Um importante diferencial competitivo das empresas distribuidoras de energia elétrica é a gestão da utilização dos seus ativos elétricos. Dentre eles destaca-se o transformador de potência em função de sua importância estratégica no fornecimento de energia aos grandes centros de carga. Para minimizar os impactos operacionais e sociais associados às interrupções constantemente monitoradas para que haja controle efetivo e garantia de funcionamento adequado e otimizado. O monitoramento das suas principais características é um ponto crítico que deve ser constantemente aprimorado, pela indiscutível importância destes ativos elétricos na continuidade do fornecimento de energia elétrica. Este trabalho apresenta proposta para avaliação em tempo real de falhas em transformadores de potência, para que sejam monitorados remotamente pela distribuidora, através do seu respectivo centro de operação do sistema elétrico, propiciando assertividade e rápida tomada de decisão gerencial em ocorrências de falhas internas, reduzindo os custos associados à interrupção do fornecimento de energia elétrica, diminuindo significativamente os tempos de restabelecimento do fornecimento e consequentemente minimizando impactos nos principais Indicadores de qualidade operacional da distribuidora. / An important competitive edge of electric power distribution companies is their electric assets utilization management. Among them stands outs the power transformers because of its strategic importance in the energy supply to high demand areas. To minimize operational and social impacts associated to the electric energy supply interruptions these equipments must to have their main characteristics constantly monitored to have effective control and optimizer functioning warranty. The main characteristics monitoring is a critical point which must be constantly improved, for the unquestionable importance of these electric assets in the electric energy supply continuity. This work shows a proposal to the real time power transformer failure, to remote monitoring by the utilities thru its respective electric system operation center, enabling assertively and fast management decision making in internal failure occurrences, reducing costs associated with electric energy supply interruption, decreasing the supply reestablishing times and consequently minimizing the impacts on the main distribution operational quality indicators.

Nous avons contribué à l’amélioration du modèle global de 12C2H2. Ce modèle, exploitant la notion de polyade, a pris en compte l’ensemble des données spectrales de vibration-rotation de la littérature concernant des niveaux de vibration jusqu’à 8900 cm-1. Au terme de notre travail, les 18415 raies publiées dans la littérature sont reproduites par le modèle endéans 3 fois leur incertitude expérimentale qui est typiquement de l’ordre voire meilleure que 0,001 cm-1. L’introduction des interactions de type Coriolis, réalisée pour la première fois pour l’acétylène dans une perspective globale aux côtés des interactions de type vibrationnel, s’est révélée déterminante dans la qualité des résultats. La totalité des énergies de vibration-rotation de la molécule a été prédite jusqu’à des énergies de l’ordre du visible et pour des valeurs du nombre quantique de rotation allant jusqu’à 120. Nous avons exploité ces résultats pour calculer de manière exhaustive les intensités spectrales dans les régions importantes pour la détection de 12C2H2 dans les atmosphères stellaires et planétaires, impliquant un calcul des fonctions de partition jusqu’à 2000 K avec une précision inégalée dans la littérature. D’autres paramètres thermodynamiques, énergie de Helmholtz, entropie, enthalpie et capacité calorifique à pression constante ont été calculées dans la foulée, tenant compte des deux isomères de spin de la molécule. <p>Au cours de ce travail, une banque de donnée a été mise sur pied, rassemblant les positions de toutes les raies de vibration-rotation connues de 12C2H2 et impliquant des niveaux de vibration jusqu’à 8900 cm-1. Nous avons alimenté cette banque de données, base du modèle global, en nous focalisant sur l’analyse de trois régions spectrales à partir de nouveaux spectres acquis via des collaborations internationales.<p>La première région considérée est celle de l’infrarouge lointain, les spectres étant enregistrés par le Dr A. Predoi-Cross utilisant le rayonnement synchrotron de la « Canadian Light Source ». Les niveaux de pliage à basse énergie sont impliqués, entre 0 et 3000 cm-1. Nous avons étudié en particulier la bande de différence v5-v4 située vers 117 cm-1 et les bandes chaudes associées. Un ensemble de 731 nouvelles raies ont été attribuées sur ce spectre. De nouvelles données ont été obtenues sur 12C13CH2 à cette occasion. <p>La seconde région qui nous a occupé est celle de la première excitation –CH, vers 3300 cm-1. Des spectres d’émission à très haute température (~1455 K) ont été enregistrés par le groupe du Prof. R. Georges à l’université de Rennes. 