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Active research of SMAs has shown that its Seebeck coefficient is sensitive to its martensitic phase transformation and has the potential to determine the SMAs state of transformation. The combination of Shape Memory Alloys, which have a positive Seebeck coefficient, and Constantan which has a negative Seebeck coefficient (-35 mV/K) results in a thermocouple capable of measuring temperature. The work presented in this thesis is based on the development and design of this sensor. This sensor is used to study the hysteretic behaviour of SMAs. Although Shape Memory Alloys (SMAs) exhibit a myriad of nonlinearities, SMAs show two major types of nonlinear hysteresis. During cyclic loading of the SMAs, it is observed that one type of hysteretic behavior depends on the rate of heating the SMAs, whilst the variation of maximum temperature of an SMA in each cycle results in the other hysteretic behavior. This later hysteretic behavior gives rise to major and minor nonlinear loops of SMAs. The present work analyzes the nonlinearities of hysteretic envelopes which gives the different maximum temperatures reached for each hysteretic cycle with respect to stress and strain of the SMA. This work then models this behavior using Adaptive Neuro Fuzzy Inference System (ANFIS) and compares it to experimental results. The nonlinear learning and adaptation of ANFIS architecture makes it suitable to model the temperature path hysteresis of SMAs. / Master of Science

Thermoelectric phenomenon describes the relationship between the flow of heat and electricity. Two main categories encompassed in thermoelectric theory are the Seebeck and Peltier effects. The Seebeck effect is the generation of a voltage in a device that consists of two different materials in the presence of a temperature gradient, while the Peltier effect is the generation of a temperature gradient across a device of two different materials in the presence of an electrical current. This project focuses on the first of these two phenomena, where the Seebeck effect is used in a novel heat flux sensor that is transverse in nature. Transverse thermoelectric devices are characterized by their anisotropy, meaning that a temperature gradient generated across a device will be perpendicular to the flow of electricity through the device. This orthogonal arrangement allows for the manipulation of material properties, device arrangement, and construction methods for device optimization. This project characterizes the heat flux sensing capabilities of an artificially anisotropic transverse thermoelectric device via experimental and theoretical methods. The device tested is constructed out of bismuth telluride and titanium grade 5. Bismuth telluride is a standard thermoelectric material, while the titanium is used because of its high melting point and good electrical conductivity. The device is constructed by alternating rectangular pieces of these two materials. These pieces are bonded together at a given angle to simulate anisotropy. Several devices are constructed in a range of angles from 59 to 88°. These devices are each tested in a vacuum chamber where a heater heats one side of the device. This heat flux into the device creates a temperature gradient across the device and the device generates a voltage perpendicular to this temperature gradient. Steady state data are collected for both the temperature difference between the two sides of the device and the voltage generated by the device. This procedure is repeated on each device for a range of heat fluxes from 0 to 2.6 W/cm². This range generates voltage signals up to 14341 µV for an angle of 59°. Data collected are then used to generate a linear trend line that describes the devices response to a given heat flux. These experimental results are compared to theoretical predictions using thermoelectric theory. The results indicate that the device does exhibit transverse thermoelectric characteristics and the experimental data follow the predicted trends. This thesis documents the process of constructing, testing, and analyzing this device. / Master of Science

While thermoelectric technology has developed steadily over the last 50 years, transverse thermoelectrics have generally been ignored in the industrial and commercial uses of thermoelectric devices to date. This project focuses on investigating transverse thermoelectric effects for localized cooling and heat flux sensing. Thermoelectric cooling devices are useful when their advantages (small size, solid state, active temperature control) outweigh their relatively poor efficiency. Transverse heat flux sensors, which generate an electric field in a direction orthogonal to the heat flow, have the advantage that the signal depends on the length of the device rather than the thickness. Thus, they can be made very thin for fast response times while maintaining a large signal. A prototype transverse device was built out of bulk samples of bismuth and bismuth telluride, which are common thermoelectric materials. The device was constructed of alternating layers of the constituent materials to simulate the effects of an intrinsically anisotropic material. The device was tested for its cooling and heat flux sensing capabilities, and the results of this testing were compared to predicted values. Although the device failed to demonstrate cooling, its heat flux sensing capabilities were promising. The device was tilted to several angles of inclination between 44° and 84° from horizontal, and the output voltage was recorded for several values of heat flux. The signal strength varied between 190.2 and 2321.6 ìV/(W/cm2), at inclination angles of 84° and 44°, respectively. The results followed the trend of the predicted values well, but the magnitude of the output voltage was significantly lower than expected. An uncertainty analysis was performed, and it was determined that the most likely source of error was the uncertainty in the amount of heat flux that went through the device during testing. This thesis outlines the process of building and testing the device, and the analysis of the results. Recommendations for future work are also given. / Master of Science

