Antarctica is home to numerous perennially ice-covered (PIC) lakes that host rich benthic microbial ecosystems. These lakes are covered by a thick floating ice cover year-round and often have water columns supersaturated in dissolved gases, resulting in heavily bubbled ice covers, altering the optical properties of the ice and the amount of light that penetrates into the water column. Thus, understanding the optical properties of perennial lake ice can have important scientific implications to the study of life on Earth and the search for extraterrestrial life. Synthetic aperture radar (SAR) remote sensing has been used rigorously for over 50 years to study and monitor the seasonal response and long-term trends of backscatter over seasonally ice-covered (SIC) Arctic lakes. Limited studies have assessed the impacts of dissolved gases and ice/water interface bubbles on SAR backscatter variability over SIC lakes. The seasonal backscatter response of Antarctic PIC lakes remains unexplored; their physical nature asserts that their backscatter response should largely be decoupled from seasonal factors according to SIC lake backscatter theory. Additionally, gas supersaturated PIC lakes are ideal candidates to better understand the role of gas buildup and bubble formation on the backscatter response from floating ice covers. This thesis leverages a dense stack of Sentinel-1 C-band SAR imagery over Lake Untersee, a well-sealed PIC lake in East Antarctica, to explore the relationships between SAR backscatter and ice/water interface bubbles. This analysis integrates field measurements and temporal observations at the ice/water interface. Lastly, a brief comparative analysis extends to other ice covers, including moat-forming PIC lakes, as well as first-year and multi-year Arctic sea and lake ice. It is shown that Lake Untersee has a seasonal backscatter regime that is linked to air temperature. A strong correlation is found between the timing of backscatter intensity increase in winter and ice thickness. This relationship is attributed to variations in ice thickness which affect the length of the freezing period under the ice, the rate of dissolved gas accumulation, and ultimately, the nucleation and abundance of bubbles at the ice/water interface. These findings can be applied to other PIC lakes that have seasonal gas regimes. This research provides valuable insights into the complex interplay between ice cover characteristics, gas dynamics, interface bubbles, and SAR backscatter, enhancing our understanding of polar aquatic ecosystems and their broader implications for global environments.

The power industry relies on high voltage transformers as the backbone of power distribution networks. High voltage transformers are designed to handle immense electrical loads in hostile environments. Long term placement is desired, however by being under constant heavy load transformers face mechanical, thermal, and electrical stresses which lead to failures of the protection systems in place. The service life of a transformer is often limited by the life time of its insulation system. Insulation failures most often develop from thermal faults, or hotspots, and electrical faults, or partial discharges. Detecting hotspots and partial discharges to predict transformer life times is imperative and much research is focused towards these topics. As these protection systems fail they often generate gas or acoustic signals signifying a problem. Research has already been performed discovering new ways integrate optical fiber sensors into high voltage transformers. This thesis is a continuation of that research by attempting to improve sensor sensitivity for hydrogen and acetylene gasses. Of note is the fabrication of new hydrogen sensing fiber for operation around a larger absorption peak and also the improvement of the acetylene sensor's light source stability. Also detailed is the manufacturing of a field testable prototype and the non-sensitivity testing of several other gasses. The developed sensors are capable but still could be improved with the use of more powerful and stable light sources. / Master of Science

This thesis presents an artificial neural network (ANN) approach to diagnose and detect faults in oil-filled power transformers based on dissolved gas-in-oil analysis. The goal of the research is to investigate the available transformer incipient fault diagnosis methods and then develop an ANN approach for this purpose. This ANN classifier should not only be able to detect the fault type, but also should be able to judge the cellulosic material breakdown. This classifier should also be able to accommodate more than one type of fault. This thesis describes a two-step ANN method that is used to detect faults with or without cellulose involved. Utilizing a feedforward artificial neural network, the classifier was trained with back-propagation, using training samples collected from different failed transformers. It is shown in the thesis that such a neural-net based approach can yield a high diagnosis accuracy. Several possible design alternatives and comparisons are also addressed in the thesis. The final system has been successfully tested, exhibiting a classification accuracy of 95% for major fault type and 90% for cellulose breakdown. / Master of Science

