No description available.

No description available.

No description available.

<p>With the rising prices of energy and the harmful environmental effects many of conventional energy generation techniques the world is pushing for new, cleaner, more efficient and more environmental renewable energy sources. Thermoelectric generators are one of the potential solutions to these problems of unclean and expensive energy. Thermoelectric generators are solid state devices that convert thermal energy into useful electrical energy.</p> <p>Over the last ten years the progress in materials science have led to advancements in thermoelectrics. However as of yet no standardised method of testing thermoelectric generators has been established and as such data provided for thermoelectric generators is regarded as questionable. This thesis deals with two commercial thermoelectric generator models, TEG1 12610-5.1 AND TEG1B 12610-5.1, and quantifies the deviation of the manufacturer’s specifications to what is experimentally achieved by the generators as 147% and 22% respectively. The variance of the outputs between thermoelectric generators was measured by comparing the maximum power output for the models in question over a sample size of four, it was found to be as much as 20% and 8% respectively.</p> <p>A full characterisation of the thermoelectric generators is performed on the two generator models to obtain the data as to their power output and thermal conductivity for the purpose of design of a waste energy harvesting device. The full characterisation was also used to validate the testing apparatus as a device capable for the use as a standardised method of characterising the performance of thermoelectric generation modules.</p> <p>A mechanistic model is created using the experimental characterisation data. This mechanistic model has the ability to accurately predict the voltage and current output of the thermoelectric generator models under any given temperatures and electrical loading condition with a minimum R-squared value of 0.94. The thermal conductivity is also found to be predictable using an established equation modified with an empirical constant.</p> / Master of Applied Science (MASc)

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

Les matériaux thermoélectriques en tant que générateurs d’électricité peuvent être utilisés dans de nombreux domaines tels que la conversion de la chaleur perdue des automobiles et des industries, le couplage avec le photovoltaïque, ou la génération de puissance par radioisotopes pour l’exploration spatiale. A ce jour, la plupart des éléments constitutifs des matériaux thermoélectriques proviennent de ressources rares et sont toxiques ce qui peut induire une pollution environnementale. Les siliciures ont montré qu’ils possèdent de bonnes performances thermoélectriques à haute température et n’ont pas les défauts sus mentionnés. Parmi les siliciures, les siliciures de manganèse riches en silicium MnSix, x variant de 1,71 à 1,75, sont particulièrement intéressants pour leurs propriétés thermoélectriques. Ces composés existent sous plusieurs formes tétragonales correspondant à Mn4Si7, Mn11Si19, Mn15Si26 et Mn27Si47. Dans cette thèse nous examinons d’un point de vue expérimental la stabilité de ces phases. L’étude a été réalisée pour des composés massifs et en films minces. La forme Mn4Si7 est celle qui semble être la plus intéressante pour les applications thermoélectriques, nous avons donc exploré différentes voies de synthèse pour ce composé. Des calculs théoriques utilisant la théorie de la fonctionnelle de la densité couplée à la théorie du transport de Boltzmann ont enfin permis de prédire les propriétés thermoélectriques de la forme Mn4Si7 substituée. La finalité de ces calculs est de trouver des substitutions d’atomes conduisant à une amélioration de l’efficacité thermoélectrique de ce composé. / Thermoelectric materials as electric power generators can be used in many fields, such as the conversion of automobile exhausting heat and industrial waste heat, solar photovoltaic-thermoelectric hybrid power generation, or RTG (Radioisotope thermoelectric generator) for deep space exploration. To date, most of the constituent elements of thermoelectric materials are scarce resource and are toxic, resulting in environmental pollution. Silicide materials have shown to exhibit good thermoelectric performances at high temperature without suffering from the aforementioned drawbacks. Among the silicide compounds, silicon-rich silicides MnSix, with x comprised between 1.71 and 1.75, are particularly interesting for their thermoelectric properties. These so-called higher manganese silicides (HMS) exhibit several tetragonal structures that correspond to Mn4Si7, Mn11Si19, Mn15Si26 and Mn27Si47. In this thesis, we examine from an experimental point of view the stability of these compounds. The investigations have been performed on both bulk and thin film materials. Mn4Si7 seems to be the most interesting HMS for thermoelectric applications; hence various synthesis routes have been explored for this compound. Finally, theoretical calculations, based on density-functional theory and Boltzmann’s transport theory, have allowed us to predict the thermoelectric properties of substituted Mn4Si7. The objectives were to find substitutional atoms leading to an improvement of the thermoelectric efficiency of Mn4Si7.