Thermoelectric devices are useful for a variety of applications due to their ability to either convert heat directly into electricity, or to generate a temperature gradient from an electric current. These devices offer several attractive features including compact size, no moving parts, limited maintenance requirements, and high reliability. Thus thermoelectric devices are used for temperature-control, cooling, or power generation in various industrial systems such as automobiles, avionics, refrigerators, chillers, laser diodes, dehumidifiers, and a variety of sensors. In order to improve the efficiency of thermoelectric devices, many endeavors have been made to design and fabricate materials with a higher dimensionless thermoelectric figure of merit (ZT), as well as to optimize the device structure and packaging to manage heat more effectively. When evaluating candidate thermoelectric materials, one must accurately characterize the electrical conductivity, thermal conductivity, and the Seebeck coefficient over the temperature range of potential use. However, despite considerable research on thermoelectric materials for decades, there is still significant scatter and disagreement in the literature regarding accurate characterization of these properties due to inherent difficulties in the measurements such as requirements for precise control of temperature, simultaneous evaluation of voltage and temperature, etc. Thus, a well-designed and well-calibrated thermoelectric measurement system that can meet the requirements needed for multiple kinds of thermoelectric materials is an essential tool for the development of advanced thermoelectric devices. In this dissertation, I discuss the design, fabrication, and validation of a measurement system that can rapidly and accurately evaluate the Seebeck coefficient and electrical resistivity of thermoelectric materials of various shapes and sizes from room temperature up to 600 K. The methodology for the Seebeck coefficient and electrical resistivity measurements is examined along with the optimization and application of both in the measurement system. The calibration process is completed by a standard thermoelectric material and several other materials, which demonstrates the accuracy and reliability of the system. While a great deal of prior research has focused on low temperature thermoelectric materials for cooling, such as Bi2Te3, high temperature thermoelectric materials are receiving increasing attention for power generation. With the addition of commercial systems for the Seebeck coefficient, electrical resistivity, and thermal conductivity measurements to expand the temperature range for evaluation, a wide range of materials can be studied and characterized. Chapter Two of this dissertation describes the physical properties characterization of a variety of thermoelectric materials, including room temperature materials such as Bi0.5Sb1.5Te3, medium temperature level materials such as skutterudites, and materials for high temperature applications such as half-Heusler alloys. In addition, I discuss the characterization of unique oxide thermoelectric materials, which are Al doped ZnO and Ca-Co-O systems for high temperature applications. Chapter Four of this dissertation addresses the use of GaSn alloys as a thermal interface material (TIM), to improve thermal transport between thermoelectric devices and heat sinks for power generation applications at high temperature. I discuss the mechanical and thermal behavior of GaSn as an interface material between electrically insulating AlN and Inconel heat exchangers at temperatures up to 600 °C. Additionally, a theoretical model for the experimental thermal performances of the GaSn interface layer is also examined. / Ph. D. / Thermoelectric materials can directly convert heat into electricity for power generation, or they can be used for cooling or refrigeration applications when supplied with electric power. This dissertation primarily focuses on the evaluation of materials used in thermoelectric generators (TEGs). Specifically, Chapter Two of this work describes the design, development, and validation of a developed measurement system that can evaluate two important properties, the Seebeck coefficient and electrical resistivity, for a variety of thermoelectric materials. Next, Chapter Three discusses the work using other commercial measurement systems to evaluate several types of thermoelectric materials, including Bi2Te3 based materials, skutterudites, half-Heusler alloys, ZnO, and Ca-Co-O for a TEG module. Finally, I discuss the use of GaSn, a liquid metal alloy, as a thermal interface material to improve heat transport between dissimilar materials for TEGs. The GaSn was applied between a thermoelectric device and a heat exchanger for use in energy harvesting devices. The mechanical robustness and thermal reliability were tested, and the GaSn was shown to improve thermal performances both in experiments and through modeling.

