O presente trabalho visa o desenvolvimento de um sistema de monitoramento de disjuntor voltado a coletar informações para manutenção preditiva. São analisadas as características das variáveis que são monitoradas através de sensores ligados ao disjuntor, sua aquisição e o tratamento das informações. Um protótipo foi desenvolvido e instalado na subestação de Sumaré 440kV de ETEO (Empresa de Transmissão de Energia do Oeste Paulista). Um assunto importante para a manutenção é a avaliação dos tempos envolvidos na movimentação dos contatos principais do disjuntor principalmente na operação de abertura do curto circuito. Para tal é proposto um sistema não intrusivo que analise a oscilografia das tensões e correntes no disjuntor sincronizado com as correntes no circuito de disparo deste equipamento. A Transformada de Fourier aplicada no sinal de corrente/tensão sem perturbação permite determinar o valor do componente fundamental desse sinal. Com esse valor pode-se gerar uma senóide que superposta com o sinal coletado pelo oscilógrafo permite visualizar a alteração. A Transformada Wavelet é realizada através de filtros decompondo-se o sinal de corrente ou tensão em Análise Multiresolução, em diferentes estágios obtendo-se em cada, uma versão chamada aproximação (baixas freqüências) e uma de detalhes (altas freqüências), sendo assim, os distúrbios podem ser detectados e localizados no tempo em função do seu conteúdo de freqüência. / The present work addresses the development of a circuit breaker monitoring system so as to collect information for predictive maintenance. The characteristics of the variables that are monitored through certain sensors linked to the circuit breaker, its acquisition and the treatment of the information, are analyzed. A prototype was developed and installed at the 440kV Sumaré substation of ETEO (Empresa de Transmissão de Energia do Oeste Paulista) a Brazilian Transmission Company. An important aspect for the maintenance is the evaluation of the times involved in the movement of the circuit breaker main contacts, mainly at the opening operation for example during a short circuit. On this respect, a non-intrusive system that analyzes the oscillography of both voltages and currents in the circuit breaker synchronized with the currents in the tripping circuit of this equipment is proposed. The Fourier Transform applied to the current or voltage signal with no disturbance allows to determine the value of the fundamental component of this signal. With that value, it can be generated a pure sine wave which when overlapped to the signal collected by the oscillograph allows to visualize alterations. The Wavelet Transform is realized through filters and decomposing the current or voltage signal through the Multiresolution Analysis at different levels, in this way, obtaining in each level, a version called approximation (low frequencies) and another with details (high frequencies), thus, the disturbances can be detected and located in the time and as a function of its frequency content.

This work has two interlocking themes. It is primarily concerned with the development of precise, broad band, Fourier transform spectrometric techniques for the determination of the optical constants of solids at millimetre and submillimetre wavelengths. One such technique cannot easily accomodate the wide range of optical constants found in solids, leading to specimens which range from the virtually transparent to the virtually opaque, and it was therefore necessary to develop transmission and reflection techniques. The intercomparison of these techniques, their particular experimental difficulties and susceptibilities to random and systematic error, was performed by using each method to determin'the optical constants of soda lime silica glass over as wide a spectral range as possible. Previous to this work there had been no systematic study of this important material at these wavelengths and,thus, this investigation gave the second theme of this work, the quantitative determination of the optical constants of soda lime silica glass at millimetre and submillimetre wavelengths. The results of this study are presented in four chapters. First, in chapter 5, power transmission Fourier transform spectrometry has been used to investigate the spectral variation of the optical constants of the glass between 3 and 50cm, using an analysis of channel spectra to give the refractive index. This chapter also contains the results of measurements made with a grating instrument between 1000 and k000cm. Secondly, in chapter 6, the results of the first direct determinations of the optical constants by dispersive transmission Fourier transform spectrometry are presented and shown to indicate the presence of a hitherto unknown loss process below 20er that is tentatively associated with a similar process previously observed in fused silica. Thirdly, in chapter 7, dispersive reflection Fourier transform spectrometry has been used to determin the optical constants up to 360em, well into the midinfrared region of opacity of this glass. The results of chapters 6 and 7 provide the first quantitative description of the optical constants of this glass betweem 3 and 360em Finally, in chapter 8, the dispersive reflection measurements are extended to simple binary and ternary silicate glasses, and these results used to identify the contributions to the mid-infrared absorption of the metal ions associated with the various metal oxide additives of the glass. From this it was possible to account for all of the absorption in soda lime silica glass as a superposition of contributions from the near-infrared bands of the SiO1 network of the glass and the four main metal ions.

