new technologies for wireless communication presents a multidisciplinary study that covers from the new geometries for passive antennas, active up to the development of materials for devices that improve the performance at the frequency range of operation. Recently, planar antennas have attracted interest due to their characteristics and advantages when compared with other types of antennas. In the area of mobile communications the need for antennas of this type has become increasingly used, due to intensive development, which needs to operate in multifrequency antennas and broadband. The microstrip antennas have narrow bandwidth due to the dielectric losses generated by irradiation. Another limitation is the degradation of the radiation pattern due to the generation of surface waves in the substrate. Some techniques have been developed to minimize this limitation of bandwidth, such as the study of type materials PBG - Photonic Band Gap, to form the dielectric material. This work has as main objective the development project of a slot resonator with multiple layers and use the type PBG substrate, which carried out the optimization from the numerical analysis and then designed the device initially proposed for the band electromagnetic spectrum between 3-9 GHz, which basically includes the band S to X. Was used as the dielectric material RT/Duroid 5870 and RT/Duroid 6010.LM where both are laminated ceramic-filled PTFE dielectric constants 2.33 and 10.2, respectively. Through an experimental investigation was conducted an analysis of the simulated versus measured by observing the behavior of the radiation characteristics from the height variation of the dielectric multilayer substrates. We also used the LTT method resonators structures rectangular slot with multiple layers of material photonic PBG in order to obtain the resonance frequency and the entire theory involving the electromagnetic parameters of the structure under consideration. xviii The analysis developed in this work was performed using the method LTT - Transverse Transmission Line, in the field of Fourier transform that uses a component propagating in the y direction (transverse to the real direction of propagation z), thus treating the general equations of the fields electric and magnetic and function. The PBG theory is applied to obtain the relative permittivity of the polarizations for the sep photonic composite substrates material. The results are obtained with the commercial software Ansoft HFSS, used for accurate analysis of the electromagnetic behavior of the planar device under study through the Finite Element Method (FEM). Numerical computational results are presented in graphical form in two and three dimensions, playing in the parameters of return loss, frequency of radiation and radiation diagram, radiation efficiency and surface current for the device under study, and have as substrates, photonic materials and had been simulated in an appropriate computational tool. With respect to the planar device design study are presented in the simulated and measured results that show good agreement with measurements made. These results are mainly in the identification of resonance modes and determining the characteristics of the designed device, such as resonant frequency, return loss and radiation pattern

Análise de superfícies seletivas de freqüência para aplicações em ondas milimétricas

This work consists in the development of a theoretical and numerical analysis for frequency selective surfaces (FSS) structures with conducting patch elements, such as rectangular patches, thin dipoles and cross dipoles, on anisotropic dielectric substrates. The analysis is developed for millimeter wave band applications. The analytical formulation is developed in the spectral domain, by using a rigorous technique known as equivalent transmission line method, or immitance approach. The numerical analysis is completed through the use of the Galerkin's technique in the Fourier transform domain, using entire-domain basis functions. In the last decades, several sophisticated analytical techniques have been developed for FSS structure applications. Within these applications, it can be emphasized the use of FSS structures on reflecting antennas and bandpass radomes. In the analysis, the scattered fields of the FSS geometry are related to the surface induced currents on the conducting patches. After the formulation of the scattering problem, the numerical solution is obtained by using the moment method. The choice of the basis functions plays a very important role in the numerical efficiency of the numerical method, once they should provide a very good approximation to the real current distributions on the FSS analyzed structure. Thereafter, the dyadic Green's function components are obtained in order to evaluate the basis functions unknown coefficients. To accomplish that, the Galerkin's numerical technique is used. Completing the formulation, the incident fields are determined through the incident potential, and as a consequence the FSS transmission and reflection characteristics are determined, as function of the resonant frequency and structural parameters. The main objective of this work was to analyze FSS structures with conducting patch elements, such as thin dipoles, cross dipoles and rectangular patches, on anisotropic dielectric substrates, for high frequency applications. Therefore, numerical results for the FSS structure main characteristics were obtained in the millimeter wave bando Some of these FSS characteristics are the resonant

Otimização de superfícies seletivas de frequência com elementos pré-fractais utilizando rede neural MLP e algoritmos de busca populacional

This thesis describes design methodologies for frequency selective surfaces (FSSs) composed of periodic arrays of pre-fractals metallic patches on single-layer dielectrics (FR4, RT/duroid). Shapes presented by Sierpinski island and T fractal geometries are exploited to the simple design of efficient band-stop spatial filters with applications in the range of microwaves. Initial results are discussed in terms of the electromagnetic effect resulting from the variation of parameters such as, fractal iteration number (or fractal level), fractal iteration factor, and periodicity of FSS, depending on the used pre-fractal element (Sierpinski island or T fractal). The transmission properties of these proposed periodic arrays are investigated through simulations performed by Ansoft DesignerTM and Ansoft HFSSTM commercial softwares that run full-wave methods. To validate the employed methodology, FSS prototypes are selected for fabrication and measurement. The obtained results point to interesting features for FSS spatial filters: compactness, with high values of frequency compression factor; as well as stable frequency responses at oblique incidence of plane waves. This thesis also approaches, as it main focus, the application of an alternative electromagnetic (EM) optimization technique for analysis and synthesis of FSSs with fractal motifs. In application examples of this technique, Vicsek and Sierpinski pre-fractal elements are used in the optimal design of FSS structures. Based on computational intelligence tools, the proposed technique overcomes the high computational cost associated to the full-wave parametric analyzes. To this end, fast and accurate multilayer perceptron (MLP) neural network models are developed using different parameters as design input variables. These neural network models aim to calculate the cost function in the iterations of population-based search algorithms. Continuous genetic algorithm (GA), particle swarm optimization (PSO), and bees algorithm (BA) are used for FSSs optimization with specific resonant frequency and bandwidth. The performance of these algorithms is compared in terms of computational cost and numerical convergence. Consistent results can be verified by the excellent agreement obtained between simulations and measurements related to FSS prototypes built with a given fractal iteration