This PhD thesis presents investigations of perovskite-related compounds in systems of interest for applications in components in solid oxide fuel cells. The compound compositions derive from substitutions in the parent compounds LaCoO3, LaCrO3 and SrFeO3. Novel phases La2Co1+z(MgxTi1-x)1-zO6 were synthesized and investigated with regard to structure, thermal expansion, electronic and magnetic properties. The study focused on the composition lines La2Co(MgxTi1-x)O6 (z=0), where the oxidation state of Co nominally changes from +2 (x=0.0) to +3 (x=0.5), and La2Co1+z(Mg0.5Ti0.5)1-zO6, with a varying fraction of Co3+ ions. XANES data show that the Co ions in the system have discrete oxidation states of +2 and +3. The TEC increases with increasing x due to an increasing contribution from spin state transitions of the Co3+ ions. Novel compounds La2Cr(M2/3Nb1/3)O6 with M=Mg, Ni, Cu were synthesized and characterized with respect to structure and magnetic properties. XRPD and NPD data indicate Pbnm symmetry; however, SAED patterns and HREM images indicate a P21/n symmetry for M=Mg, and Cu. The magnetic measurements results were rationalized using the Goodenough-Kanamori rules. Oxygen-deficient phases with x≥0.63 in SrxY1-xFeO3-δ and Sr0.75Y0.25Fe1-yMyO3-δ (M=Cr, Mn, Ni and y=0.2, 0.33, 0.5), were synthesized and characterized with respect to structure, oxygen content, thermogravimetry, TEC, conductivity and magnetic properties. Powder patterns of phases agree with cubic  perovskite structures. NPD data for x=0.75 reveal anisotropic displacement for the O atom, related to local effects from Fe3+/Fe4+ ions. SAED patterns for x=0.75 reveal the presence of an incommensurate modulation. The compounds start to lose oxygen in air at ~ 400°C. The TEC up to ~400°C for x=0.75 is ~10.5 ppm/K and increase to ~17.5 ppm/K at higher temperatures. The conductivity for x=0.91 is 164 S/cm at 400°C. Partial substitution of Fe by Cr, Mn or Ni does not increase the conductivity or decrease TEC.

This work aims at improving the understanding of the fundamental physics behind molecular doping of organic semiconductors, being a requirement for efficient devices like organic light-emitting diodes (OLED) and organic photovoltaic cells (OPV). The underlying physics is studied by electrical conductivity and thermoelectrical Seebeck measurements and the influences of doping concentration and temperature are investigated. Thin doped layers are prepared in vacuum by thermal co-evaporation of host and dopant molecules and measured in-situ. The fullerene C60, known for its high electron mobility, is chosen as host for five different n-dopants. Two strongly ionizing air-sensitive molecules (Cr2(hpp)4 and W2(hpp)4) and three air-stable precursor compounds (AOB, DMBI-POH and o-MeO-DMBI-I) which form the active dopants upon deposition are studied to compare their doping mechanism. High conductivities are achieved, with a maximum of 10.9 S/cm. Investigating the sample degradation by air-exposure, a method for regeneration is proposed, which allows for device processing steps under ambient conditions, greatly enhancing device fabrication possibilities. Various material combinations for p-doping are compared to study the influence of the molecular energy levels of host (MeO-TPD and BF-DPB) and dopant (F6-TCNNQ and C60F36). Corrections for the only estimated literature values for the dopant levels are proposed. Furthermore, the model system of similar-sized host pentacene and dopant F4-TCNQ is studied and compared to theoretical predictions. Finally, a model is developed that allows for estimating charge carrier mobility, density of free charge carriers, doping efficiency, as well as the transport level position from combining conductivity and Seebeck data. / Diese Arbeit untersucht organische Halbleiter und den Einfluss von molekularer Dotierung auf deren elektrische Eigenschaften, mit dem Ziel effizientere Bauelemente wie organische Leuchtdioden oder Solarzellen zu ermöglichen. Mittels Leitfähigkeitsuntersuchungen sowie thermoelektrischen Seebeck-Messungen werden die Einflüsse der Dotierkonzentration sowie der Temperatur auf die elektrischen Eigenschaften dünner dotierter Schichten analysiert. Das Abscheiden der Schichten durch Koverdampfen im Vakuum ermöglicht eine in-situ Analyse. Das Fulleren C60, bekannt für besonders hohe Elektronenbeweglichkeit, wird als Wirt für fünf verschieden n-Dotanden, zwei extrem stark ionisierende luftreaktive (Cr2(hpp)4 und W2(hpp)4) sowie drei luftstabile (AOB, DMBI-POH und o-MeO-DMBI-I), verwendet. Dies ermöglicht Schlüsse auf die unterschiedlichen zugrunde liegenden Dotiermechanismen und das Erreichen von Leitfähigkeiten von bis zu 10.9 S/cm. Für einen der luftreaktiven Dotanden wird die Probendegradation an Luft untersucht und eine Regenerationsmethode aufgezeigt, die Prozessierungsschritte in Luft erlaubt und somit entscheidend für zukünftige Bauelementfertigung sein könnte. Verschiedene p-dotierte Materialkombinationen werden untersucht, um den Einfluss der molekularen Energieniveaus von Wirt (MeO-TPD und BF-DPB) und Dotand (F6-TCNNQ und C60F36) auf die Dotierung zu studieren. Dies ermöglicht Schlussfolgerungen auf die in der Literatur bisher nur abgeschätzten Energieniveaus dieser Dotanden. Ferner werden die Eigenschaften des bereits theoretisch modellierten Paares Pentacen und F4-TCNQ mit den Vorhersagen verglichen und die Abweichungen diskutiert. Abschießend wird ein Modell entwickelt, das die Abschätzung von Dotiereffizienz, Ladungsträgerkonzentration, Ladungsträgerbeweglichkeit sowie der Position des Transportniveaus aus Leitfähigkeits- und Seebeck-Messungen erlaubt.