Oxide materials exhibit a wide variety of structures and properties. In particular, transition metal oxides tend to be highly stable while exhibiting a wide range of properties that can be used for numerous applications. This work focuses on investigating how the structures��� of 4d and 5d transition metal oxides influences their properties. Specifically oxides of Ru, Rh and Ir were investigated. A complete solid solution was found between isostructural Pb���Mn���O������ and Pb���Rh���O������. Pb���Rh���O������ shows a Verwey-type transition at 185 K. This transition remains with a 3 % substitution of Mn for Rh but disappears with a 4 % substitution of Mn for Rh. The structure was found to expand in the direction perpendicular to the layers of the structure, which is the c-axis, despite a contracting unit cell. Bi for Pb substitution in Pb���Mn���O������ was found to be limited as compared to in Pb���Rh���O������. Alkali metal substitution on the A-site of the orthorhombic perovskite SrRuO��� showed only low substitution levels were possible. Nonetheless, the substituted phases showed decreased ferromagnetic Curie temperatures, increased electrical resisitivity and relatively unchanged Seebeck coefficients. Thermoelectric studies of Sr[subscript 2-x]La[subscript x]CoRuO��� perovskite phases showed Sr���.���La���.���CoRuO��� with the best thermoelectric performance. This system showed possible correlations between cation ordering on the B-site and the charge carrier transport. A similar thermoelectric study of (RhV)[subscript 1+x]Ti[subscript 1-2x]O��� phases crystallizing in a disordered trirutile structure was done. Electron carriers were found to be dominant and dependent on Ti content. The electron carriers appear to become diminished at higher temperatures. Sr���IrO��� crystallizes in a K���NiF���-type structure. Effects of Ti, Fe and Co substitution for Ir were investigated. A complete Sr���Ir[subscript 1-x]Ti[subscript x]O��� solid solution was synthesized and characterized while limited solubility was found for Fe and Co substitutions. All substitutions showed a decrease in the c-cell parameter coupled with a decrease in octahedral tilting. All substitutions also showed a decrease in magnetic susceptibility and an increase in the paramagnetic effective moment was observed for Co and Fe doped samples. An incomplete solid solution was formed for Sr���Ti[subscript 1-x]Rh[subscript x]O��� phases; however effects of increased octahedral tilting with higher Rh content were observed. / Graduation date: 2013