Análise de antenas de microfita em rampa com múltiplas camadas dielétricas

The present work deals with the ana1ysis of microstrip patch antennas printed on tapered dielectric substrates. We investigate the influence ofthe substrate height variations on the properties of configurations such as microstrip patch antennas, microstrip patch antennas with overlay and suspendeô microstrip patch antennas. The dielectric substrates can be isotropic or anisotropic ones. This accurate analysis is based on the full-wave formulation. It is carried out initially for the determination of the impedance matrix, through the use of the spectral¬domain immitance approach. We use a model based on a segmentation of the considered line into uniform microstrip line subsections. Normalized phase constants and characteristic impedances are obtained by means of the Galerkin numerical technique. Then, the cascaded combination of the uniform microstrip subsections are analyzed through an interactive procedure. Numerical results are presented for the input reflection coefficient, voltage standing wave ratio, resonant frequency, and radiation pattems ofthe E_plane and H-plane diagrams. It is found that the variations in the substrate height profile produce a great influence on the bandwidth of microstrip antennas. This procedure gives bandwidth improvements without altering considerably the resonant frequency. Furthermore, the tapered microstrip antenna can be used as a lightweight altemative for bandwidth control and to eXtend the use of microstiip antenna technology to a wider variety of applications. Finally, suggestions for the continuity of this work are presented

Uma fonte chaveada de 50kW com correção de fator de potência para alimentação de uma tocha de plasma Indutiva utilizando técnicas de controle digital

This work deals with the development of an experimental study on a power supply of high frequency that provides the toch plasmica to be implemented in PLASPETRO project, which consists of two static converters developed by using Insulated Gate Bipolar Transistor (IGBT). The drivers used to control these keys are triggered by Digital Signal Processor (DSP) through optical fibers to reduce problems with electromagnetic interference (EMI). The first stage consists of a pre-regulator in the form of an AC to DC converter with three-phase boost power factor correction which is the main theme of this work, while the second is the source of high frequency itself. A series-resonant inverter consists of four (4) cell inverters operating in a frequency around 115 kHz each one in soft switching mode, alternating itself to supply the load (plasma torch) an alternating current with a frequency of 450 kHz. The first stage has the function of providing the series-resonant inverter a DC voltage, with the value controlled from the power supply provided by the electrical system of the utility, and correct the power factor of the system as a whole. This level of DC bus voltage at the output of the first stage will be used to control the power transferred by the inverter to the load, and it may vary from 550 VDC to a maximum of 800 VDC. To control the voltage level of DC bus driver used a proportional integral (PI) controller and to achieve the unity power factor it was used two other proportional integral currents controllers. Computational simulations were performed to assist in sizing and forecasting performance. All the control and communications needed to stage supervisory were implemented on a DSP

Arranjos Log-Periódicos Compactos em Microfita com Elementos Fractais de Koch

This work aims to present how the application of fractal geometry to the elements of a log-periodic array can become a good alternative when one wants to reduce the size of the array. Two types of log-periodic arrays were proposed: one with fed by microstrip line and other fed by electromagnetic coupling. To the elements of these arrays were applied fractal Koch contours, at two levels. In order to validate the results obtained some prototypes were built, which were measured on a vector network analyzer and simulated in a software, for comparison. The results presented reductions of 60% in the total area of the arrays, for both types. By analyzing the graphs of return loss, it was observed that the application of fractal contours made different resonant frequencies appear in the arrays. Furthermore, a good agreement was observed between simulated and measured results. The array with feeding by electromagnetic coupling presented, after application of fractal contours, radiation pattern with more smooth forms than the array with feeding by microstrip line

Ressoador retangular defenda com quatro camadas fotônicas

Recently, planar antennas have attracted interest due to its characteristics as well as the advantages they offer compared to other types of antennas. In the area of mobile communications the need for such antennas has become increasingly intense due to development, which requires antennas that operate in multifrequency and broadband. The microstrip antennas have narrow bandwidth due to losses in the dielectric caused by irradiation. Another limitation is the radiation pattern degradation due to generation of surface waves in the substrate. Some techniques are being developed to minimize this bandwidth limitation, as is the case in the study of type materials PBG - Photonic Band Gap, to compose the dielectric material. The analysis developed in this work were performed with use of the method LTT - Transverse Transmission Line, in the field of Fourier transform that uses a component propagating in the y direction (transerve real direction of propagation z), thus treating the general equations of the fields electric and magnetic fields as a functions of y E and Hy . This work has as main objective the method LTT structures resonator line slot with four layers of material photonic PBG, for obtaining the complex resonant frequency and efficiency of this structure. PBG theory is applied to obtain the relative permittivity for the substrate biases sep compounds photonic material. Numerical-computational results in graph form in two dimensions for all the analysis are presented for the proposed structures that have photonic materials, as substrates