Substation apparatus failure plays a major role in reliability of power delivery systems. Traditionally, most utilities perform regular maintenance in order to prevent equipment breakdown. Condition-based maintenance strategy monitors the condition of the equipment by measuring and analyzing key parameters and recommends optimum maintenance actions. Equipment such as transformers and standby batteries which are valuable and critical assets in substations has attracted increased attentions in recently years. An automated monitoring and diagnosis tool for power transformers based on dissolved gas analysis, ANNEPS v4.0, was developed. The new tool extended the existing expert system and artificial neural network diagnostic engine with automated data acquisition, display, archiving, and alarm notification functions. This thesis also studied substation batteries types and failure mode and surveyed the market of current on-line battery monitors. A practical battery monitoring system architecture was proposed. Analysis rules of measured parameters were developed. The above study and results can provide basics for further designing of a simple battery monitoring system in industry applications. / Master of Science

Potentiometrisch betriebene Festelektrolytsensoren auf der Basis von Yttriumoxid-stabilisiertem Zirconium(IV)-oxid als festem Oxidionenleiter weisen einen für elektrochemische Sensoren ungewöhnlich breiten Messbereich von über 30 Zehnerpotenzen sowie eine vergleichsweise hohe chemische, thermische und mechanische Stabilität auf. Dadurch konnten sich diese Sensoren in einem sehr weiten Applikationsbereich etablieren, der hauptsächlich die Abgaskontrolle von Verbrennungsprozessen betrifft. In der vorliegenden Arbeit wird der Frage nachgegangen, ob mit Festelektrolytsensoren (FES) bei coulometrischer oder potentiodynamischer Betriebsweise, die gegenüber dem potentiometrischen Prinzip Vorteile im Hinblick auf Sensitivität beziehungsweise Selektivität bieten, weitere Applikationsfelder erschlossen werden können. Dazu durchgeführte Untersuchungen, Weiterentwicklungen und Optimierungen an coulometrisch betriebenen Festelektrolytsensoren sowie deren Einbindung in ein chromatographisches Messsystem zielten auf die Applikation zur Bestimmung von Spurenbestandteilen in Gasen und Flüssigkeiten ab. Mit den Ergebnissen wird beispielhaft ein neues Anwendungsfeld für FES bei der kontinuierlichen Überwachung von Biogasprozessen eröffnet. Zur Erreichung der Ziele wird zunächst gezeigt, wie der Messbereich potentiostatisch betriebener coulometrischer FES hin zu Spurenkonzentrationen im Vol.-ppb-Bereich erweitert werden kann. Hierfür werden Fehlereinflüsse untersucht, die die Nachweisgrenze dieser Sensoren beeinflussen. Durch die Entwicklung rauscharmer elektronischer Sensoransteuerungen, durch die Optimierung von Betriebsparametern sowie durch die Bestimmung der elektronischen Leitfähigkeit wird die Nachweisgrenze von FES verglichen mit dem bisherigen Forschungsstand um vier Zehnerpotenzen verringert. Als Ergebnis dieser Weiterentwicklungen liegen die Nachweisgrenzen für den FES im Durchflussbetrieb nun bei unter 5 Vol.-ppb für die Analyte H2, O2 und CH4. Zur Steigerung der Selektivität von FES werden zwei Möglichkeiten aufgezeigt. Einerseits werden bei cyclovoltammetrischer Betriebsweise für H2-, O2- oder CO-haltige Messgase im Konzentrationsbereich unterhalb von 10^2 Vol.-ppm lineare Zusammenhänge zwischen den Konzentrationen und den Peakeigenschaften Höhe und Fläche gefunden. Auf diese Weise konnte H2 an einer katalytisch hochaktiven Pt-Elektrode in Anwesenheit eines Überschusses an Sauerstoff mit hoher Selektivität erfasst werden. Andererseits wird die Selektivität potentiostatisch betriebener coulometrischer FES drastisch gesteigert, indem diese einer gaschromatographischen Trenneinheit nachgeschaltet werden. Im Konzentrationsbereich von 10^−1 bis 10^4 Vol.-ppm zeigte sich für H2 und CH4 ein lineares Ansprechverhalten, die Nachweisgrenzen des chromatographischen Messsystems lagen für diese Gase bei 55 bzw. 40 Vol.