3811 nouvelles raies ont été attribuées sur ces spectres, les bandes chaudes observées et analysées impliquant jusqu’à 4 quanta d’excitation des modes de pliage et atteignant des niveaux de vibration jusqu’à 6000 cm-1. <p>La troisième région analysée est celle de la seconde excitation –CH, vers 6700 cm-1, sur base de spectres à très haute résolution enregistrés par le groupe du Dr. A. Campargue à l’université de Grenoble. L’analyse de ces spectres nous a permis d’attribuer 1825 nouvelles raies et, via les bandes chaudes, d’accéder aux niveaux de vibration excités jusqu’à 8900 cm-1. <p>L’ensemble de ces nouvelles raies a été ajustée simultanément avec les données de la littérature utilisant 396 paramètres effectifs dont la pertinence a été examinée. La déviation standard sans dimension est de 1.07.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Notre travail concerne l’étude par spectroscopie à haute résolution de molécules polyatomiques en phase gazeuse fortement excitées vibrationnellement. L’excitation de molécules dans leurs hauts niveaux de vibration est typiquement produite par absorption de lumière infrarouge proche, voire visible, d’où la dénomination de « vibrations colorées » ou « overtones ». L’excitation de degrés de liberté de vibration à des énergies aussi inhabituelles place la molécule dans un régime tellement anharmonique que de nouvelles approches théoriques deviennent nécessaires pour en modéliser le comportement. L’observation spectrale des ces transitions requiert une technique expérimentale ultra-sensible pour compenser les faibles intensités des raies d’absorption. Dans ce contexte, nous avons mis au point un dispositif ICLAS qui a pour objectif de surmultiplier le parcours de la lumière dans la cellule d’absorption en insérant celle-ci dans la cavité résonante d’un laser saphir-titane. Le chemin d’absorption ainsi obtenu est équivalent à plusieurs dizaines de kilomètres en fonction de la durée des impulsions lasers.<p>Nous avons ensuite couplé le dispositif ICLAS avec un spectromètre à transformée de Fourier en synchronisant l’acquisition des données avec les impulsions. L’avantage de ce couplage réside dans l’obtention d’une technique à la fois très sensible grâce à l’ICLAS mais aussi possédant une haute résolution et une large couverture spectrale grâce au spectromètre. La réalisation de ce dispositif est décrite dans la première partie de ce travail.<p>Nous avons ensuite appliqué ce dispositif instrumental à l'étude des molécules C2HD et 13C12CH2. L’analyse des spectres enregistrés est détaillée dans la seconde partie de ce travail. Celle-ci inclut également une introduction à la description théorique des niveaux d’énergie de vibration-rotation adaptée au cas de la molécule d’acétylène. L’analyse est axée principalement sur la structure rotationnelle et l’identification vibrationnelle des nouvelles bandes observées grâce aux performances du nouveau spectromètre. Les premières étapes vers la construction d’un modèle rovibrationnel global pour les deux molécules étudiées sont également décrites. / Doctorat en sciences, Spécialisation physique / info:eu-repo/semantics/nonPublished

Plasma pretreatments are environmentally benign and energy efficient processes for modifying the surface chemistry of materials. In an effort to improve the strength of the titanium alloy/FM-5 polyimide adhesive joint for aerospace applications, oxygen plasma pretreatments and novel thin plasma polymerized (PP) films were investigated as adhesion promoters. Plasma treatments were carried out using custom-built, low pressure, radio frequency, inductively coupled plasma reactors. Ti-6Al-4V coupons were plasma treated and used to prepare miniature single lap shear (SLS) joints. The effects of plasma pretreatments on surface chemistry were studied using x-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), Fourier transform infrared analysis (FTIR), and contact angle measurements. Relationships between composition, mechanical properties, and adhesion of PP films on Ti-6Al-4V and silicon wafers were investigated. The nanomechanical properties (modulus, hardness and adhesion) were studied using atomic force microscopy (AFM) nanoindentation and nanoscratch testing. A design of experiments (DOE) three factorial model was used to optimize the parameters for oxygen plasma treatments. Oxygen plasma pretreatments enhanced joint strength by cleaning the titanium surface and creating an extended oxide layer. Nanoindentation of oxygen plasma treated substrates showed no change in the surface mechanical properties due to the oxygen plasma treatment. This suggested that the improved SLS strength of the oxygen plasma pretreated substrates was due to the cleaning of the substrate and the removal of carbonaceous contaminants, rather than any changes in the morphology of the oxide layer. PP acetylene films were predominantly carbon, with oxygen as the other main constituent (incorporated mostly as C-O and C=O). For all SLS specimens tested, the adhesion between PP acetylene and FM-5 adhesive was adequate. However, the strength of SLS joints was limited by the adhesion of the PP acetylene to