O objetivo deste estudo foi avaliar os métodos de espectroscopia Raman e espectroscopia de absorção de infravermelho (FTIR) na identificação da degradação do trans-1,4-poliisopreno de cones de guta-percha sem uso, e o comportamento do material após diferentes períodos decorridos de sua fabricação por testes de indentação de nanodureza (IHT). Para a análise, foram selecionadas 27 amostras de cones de guta-percha sem uso, de 5 marcas comerciais vendidas no mercado brasileiro, cedidas por Cirurgiões-dentistas. As amostras foram avaliadas através de espectroscopia Raman, com base no sinal da ligação C=C, indicando a presença de trans-1,4-poliisopreno; FTIR, levando-se em consideração a ligação C=O, indicativa de oxidação do material; IHT, avaliando-se rigidez e módulo de elasticidade. Os dados foram analisados de maneira descritiva. Observam-se, nos espectros de Raman, amostras nas quais os picos relativos à ligação C=C foram identificados, bem como outras em que não foi percebido o referido pico, sem uma relação direta com os tempos decorridos da fabricação dos cones de guta-percha sem uso. Em relação ao FTIR, em todas as amostras analisadas foram observados picos relativos à ligação C=O, indicando haver algum grau de oxidação no material. Os testes de nanodureza, realizados em cones sem uso, mostraram não haver homogeneidade dos valores de dureza e módulo de elasticidade. A análise pelos métodos de espectroscopia Raman e FTIR em cones de guta-percha é dificultada pelos vários componentes presentes no material e a separação do polímero trans-1,4-poliisopreno pode evitar número excessivo de picos e facilitar a interpretação dos espectros. Espectroscopia Raman e FTIR são capazes de identificar a degradação do poliisopreno. A presença, ou não, da ligação C=C, nos espectros de Raman, não teve relação direta com a idade dos cones. Os cones de guta-percha sem uso apresentaram algum grau de degradação, devido à presença da oxigênio no polímero. As análises de nanodureza não foram conclusivas quanto ao comportamento do material relacionado ao envelhecimento. / The aim of the present study was to evaluate the methods Raman spectroscopy and infrared absorption spectroscopy (FTIR) to analyze the degradation of trans-1,4-polyisoprene polymer in gutta-percha points, before use. Mechanical properties were assessed through the instrumented hardness tests (IHT). Twenty-seven samples of gutta-percha cones collected before use, belonging to five different commercial brands sold in Brazil, were obtained from Dental Surgeons. The samples were evaluated by Raman spectroscopy, based on the sign of the C=C bond (representing the trans-1,4-polyisoprene polymer); FTIR, considering the C=O bond (indicating polymer oxidation), and instrumented hardness tests (IHT), to assess both rigidity and elasticity modulus. Descriptive analysis was performed. Raman spectra showed that there were samples of gutta-percha before use where the C=C was identified, an others no. There was no relation between its detection and the time from manufacturing. FTIR showed C=O bond in all samples, indicating that there was some degree of oxidation on the material. Nanoindentation tests showed no homogeneity between hardness and modulus of elasticity. The analysis by Raman and FTIR in gutta-percha points is difficult because there are several components that form the material, and polymer isolation can facilitate the interpretation of the spectra. Both methods were able to evaluate polymers’ degradation. The presence of C=C bond, in Raman spectra, have no relation to their age. The gutta-percha points showed some degree of degradation, due to the presence of oxygen in the polymer. Nanoindentation tests did not provid conclusive results regarding the material’s aging behavior.

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1980. / MICROFICHE COPY AVALABLE IN ARCHIVES AND SCIENCE. / Vita. / Includes bibliographical references. / by Edmond Joseph Murphy, Jr. / Ph.D.

No presente trabalho procurou-se desenvolver um sistema computacional para a automação de um Espectrofotômetro de Varredura Refrativa. Este sistema é baseado em um computador hospedeiro da linha IBM-PC, que pode ser de qualquer modelo, desde que possua barramento ISA de 16 bits. O sistema se divide em dois módulos - aquisição e processamento. O modulo de aquisição e capaz de atingir taxas de aquisição de ate 200 KHz, com resolução de 12 bits. É independente de controle do hospedeiro pois possui lógica de controle e sistema de armazenamento próprio. O módulo de processamento envolve o uso de um processador vetorial de sinais digitais ZORAN ZR34161 dedicado a efetuar eficientemente a Transformada Rápida de Fourier (FFT). Também opera independentemente do computador hospedeiro. Este módulo é capaz de efetuar a FFT em um vetor real de 4096 pontos em 19,64 ms / This work was intended to develop a computational system to control a fast Fourier spectrophotometer. This system is based in an IBM-PC type host computer, with ISA bus 16 bits wide. The system has two modules - acquisition and processing. The acquisition module works at 200 KHz sample rate, with 12 bits of resolution, and also works without host control, due to its own memory system and control logic. The processing module uses a ZORAN ZR34161 vector signal processor, dedicated to do the Fast Fourier Transform (FFT) in the most efficient way. No management of host is required, and it can compute a FFT of a 4096 points real vector in 19,64 ms