-ppb. Mit einem neuartigen In-situ-Messsystem, das auf dem Prinzip der kontinuierlichen membranfreien Gasextraktion und anschließender intervallmäßiger chromatographischer Trennung und Detektion mit einem potentiostatisch betriebenen coulometrischen FES basiert, wurden im Gärmedium von Biogasanlagen Spuren von gelöstem H2 und O2 sowie das vielfach höher konzentrierte CH4 parallel erfasst. Es wird gezeigt, dass Instabilitäten im Biogas-Entstehungsprozess, die durch Überfütterung des Fermenters hervorgerufen werden, anhand des Verlaufs des gelösten H2 deutlich früher erkannt werden, als es durch die H2-Bestimmung im Biogas durch kommerziell verfügbare Gassensoren möglich ist. Auf diese Weise ließ sich mit dem FES ein praxistaugliches langzeitstabiles, robustes und wartungsarmes Messsystem für diese Kenngrößen entwickeln. Bei der coulometrischen Bestimmung von Essigsäure mit dem FES kommt es zur Blockierung der Platinelektroden. Infrarotspektroskopische Untersuchungen des Abgases aus dem FES belegen die thermische Zersetzung dieses Analyts bei 750 °C, die mit der Bildung eines Kohlenstofffilms auf der messgasseitigen Pt-Elektrode einhergeht. Diese Blockierung führt zur Peakverbreiterung und verhindert so die Detektion der Carbonsäuren mit zwei bis fünf Kohlenstoffatomen im Molekül. In dieser Arbeit wird gezeigt, dass dieser ungünstige thermische Zerfall durch die Einbringung einer beheizbaren Katalyseeinheit in die Gasleitung zwischen Gaschromatograph und FES verhindert werden kann. Die Säuren zerfallen dann an der Pt-Oberfläche des Katalysators bei 800 °C, so dass nur die gasförmigen Zerfallsprodukte in den FES gelangen, wo sie ohne die Bildung von Pyrolyseprodukten an den Elektroden coulometrisch umgesetzt werden. Mittels Austausch des FES durch einen Flammenionisationsdetektor konnte mit dem In-situ-Messsystem gelöste Essigsäure über einen Zeitraum von achtzehn Tagen im Gärmedium einer Biogasanlage mit hinreichender Langzeitstabilität erfasst werden. Damit werden in der vorliegenden Arbeit wesentliche Beiträge zur Weiterentwicklung von coulometrischen Festelektrolytsensoren im Hinblick auf die Erniedrigung der Nachweisgrenze, die Erhöhung der Selektivität und die Verbreiterung des Anwendungsspektrums geleistet. / Potentiometric solid electrolyte sensors made of the solid oxygen ion conductor 'yttria stabilized zirconia' exhibit a very broad measuring range of more than 30 orders of magnitude as well as comparatively high chemical, thermal and mechanical stability. Therefore, these sensors were established in a large application range which covers mainly the field of exhaust gas control of combustion processes. This work tries to answer the question if it is possible to address new fields of application with coulometrically or potentiodynamically operated solid electrolyte sensors (ses) because of their generally higher sensitivity and selectivity compared to potentiometrically operated ses. Investigations, advancements and optimizations executed for this aim on coulometrically operated ses as well as the integration of these sensors into a chromatographic measuring system were directed on the detection of traces of analytes in gas mixtures and liquids. The results of this work unlock a new field of application for ses in the continuous monitoring of biogas processes. For the achievement of these goals it is firstly demonstrated how the measuring range of potentiostatically operated coulometric ses can be expanded in the direction of trace concentrations in the range of some vol.-ppb. Therefore, error sources influencing the detection limit are investigated. Compared to the current state of research, this limit is decreased by four orders of magnitute by developing low-noise sensor controllers, by optimizing operation conditions and by determining the electronic conductivity of the solid electrolyte material. As a result, the detection limits of the sensor operating in continuous flow-through mode range now below 5 vol.-ppb for the analytes H2, O2 and CH4. Furthermore, two approaches for the increasement of the selectivity of ses are presented. One of them concerns an optimized cyclovoltammetric operation of these sensors, resulting in a linear increase of peak height and peak area with increasing concentrations up to 10^2 vol.-ppm for H2, O2 or CO in nitrogen based gas mixtures. Thus, hydrogen could be detected on a Pt electrode with high catalytic activity in presence of an excess of oxygen in the measuring gas. The second approach is directed on the significant improvement of selectivity by operating coulometric ses in potentiostatic mode downstream of a gas chromatographic separation unit. For H2 and CH4 this chromatographic measuring system exhibited linear operation in the concentration range from 10^-1 - 10^4 vol.-ppm and offered detection limits of 55 and 40 vol.