Dans son ensemble, cette thèse porte sur la synthèse, l’étude structurale et l’étude des propriétés magnétiques et de transport de différentes familles d’oxydes de ruthénium, présentant des comportements électroniques et magnétiques variés, de structure rutile, hexaferrite de type R et hollandite. Le but de ce travail était l’étude des particularités des oxydes de ruthénium sondées par l’effet Seebeck dans les matériaux suivants : RuO2 de structure rutile (chaînes d’octaèdres de RuO6 liés par leurs arêtes, interconnectées par leurs sommets) à transport de type Boltzmann dominé par les interactions électron-phonon, les hexaferrites de type R BaCo2Ru4O11 et BaMn2Ru4O11 (octaèdres de RuO6 liés par les arêtes, formant des plans kagomé, et octaèdres de RuO6 liés par une face) ferromagnétiques doux et mauvais métaux, et deux nouvelles hollandites Sr1.5Ru6.1Cr1.9O16 et Ba1.5Ru6.1Cr1.9O16 (doubles chaînes de RuO6 liés par les arêtes, interconnectées par les sommets) avec agglomérats de spins localisés. La synthèse de ces deux nouvelles hollandites par réaction à l’état solide a permis de mettre en évidence l’existence de magnétorésistance négative dans cette famille de composés. Cette thèse montre que le comportement du coefficient Seebeck S d'oxydes de ruthénium à structures constituées d'octaèdres RuO6 majoritairement liés par leurs arêtes présente deux comportements différents. À basse T, S dépend fortement de la structure cristallographique et de la structure électronique associée. Par contre, dans la limite haute T, S tend vers une valeur commune indépendamment de la structure comme rapporté ici pour les hexaferrites de type R et les hollandites, et comme observé précédemment dans la pérovskite SrRuO3 (octaèdres RuO6 liés par les sommets) ferromagnétique métallique et dans la quadruple pérovskite LaCu3Ru4O12 (octaèdres RuO6 liés par les sommets) métallique présentant un magnétisme de type Pauli. Dans ces hexaferrites de type R BaCo2Ru4O11 et BaMn2Ru4O11 et dans ces deux nouvelles hollandites Sr1.5Ru6.1Cr1.9O16 et Ba1.5Ru6.1Cr1.9O16, le coefficient Seebeck à haute température atteint une valeur dominée par l’entropie de spin du ruthénium. / This thesis deals with the synthesis, the structural study and the magnetic properties and electronic transport studies of different ruthenium oxide families, presenting various magnetic and electronic behaviors, with rutile, R-type hexaferrite and hollandite structures. The goal of this thesis was the study of the ruthenium oxide peculiarities probed by the Seebeck effect in the following materials: RuO2 rutile (edge-shared RuO6 chain interconnected by their vertices) with Boltzmann type transport dominated by electron-phonon interactions, BaCo2Ru4O11 et BaMn2Ru4O11 R-type hexaferrites (edge-shared RuO6 octahedra, forming kagome planes, and face-shared RuO6 octahedra) soft ferromagnetic bad metals, and two new hollandites Sr1.5Ru6.1Cr1.9O16 et Ba1.5Ru6.1Cr1.9O16 (double chains of edge-shared RuO6 octahedra, interconnected by their vertices) with localized transport and cluster-glass behavior. The synthesis of both new hollandites by solid state reaction allowed us to show the existence of negative magnetoresistance in this compound family. This thesis shows that the behavior of the Seebeck coefficient of ruthenium oxides with structures mainly consisting of edge-shared RuO6 octahedra presents two different behaviors. At low T, S strongly depends on the crystallographic structure and on the associated electronic structure. On the other hand, in the high T limit, S tends a common value independently of the structure as reported here for the R-type hexaferrites and the hollandites and as previously observed in the ferromagnetic metal SrRuO3 perovskite (apex-shared RuO6 octahedra) and in the metallic with Pauli-type magnetism quadruple perovskite LaCu3Ru4O12 (apex-shared RuO6 octahedra). In these R-type hexaferrites BaCo2Ru4O11 and BaMn2Ru4O11 and these two new hollandites Sr1.5Ru6.1Cr1.9O16 and Ba1.5Ru6.1Cr1.9O16, the high temperature Seebeck coefficient reaches a value dominated by the Ru spin entropy term.