Microplastics are particles that are < 5 mm in size and come from a wide range of sources. The global distribution in terrestrial and aquatic environments indicates they are likely to cause harm to living organisms. They are used in a variety of personal care products and kitchen scourers. To advance further studies, different approaches have been developed in recent years. In this research, a comparison of methods and analytical techniques were applied to characterise microplastics in two toothpastes and two facial scrubs. The analysis of microplastics was determined using light microscopy, laser diffraction, Fourier-transform infrared spectroscopy. This research reports for the first time, the application of Imaging flow cytometry to characterise microplastics, and was explored to characterise smaller sized particles in each product. The methods developed where validated by characterising particles abraded from kitchen scourers. Two market leading and three chain store brands of kitchen scourers were utilised for the characterisation of microplastics. The application of the different techniques indicated differences in the size, number and morphological characteristics of the particles analysed. The different approaches developed for particle extraction, and the analytical techniques had an apparent influence on the results produced. Currently, there are no universally accepted laboratory protocol and analytical techniques to characterise microplastics. However, this research can serve as a reference point to promote more studies on laboratory methods and analytical techniques to characterise microplastics, with the hope of understanding better these complex particles.

Analysis in chemistry has always been hindered by the presence of impurities in samples or mixtures that are difficult to separate. Nuclear magnetic resonance has proven to be one of the most powerful analysis techniques to enable the study of mixtures by pseudoseparation using molecular parameters such as the diffusion coefficient through the application of the DOSY technique. In order to extend the application of this technique, an improvement has been proposed know as matrix-assisted DOSY (MAD-DOSY) or chromatographic NMR. This technique is based on the addition of a sample modifier that will interact differently with the molecules, varying and separating their diffusion coefficients, or even changing slightly the chemical shifts. To extend the application of chromatographic NMR, size exclusion stationary phases have been combined with DOSY experiments. These studies have been applied to analyze mixtures modifying the diffusion coefficient in terms of size exclusion behavior and to increase the understanding of the interactions between the analytes and the stationary phase. These studies have been published in Magnetic Resonance in Chemistry. One of the main issues when using DOSY is spectral overlapping, which is the main cause of poor resolution. In addition to this problem, a consequence of using stationary phases is the appearance of increased broadening of the signals due to differences in magnetic susceptibility. Thus, to achieve the aim, the study of diffusion properties have been performed under HR-MAS conditions which can help to remove susceptibility effect, but has complicating effects on the DOSY experiment. A method to obtain reliable diffusion measurements under HR-MAS have been developed using a D2O sample. Different conditions have been investigated including different pulse sequences, variation of parameters of the pulse sequence (diffusion delay or gradient strength), spinning rate and synchronization of the pulse sequence with the sample spinning. Also improvements in sample preparation as the addition of spacers in different locations of the sample rotor, to both reduce radial field variations and the sample volume, in order to obtain the most accurate diffusion values. This method have been published in Magnetic Resonance in Chemistry. The method have been applied to a wide range of molecules to extend the understanding of diffusion under HR-MAS conditions. In order to extend the range of application of NMR chromatography, a complementary study of the analysis of a mixture of different enantiomers including ethylenediamine cobalt complexes, aminoacids and some other organic small molecules adding to the sample a chiral stationary phase as a sample modifier is included in the final chapter of this thesis.

In this thesis we study the short-time Fourier transform. The short-time Fourier transform of a function f(x) is obtained by restricting our function to a short time segment and take the Fourier transform of this restriction. This method gives information locally of f in both time and frequency simultaneously.To get a smooth frequency localization one wants to use a smooth window, whichmeans that the windows will overlap. The continuous short-time Fourier transform is not appropriate for practical purpose, therefore we want a discrete representation of f. Using Gabor theory, we can write a function f as a linear combination of time- and frequency shifts of a fixed window function g with integer parameters a; b &gt; 0. We show that if the window function g has compact support, then g generates a Gabor frame G(g; a; b). We also show that for such a g there exists a dual frame such that both G(g; a; b) and its dual frame has compact support and decay fast in the Fourier domain. Based on [2], we show that B-splines generates a pair of Gabor frames.