-ppb respectively. A novel in-situ measuring system is based on continuous membrane-free extraction, followed by periodic chromatographic separation and subsequent coulometric detection by a potentiostatically operated coulometric ses. With this measuring system, traces of H2 and O2 as well as the much larger amount of generated CH4 were determined simultaneously in the digestion medium of biogas plants. It is shown that instabilities in the microbial biogas process which are caused by fermenter overfeeding can be realized on the basis of the course of dissolved hydrogen. The novel measuring system indicates these instabilities much earlier than commercially available hydrogen sensors positioned in the biogas stream. Thus, a practicable longterm-stable, robust and low-maintenance measuring system could be developed for these parameters with the use of ses. The ses equipped with platinum electrodes shows electrode blocking during the coulometric measurement of acetic acid. Infrared spectrometric investigations of the ses exhaust gas clearly indicate thermal decomposition of this analyte at 750 °C, which is accompanied with carbon film formation on the Pt electrode surface. This blockage leads to peak broadening and therefore prevents appropriate detection of carboxylic acids containing between 2 and 5 carbon atoms. It could be demonstated in this work that this detrimental thermal decomposition on the ses electrodes could be circumvented by integrating a heated Pt catalyst between separation column and ses detector. The acids decompose then at the Pt surfaces of the catalyst at 800 °C and the decomposition products are detected by ses immediatly without formation of pyrolysis products on the electrodes. By replacing the ses in the measuring system with a flame ionization detector, acetic acid could be measured with appropriate long-term stability in the digestion medium of a biogas plant over a period of eighteen days. In summary this work presents substancial contributions to the advancement of coulometric solid electrolyte sensors by lowering their detection limits, increasing their selectivity and thus broadening their application spectrum significantly.

This dissertation thesis is focused on the evaluation of the dissolved gas analysis in the power oil transformer diagnosis. This thesis derives from known, in standards, directives and literature shows realities which are fill in new pieces of knowledge as determining of gases important for evaluation of the transformer condition, specifying of current methods accuracy and investigating of accuracy change for interpretation of dissolved gases. The part of this thesis is the application of mathematic methods for detailed description of individual transformer failures and determining of dominant gas which are generating in power oil transformer. Obtain conclusion will be contribution for transformer diagnostics and will be applicable in industrial practice.

Existem inúmeras ferramentas e metodologias para o diagnóstico de falhas em transformadores de potência, tanto para a monitoração e acompanhamento do equipamento em operação (planta fixa) como àquele retirado e abrigado em laboratórios de unidades fabris. Em função dos custos envolvidos no transporte dos equipamentos, manuseio para a substituição, energia não faturada nos períodos de manobras e custos adicionais dos ensaios para voltar com o equipamento em operação, as principais metodologias que se destacam são aquelas direcionadas ao equipamento em operação e também as escolhidas para serem analisadas neste trabalho. Após um estudo sistemático dessas metodologias, tais como termográfica, emissão acústica e análise dos gases dissolvidos no óleo, denominada cromatografia, verificou-se que esta última se destaca como a mais econômica e a mais difundida na identificação das falhas. Contudo, na cromatografia, existem diferentes critérios de análise baseados nas relações e quantidades de diferentes tipos de gases e que são usados pelas companhias concessionárias de forma indiscriminada, gerando muitas dúvidas quanto à sua validade. Esta pesquisa teve como principal foco a comparação desses critérios usando como base de dados àqueles fornecidos pela IEC e pela Companhia Paulista de Força e Luz (CPFL). A base de dados da CPFL contem aproximadamente quatro mil ensaios cromatográficos, colhidas nas ultimas três décadas correspondendo a 500 unidades transformadoras, nas potências de 5,0 a 50 MVA, instaladas em subestações nas tensões primárias de 69 e 138 kV, e secundária de 13,8 kV. Também fez parte dessa pesquisa a definição de um conjunto de critérios que melhor identificam as falhas em transformadores. / There are numerous tools and methodologies for fault diagnosis in