the Ti-6Al-4V substrate. The effects of a large number of plasma parameters, such as substrate pretreatment, carrier gas, input power, flow rate and film thickness were investigated. All samples failed at the PP film/Ti-6Al-4V interface or within the PP acetylene film, and thicker PP films yielded lower SLS strengths. PP films deposited at lower power exhibited higher hardness and reduced modulus than films deposited at higher power. Overall, thinner films exhibited higher hardness and reduced Young's modulus than thicker films. PP films of higher hardness yielded higher critical loads at debond (thickness normalized) during the nanoscratch test. Thin films were developed via the vapor plasma polymerization of titanium(IV) isobutoxide (TiiB). XPS results suggested that titanium was incorporated into the film as TiO2 clusters dispersed in an organic matrix. No evidence for Ti-C was obtained from the XPS spectra. PP films of TiiB were much more compliant than PP acetylene films. This behavior was attributed to decreased fragmentation and lower crosslinking that occurred during PP TiiB film deposition. These PP films did not exhibit sol-gel-like qualities, and because of the way titanium was incorporated into the films, a more appropriate name for these films might be "titanium dioxide-doped plasma polymerized films." / Ph. D.

Diode lasers are a convenient and economical source of near-infrared radiation, which may usefully be applied to a host of different sensitive detection methods; this thesis presents novel extensions of these methods, making use of the favourable characteristics of this type of light source. The first part of this thesis details the development of an optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) apparatus, including the development of the optical system, the sample handling, and the electronics for feedback phase control. A preliminary demonstration of the system is reported, presenting the detection of atmospheric water absorptions close to 1596 nm. Optimisation and application of the OF-CEAS spectrometer are then demonstrated, after which the spectrometer is applied to the sensitive detection of carbon dioxide absorptions suitable as a diagnostic aid in identifying Heliobacter pylori infection. A time-normalised α-min value of 5.8 × 10⁻⁹ cm⁻¹s^1/2 was measured for these spectra. Further optimisation of the system leads to an ultimate detection sensitivity of 1.42 × 10⁻⁹ cm⁻¹s^1/2, measured on absorption transitions in acetylene close to 1532 nm. In order further to characterise the performance of the OF-CEAS system, analogous experiments are presented using the OF-CEAS setup and a standard diode-laser cavity-enhanced absorption spectroscopy (CEAS) apparatus. Detection is carried out on the P(6) line of the ν₁ + ν₃ vibrational band of the mixed isotopologue of acetylene, ¹²-C¹³-CH₂. Direct comparison is made between the sensitivities of the two methods, and in light of this the suitability of each technique for detection in different environments is considered. The well-characterised and consistent frequency scale which is inherent to the OF-CEAS technique is then applied to a line shape analysis for the presented absorption spectra. Pressure-broadening coefficients are determined for selected absorptions in the ν₁ + ν₃ band of acetylene. In spite of the low resolution associated with this technique, this accurate frequency scaling allows observation of subtle line shape effects such as Dicke collisional narrowing using the data presented in Chapter 3 for the R(60) line in the 3ν₁ + ν₃ vibrational band of CO₂. These effects are quantified through use of a Galatry fit to each absorption spectrum. The statistical significance associated with the use of such a model, and the physical meaning of the results, are examined and discussed. An alternative strategy for increasing the sensitivity of a diode-laser-based gas monitoring technique lies in moving detection to the mid-infrared region, where the absorption cross-sections are generally larger. With this motivation, difference frequency generation is presented, to produce radiation close to 3.5 µm which is then applied to a series of different enhanced spectroscopy techniques. The optimal sensitivity, of 32 ppb NO2 at 45 Torr total sample pressure, was achieved using wavelength modulation spectroscopy. The different techniques are compared and possible improvements to them are put forward. Finally, proof-of-principle work is presented seeking to combine the enhanced circulating power associated with the optical-feedback-locked techniques and non-linear optical techniques to move detection to a more favourable spectral region. Light close to 429 nm is generated by second harmonic generation in a crystal of potassium niobate, with resonance-enhancement afforded by a feedback V-cavity of the sort employed in OF-CEAS. The potential of such a system for diode-laser-based generation of blue and ultraviolet light is demonstrated and discussed, along with improvements that might be implemented to increase the efficiency of the system.