Os catalisadores eletroquímicos binários de PtSn/C, PdSn/C e PtPd/C foram sintetizados em diferentes proporções pelo método da redução via borohidreto, posteriormente estes foram caracterizados por microscopia eletrônica de transmissão, difração de raios X, espectroscopia no infravermelho por transformada de Fourier (PtSn/C e PdSn/C) e energia dispersiva de raios X. As atividades eletroquímicas dos diferentes materiais preparados foram avaliadas por intermédio de voltametria cíclica, cronoamperometria e curvas de polarização em célula a combustível alimentada diretamente por etileno glicol em eletrólito alcalino. As curvas de densidade de potência indicaram que os catalisadores eletroquímicos contendo Sn e Pd são mais ativos para a reação de oxidação do etileno glicol, especialmente a composição 70%:30% - relação molar entre os metais suportados em carbono - dos catalisadores PtSn/C, PdSn/C e PtPd/C todos superando as medidas de potência do Pt/C. Este resultado indica que a adição de Sn e Pd favorece a oxidação do etileno glicol em meio alcalino. O melhor desempenho observado para os catalisadores eletroquímicos PtSn/C, PdSn/C e PtPd/C (70%:30%) poderia estar associado à sua maior seletividade quanto a formação de oxalato, ou seja , a formação deste produto resulta em um maior número de elétrons, por consequência em maiores valores de corrente. / Binary electrochemical catalysts PtSn/C, PdSn/C and PtPd/C were synthesized in different proportions by the method of reduction via borohydride. These were characterized by transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy (PtSn/C and PdSn/C) and energy dispersive X-ray. The electrochemical activities of the different materials prepared were evaluated by cyclic voltammetry, chronoamperometry and polarization curves for fuel cell powered directly by ethylene glycol in an alkaline electrolyte. Power density curves indicated that the electrochemical catalysts Sn-containing or Pd-containing are more active for ethylene glycol oxidation reaction, particularly the (70%:30%) composition of PtSn/C, PdSn/C and PtPd/C, all of them exceeding power measurements of Pt/C. These results indicate that the addition of Sn and Pd promotes the oxidation of ethylene glycol in an alkaline medium and this improved performance may be associated with a higher selectivity for the formation of oxalate that results in a larger number of electrons, consequently enhancing the current values.

O presente trabalho visa o desenvolvimento de um sistema de monitoramento de disjuntor voltado a coletar informações para manutenção preditiva. São analisadas as características das variáveis que são monitoradas através de sensores ligados ao disjuntor, sua aquisição e o tratamento das informações. Um protótipo foi desenvolvido e instalado na subestação de Sumaré 440kV de ETEO (Empresa de Transmissão de Energia do Oeste Paulista). Um assunto importante para a manutenção é a avaliação dos tempos envolvidos na movimentação dos contatos principais do disjuntor principalmente na operação de abertura do curto circuito. Para tal é proposto um sistema não intrusivo que analise a oscilografia das tensões e correntes no disjuntor sincronizado com as correntes no circuito de disparo deste equipamento. A Transformada de Fourier aplicada no sinal de corrente/tensão sem perturbação permite determinar o valor do componente fundamental desse sinal. Com esse valor pode-se gerar uma senóide que superposta com o sinal coletado pelo oscilógrafo permite visualizar a alteração. A Transformada Wavelet é realizada através de filtros decompondo-se o sinal de corrente ou tensão em Análise Multiresolução, em diferentes estágios obtendo-se em cada, uma versão chamada aproximação (baixas freqüências) e uma de detalhes (altas freqüências), sendo assim, os distúrbios podem ser detectados e localizados no tempo em função do seu conteúdo de freqüência. / The present work addresses the development of a circuit breaker monitoring system so as to collect information for predictive maintenance. The characteristics of the variables that are monitored through certain sensors linked to the circuit breaker, its acquisition and the treatment of the information, are analyzed. A prototype was developed and installed at the 440kV Sumaré substation of ETEO (Empresa de Transmissão de Energia do Oeste Paulista) a Brazilian Transmission Company. An important aspect for the maintenance is the evaluation of the times involved in the movement of the circuit breaker main contacts, mainly at the opening operation for example during a short circuit. On this respect, a non-intrusive system that analyzes the oscillography of both voltages and currents in the circuit breaker synchronized with the currents in the tripping circuit of this equipment is proposed. The Fourier Transform applied to the current or voltage signal with no disturbance allows to determine the value of the fundamental component of this signal. With that value, it can be generated a pure sine wave which when overlapped to the signal collected by the oscillograph allows to visualize alterations. The Wavelet Transform is realized through filters and decomposing the current or voltage signal through the Multiresolution Analysis at different levels, in this way, obtaining in each level, a version called approximation (low frequencies) and another with details (high frequencies), thus, the disturbances can be detected and located in the time and as a function of its frequency content.