power transformers, either for monitoring and tracking equipment in operation (fixed plant) or for those removed and housed in laboratories plants. Due to the costs involved in transporting the equipment, handling for the replacement, unbilled energy during periods of maneuvers and additional costs of the tests to return with the equipment in operation, the main methodologies that stand out are those using the equipment in operation and also those chosen to be analyzed in this work. After a systematic study of these methods such as thermography, and acoustic emission and analysis of gases dissolved in the oil, known as chromatography, it was found that the latter stands out as the most economical and most widely in the identification of faults. However, in chromatography, there are different criteria based on the relationships of different types and quantities of gases that are used by electrical companies indiscriminately, raising many questions about its validity. This research was mainly focused on the comparison of these criteria using the database as those provided by IEC and the Companhia Paulista de Força e Luz (CPFL). The database of CPFL contains approximately four thousand chromatographic assays from the last three decades, corresponding 500 transforming units, from 5 to 50 MVA, in substations with primary voltages of 138 kV and 69 and secondary of 13,8 kV. Was also studied the definition of a set of criteria which identify faults in transformers.

Existem inúmeras ferramentas e metodologias para o diagnóstico de falhas em transformadores de potência, tanto para a monitoração e acompanhamento do equipamento em operação (planta fixa) como àquele retirado e abrigado em laboratórios de unidades fabris. Em função dos custos envolvidos no transporte dos equipamentos, manuseio para a substituição, energia não faturada nos períodos de manobras e custos adicionais dos ensaios para voltar com o equipamento em operação, as principais metodologias que se destacam são aquelas direcionadas ao equipamento em operação e também as escolhidas para serem analisadas neste trabalho. Após um estudo sistemático dessas metodologias, tais como termográfica, emissão acústica e análise dos gases dissolvidos no óleo, denominada cromatografia, verificou-se que esta última se destaca como a mais econômica e a mais difundida na identificação das falhas. Contudo, na cromatografia, existem diferentes critérios de análise baseados nas relações e quantidades de diferentes tipos de gases e que são usados pelas companhias concessionárias de forma indiscriminada, gerando muitas dúvidas quanto à sua validade. Esta pesquisa teve como principal foco a comparação desses critérios usando como base de dados àqueles fornecidos pela IEC e pela Companhia Paulista de Força e Luz (CPFL). A base de dados da CPFL contem aproximadamente quatro mil ensaios cromatográficos, colhidas nas ultimas três décadas correspondendo a 500 unidades transformadoras, nas potências de 5,0 a 50 MVA, instaladas em subestações nas tensões primárias de 69 e 138 kV, e secundária de 13,8 kV. Também fez parte dessa pesquisa a definição de um conjunto de critérios que melhor identificam as falhas em transformadores. / There are numerous tools and methodologies for fault diagnosis in power transformers, either for monitoring and tracking equipment in operation (fixed plant) or for those removed and housed in laboratories plants. Due to the costs involved in transporting the equipment, handling for the replacement, unbilled energy during periods of maneuvers and additional costs of the tests to return with the equipment in operation, the main methodologies that stand out are those using the equipment in operation and also those chosen to be analyzed in this work. After a systematic study of these methods such as thermography, and acoustic emission and analysis of gases dissolved in the oil, known as chromatography, it was found that the latter stands out as the most economical and most widely in the identification of faults. However, in chromatography, there are different criteria based on the relationships of different types and quantities of gases that are used by electrical companies indiscriminately, raising many questions about its validity. This research was mainly focused on the comparison of these criteria using the database as those provided by IEC and the Companhia Paulista de Força e Luz (CPFL). The database of CPFL contains approximately four thousand chromatographic assays from the last three decades, corresponding 500 transforming units, from 5 to 50 MVA, in substations with primary voltages of 138 kV and 69 and secondary of 13,8 kV. Was also studied the definition of a set of criteria which identify faults in transformers.