A series of glasshouse and laboratory experiments was carried out to enable comparison of two woody perennial legumes, gorse and broom, with other legumes, nodulated non-legumes and other biological nitrogen fixing systems. Both species had distinct juvenile phases in which broom closely resembled herbaceous species in appearance, but adult plants of both species bore little resemblance to each other or to other legume species. Nodule development was similar to that of other legumes, but mature nodules exhibited structural adaptations to longevity - meristematic activity, a well developed vascular system and numerous cytoplasmic granules in cortical cells. Acetylene reduction and ¹⁵N₂ fixation continued for much longer following excision than has been observed in other legumes. In all experiments, broom nodules exhibited higher rates of acetylene reduction and nitrogen fixation than did gorse nodules. The first detectable product of nitrogen fixation in excised nodules - ammonia - was rapidly incorporated into amide and ∝ amino groups and another unidentified fraction. The principle free amino acid in nodules and sap was asparagine. Its preponderance increased as plants aged. Whole nodulated plants and excised nodules of both species exhibited a relatively low temperature optimum for growth and nitrogen fixation (22°C). They were very sensitive to elevated temperatures. Results indicated that gorse and broom have relatively low light requirements. When aeration was sufficient, combined nitrogen had little effect on growth of nodulated plants. Nodulation in both species was reduced by increasing amounts of combined nitrogen. High levels (100 mg/1) of nitrate and ammonia caused considerable inhibition of nitrogen function. Both species showed large responses to phosphate, but were able to grow and fix nitrogen when supplied with low amounts of phosphate. Boron deficiency reduced nitrogen fixation. Nodulation was increased to compensate for this. Considerable amounts of nitrogen can be contributed to the ecosystem in gorse end broom litter. Direct transfer between gorse or broom and Pinus radiate is likely to be small and may be masked by competition for other nutrients. These findings are discussed with respect to the use of gorse and broom to overcome nitrogen deficiency in reafforestation on the Moutere Gravels, in Nelson, N.Z.

Gegenstand der vorliegenden Arbeit sind Versuche zur Synthese von 1-Azido-1 alkinen (Ethinylaziden). Diese instabilen Verbindungen zersetzen sich leicht unter Stickstoffabspaltung zu hochreaktiven Carbenen, welche mit verschiedenen Reagenzien, explizit Tolan, Cyclooctin, DMSO sowie DMF, abgefangen werden konnten. Obwohl eine direkte spektroskopische Beobachtung der Titelverbindungen mittels Tieftemperatur-NMR-Spektroskopie nicht verwirklicht werden konnte, gelang der eindeutige Nachweis von Ethinylaziden via deren 1,3-dipolarer Cycloaddition mit dem hochgespannten cyclischen Alkin Cyclooctin. Als Strategie für die Synthese der Titelverbindungen wurden sowohl Substitutionsreaktionen ausgehend von (Chlorethinyl)aromaten als auch Eliminierungsreaktionen ausgehend von substituierten Vinylaziden herangezogen. Es konnten zahlreiche Sulfoxonium-Ylide sowie alpha-Oxocarbonsäureamide als eindeutige Folgeprodukte der Titelverbindungen isoliert und vollständig – größtenteils sogar anhand von Röntgeneinkristallstrukturanalysen – charakterisiert werden.

This master’s thesis has been elaborated as a part of master’s studies of engineering technology M2I-K, major in M-STM – Engineering technology and industrial management and deals with the problem of a transition to a self-production of previously purchased distance washers. Distance washers were purchased in six different types of similar shape, each type in four different thicknesses. One of these types was chosen as a representative for this master’s thesis. We shall explore the possibilities of self-production with the emphasis on economical validation of the transition. The distance washer is a flat part, the intermediate being sheet metal. Technologies considered for manufacturing the washers correspond to the technical facilities and equipment available at the production hall of the company this project is planned for. The company possesses technology for CO2 laser cutting, cutting by CNC punching machine and cutting in the punching tool. To provide a complex overview we shall also enquire into cooperated technologies such as water jet and plasma cutting, oxy-acetyleny cutting and CNC working. All options are evaluated with regard to the production expenses and lead to a most economically plausible method of manufacturing or, if need be, give reasons for going back to purchasing the part from the current supplier.