The main focus of this work is the preparation, chemical and structural characterization along with the investigation of physical properties of intermetallic clathrates. Starting from the history of clathrate research, classification of clathrate types, their structural properties and possible application areas are evaluated in chapter 2. The methodologies of sample preparation and materials characterization as well as quantum chemical calculations are discussed in chapter 3. The complete characterization of Ba8Ge433 ( is a Schottky-symbol standing for vacancies),12-14 which is a parent compound for the variety of ternary variants, is the subject of chapter 4. Ba8Ge433 is a high temperature phase,12 which was prepared for the first time as single phase bulk material in this work.15, 16 In this way, the intrinsic transport properties could be investigated without influence of grain boundary and impurity effects. The transport behavior is analyzed at low and high temperatures and referred to the former results. In addition, crystal structure and vacancy ordering in terms of the reaction conditions are discussed. Chemical bonding in Ba8Ge433 is investigated by topological analysis of the electron localizability indicator and the electron density. Chapter 5 deals with the preparation, phase analysis, crystal structure and physical properties of BaGe5, which constitutes a new clathrate type oP60.17, 18 So far, two clathrate types were known in the binary system Ba – Ge, namely the clathrate cP124 Ba6Ge25,19-21 and the clathrate-I Ba8Ge433. Originally, BaGe5 was detected by optical and scanning electron microscopy within the grains of Ba8Ge433.12 Once the preparation of phase-pure Ba8Ge433 was achieved, it became possible to make detailed investigations of its decomposition along with the formation of BaGe5. A detailed theoretical and experimental analysis on the relation between crystal structure and physical properties of BaGe5 is presented. In chapter 6, a thorough structural characterization and the physical properties of clathrates in the system Ba – Ni – Ge is presented based on the subtle relation between the crystal structure containing vacancies and the thermoelectric properties. During the investigations in this system, a large single crystal was grown by Nguyen et al. 22, 23 from the melt with the composition Ba8Ni3.5Ge42.10.4. A systematic reinvestigation of the phase relations in this system was performed and the influence of different Ni content to the crystal structure and physical properties is evaluated. The Si-based ternary clathrate with composition Ba8–δNixySi46–x–y is the subject of chapter 7. The phase relations and the homogeneity range are established. The crystal structure taking into account vacancies in the framework is discussed. Physical properties of bulk pieces are analyzed and the results are related to the sample composition. In addition, first-principles electronic structure calculations are carried out to assess variations in the electronic band structure, phase stability and chemical bonding.24 Chapter 8 reports on the intermetallic compound Ba3Si4,25, 26 which was encountered during the investigations on the Ba – Ni – Si phase diagram. The discussion covers issues related to preparation, crystal structure, phase diagram analysis, electrical and magnetic properties, NMR measurements, quantum mechanical calculations and oxidation to nanoporous silicon with gaseous HCl. Besides my contributions to the NoE CMA, I studied under the Priority Program 1178 of Deutsche Forschungsgemeinschaft “Experimental electron density as the key for understanding chemical interactions” with the project of “Charge distribution changes by external electric fields: investigations of bond selective redistributions of valence electron densities”. Chapter 9 deals with the preparation of chalcopyrites ZnSiP2 and CuAlS2 for experimental charge density analysis. Both phases show semiconducting properties and have non-centrosymmetric structures with high space group symmetry as needed to investigate the structural changes induced by external electric field. In this chapter, I describe the preparation and the crystal structure analyses of ZnSiP2 and CuAlS2 including issues related to the data collection as well as the results of NMR investigation.

An increasing need for effective thermal sensors, together with dwindling energy resources, have created renewed interests in thermoelectric (TE), or solid-state, energy conversion and refrigeration using semiconductor-based nanostructures. Effective control of electron and phonon transport due to confinement, interface, and quantum effects has made nanostructures a good way to achieve more efficient thermoelectric energy conversion. This thesis studies the two well-known approaches: confinement and energy filtering, and implements improvements to achieve higher thermoelectric performance. The effect of confinement is evaluated using a 2D material with a gate and utilizing the features in the density of states. In addition to that, a novel controlled scattering approach is taken to enhance the device thermoelectric properties. The shift in the onset of scattering due to controlled scattering with respect to sharp features in the density of states creates a window shape for transport integral. Along with the controlled scattering, an effective utilization of Fermi window can provide a considerable enhancement in thermoelectric performance. The conclusion from the results helps in selection of materials to achieve such enhanced thermoelectric performance. In addition to that, the electron filtering approach is studied using the Wigner approach for treating the carrier-potential interactions, coupled with Boltzmann transport equation which is solved using Rode's iterative method, especially in periodic potential structures. This study shows the effect of rapid potential variations in materials as seen in superlattices and the parameters that have significant contribution towards the thermoelectric performance. Parameters such as period length, height and smoothness of such periodic potentials are studied and their effect on thermoelectric performance is discussed. A combination of the above two methods can help in understanding the effect of confinement and key requirements in designing a nanostructured thermoelectric device that has a enhanced performance.