Interactions between hydrophobic surfaces at short separation distances (at the nanometer scale) are very important in a number of industrial applications. For example, in the froth flotation mineral separation process it is the interaction between the hydrophobic particle and the bubble which is paramount in separating the valuable minerals from the gangue. A number of studies, most notably using the atomic force microscope (AFM) and the surface force apparatus (SFA) have found the existence of a long range hydrophobic attractive force between hydrophobic surfaces that cannot be explained by classical colloidal science theories. In many cases, this force is an artefact due to the accumulation of sub-microscopic bubbles, the so called nanobubbles, at the liquid-hydrophobic solid interface. Thus, what was thought to be a hydrophobic force was actually a capillary force resulting from the gaseous bridge formed from the coalescence of nanobubbles, that is, the nanobubble bridging capillary force (NBCF). It is the purpose of this thesis to provide further insight into the accumulation of soluble gases at the liquid-hydrophobic solid interface and the resulting NBCF. Specifically, this thesis studies these phenomena from a fundamental standpoint and additionally relates the findings to froth flotation mineral separation. A systematic method to measure the NBCF by controlling the size of the gaseous capillary bridge was devised in this thesis. Control of the capillary bridge was achieved by utilising the solvent-exchange method to accumulate nanobubbles at the surface, followed by surface scanning of the colloidal probe over the flat surface to harvest nanobubbles. Thus, the NBCF has been controlled to allow for greater success in modelling the interaction, understanding the geometric parameters of the bridge, observing changes in friction force due to nanobubbles and understanding the influence of ethanol on the force. An outcome of this thesis was the development of a capillary force model which describes the NBCF. The model considers a constant volume and constant contact angle assumption for a gaseous capillary bridge of toroidal geometry. The model was very successful in describing the NBCF at long separation distances (>20nm) for both the approach and retract interactions. The close fitting between the experimental data and the model allowed accurate determinations of the advancing and receding contact angles, bridge geometry and volume. The successful implementation of the capillary force model allowed a link between the bridge volume, and the resulting adhesion to the friction force between hydrophobic solid surfaces in water. Additionally, the model allowed the change from an attractive to a repulsive NBCF to be described by a change from a concave to convex bridge geometry. Thus, this thesis has added considerable knowledge to the fundamental aspects of nanobubbles and the NBCF. The final chapters of this thesis utilised the knowledge gained from the fundamental studies to understand the influence of nanobubbles on flotation. In the first study, the influence of NaCl concentration on the morphology of gaseous domains on a graphite surface is discussed in relation to the increased recovery of coal in saline water. In the second study, methanol treatment of a ZnS ore was found to increase the floatability due to slime removal and the artificial formation of nanobubbles.

Le travail de cette thèse avait pour objectif de contribuer à apporter de solutions au problème de surveillance des transformateurs par le biais des analyses de l'huile. La méthodologie et les résultats présentés s'appuient sur des cas concrets de transformateurs expertisés et des analyses d'huile réalisées en laboratoire. Les règles de diagnostic pour les grandeurs physico-chimiques ont été établies pour chaque équipement électrique et pour chaque type de fluide. Ces règles ont montré l'importance des paramètres liés à l'échantillonnage, à la méthode d'analyse et à la conception du transformateur et notamment l'importance du régleur en charge. Un lien entre analyse, défaut et origine du défaut a été établi et constitue la base de l'outil de diagnostic proposé. Ainsi l'outil identifie, à l'aide des analyses physico-chimiques réalisées sur le fluide, des défauts possibles et propose des origines de panne du transformateur. Finalement, une piste de pronostic d'état est abordée afin de développer le diagnostic. / The scope of this thesis was designed to contribute to solving the transformer monitoring problem of monitoring of transformers by analyses oil. The methodology and the results presented are based on concrete cases of assessed de-tanked transformers and oil analysis laboratory. The rules of diagnosis for physicochemical quantities have been established for each electrical equipment and for each type of fluid. These rules showed the importance of the sampling parameters, the method of analysis and the design of the transformer and especially the significance of the on load tap changer. A link between analysis, defect and origin of the defect was established which is the basis of the proposed diagnosis tool. Thanks to the chemical analyses, this tool enables to identify potential defects in the transformer and reveals some origins of failures.