Gegenstand der vorliegenden Arbeit sind Versuche zur Synthese von 1-Azido-1 alkinen (Ethinylaziden). Diese instabilen Verbindungen zersetzen sich leicht unter Stickstoffabspaltung zu hochreaktiven Carbenen, welche mit verschiedenen Reagenzien, explizit Tolan, Cyclooctin, DMSO sowie DMF, abgefangen werden konnten. Obwohl eine direkte spektroskopische Beobachtung der Titelverbindungen mittels Tieftemperatur-NMR-Spektroskopie nicht verwirklicht werden konnte, gelang der eindeutige Nachweis von Ethinylaziden via deren 1,3-dipolarer Cycloaddition mit dem hochgespannten cyclischen Alkin Cyclooctin. Als Strategie für die Synthese der Titelverbindungen wurden sowohl Substitutionsreaktionen ausgehend von (Chlorethinyl)aromaten als auch Eliminierungsreaktionen ausgehend von substituierten Vinylaziden herangezogen. Es konnten zahlreiche Sulfoxonium-Ylide sowie alpha-Oxocarbonsäureamide als eindeutige Folgeprodukte der Titelverbindungen isoliert und vollständig – größtenteils sogar anhand von Röntgeneinkristallstrukturanalysen – charakterisiert werden.

Cette thèse fait l'étude expérimentale de dynamiques de relaxations ultrarapides au sein d'atomes et de molécules (Ar, NO2, C2H2). Les méthodes expérimentales qui sont utilisées sont basées sur l'interaction d'un rayonnement laser avec le système atomique ou moléculaire étudié et font intervenir le processus de génération d'harmoniques d'ordres élevés, ainsi que la spectrométrie d'imagerie de vecteur vitesse. Au cours de cette thèse, deux approchesexpérimentales de type pompe-sonde ont été mises en œuvre. Une première approche exploitela sensibilité du processus de génération d'harmoniques à la structure électronique dumilieu pour la sonder. Cette méthode a été utilisée sur la molécule de dioxyde d'azote pourobserver sa relaxation électronique à travers l'intersection conique des états X2A1-A2B2suite à une excitation autour de 400 nm. Une seconde approche utilise le rayonnementharmonique comme source de photons dans le domaine de l'extrême ultraviolet (EUV)pour exciter ou sonder les espèces d'intérêt. Cette approche a été couplée avec l'utilisationd'un spectromètre d'imagerie de vecteur vitesse (VMIS), qui a été développé durant lathèse. Des expériences menées sur un système modèle comme l'argon ont permis de validerle dispositif expérimental, qui a ensuite été mis en application pour étudier la photodissociationde la molécule d'acétylène, après excitation autour de 9,3 eV du complexe deRydberg 3d-4s. Les deux méthodes mises en œuvre permettent toutes-deux de réaliserdes études dynamiques résolues en temps à l'échelle femtoseconde. / Ultrafast atomic and molecular dynamics (Ar, NO2, C2H2) have been experimentally studied during this PhD. The employed techniques use the laser interaction with the atomic or molecular system produced in gas phase. High harmonic generation (HHG) pump-probe studies allow resolving dynamics on a femtosecond scale. Two applications of high harmonic generation have been implemented here. In the first one, the harmonic generation process is the probe of a vibronic relaxation induced by a pump pulse. This application is currently labeled high harmonic spectroscopy. The sensibility of the high harmonic process to the geometry of the atomic or molecular orbitals is exploited to obtain information about the electronic structure of the generating medium. This method have been used to reveal the electronic relaxation of the nitrogen dioxide molecule (NO2) through the X2A1-A2B2 conical intersection.A second way consists to use the harmonic radiation like a source of XUV photons. The produced XUV radiation permits thus to reach electronically excited energy levels of atoms or molecules, pumping only with a one photon transition. XUV photons can also be used like a probe to ionize products of a molecular reaction. Velocity map imaging spectrometer (VMIS) have been designed and built to complete this fs-VUV source. Above threshold ionization (ATI) experiments and pump-probe XUV-400 nm studies have been performed on reference system like Argon to characterize the built experimental setup. The last excitation scheme has been also applied to study the photodissociation of the Acetylene excited in the 3d-4s Rydberg complex.