According to different sources, from forty to sixty percent of the overall energy generated in the world today is squandered in waste heat. The existing energy conversion technologies are either close to their efficiency limits or too costly to justify their implementation. Therefore, the development of new technological approaches for waste heat recovery is highly demanded. The field of thermoelectrics can potentially provide an inexpensive, clean and efficient solution to waste heat underutilization, given that a new type of thermoelectric materials capable of meeting those requirements are available. This thesis reports on strategies to optimize a thermoelectric efficiency (ZT) of conducting polymers, more specifically poly(3,4-ethylenedioxythiophene) (Pedot). Conducting polymers constitute a special class of semiconductors characterized by low thermal conductivity as well as electrical conductivity and thermopower that can be readily modified by doping in order to achieve the best combination of thermoelectric parameters. Conducting polymers that have never previously been regarded as hypothetically compatible for thermoelectric energy conversion, can exhibit promising thermoelectric performance at moderate temperatures, which is a sought-after quality for waste heat recovery. A rather substandard thermoelectric efficiency of Pedot-Pss can be markedly improved by various secondary dopants whose addition usually improves polymer’s morphology accompanied by a drastic increase in electrical conductivity and, consequently, in ZT. In order to enable further enhancement in thermoelectric properties, the optimization of the charge carrier concentration is commonly used. The oxidation level of Pedot-Pss can be precisely controlled by electrochemical doping resulting in a tenfold increase of ZT. In contrast to Pedot-Pss, another conducting polymer Pedot-Tos exhibits superior thermoelectric performance even without secondary doping owning to its partially crystalline nature that allows for an improved electronic conduction. With the aid of a strong electron donor, positively doped Pedot-Tos gets partially reduced reaching the optimum oxidation state at which its thermoelectric efficiency is just four times smaller than that of Be2Te3 and the highest among all stable conducting polymers. The downsides associated with chemical doping of Pedot-Tos such as doping inhomogeneity or chemical dopants air sensitivity can be surmounted if the doping level of Pedot-Tos is controlled by acidity/basicity of the polymer. This approach yields similar maximum thermoelectric efficiency but does not necessitate inert conditions for sample preparation. Optimized Pedot-Tos/Pedot-Pss can be functionalized as a p-type material in organic thermogenerators (OTEG) to power low energy electronic devices. If printed on large areas, OTEGs could be used as an alternative technique for capturing heat discarded by industrial processes, households, transportation sector or any natural heat sources for electricity production.

When a temperature differential is applied across a semiconductor, a thermal voltage develops across it in response. The ratio of this thermal voltage to the applied temperature differential is the Seebeck coefficient, a transport coefficient that complements measurements of electrical and thermal conductivity. The physical interpretation of the Seebeck coefficient is the entropy per charge carrier divided by its charge and is hence a direct measurement of the carrier entropy in the solid state. This PhD thesis has three major outcomes. The first major outcome is a demonstration of how the Seebeck coefficient can be used as a tool to quantify the role of energetic disorder in organic semiconductors. To this end, a microfabricated chip was designed to perform accurate measurements of the Seebeck coefficient within the channel of the active layer in a field-effect transistor (FET). When measured within an FET, the Seebeck coefficient can be modulated using the gate electrode. The extent to which the Seebeck coefficient is modulated gives a clear idea of charge carrier trapping and the distribution of the density of states within the organic semiconductor. The second major outcome of this work is the observation that organic semiconducting polymers show Seebeck coefficients that are temperature independent and strongly gate voltage modulated. The extent to which the Seebeck coefficient is modulated in the polymer PBTTT is found to be larger than that in the polymer IDTBT. Taken together with conventional charge transport measurements on IDTBT, the voltage modulated Seebeck coefficient confirms the existence of a vanishingly small energetic disorder in this material. In the third and final outcome of this thesis, the magnitude of the Seebeck coefficient is shown to be larger for organic small molecules as compared to organic polymers. The basis for this is not yet clear. There are reports that such an observation is substantiated through a larger contribution from vibrational entropy that adds to the so called entropy-of-mixing contribution so as to boost the magnitude of the Seebeck coefficient in organic small molecules. As of now, this remains an open question and is a potential starting point for future work. The practical implications of this PhD thesis lie in building cost-effective and environmentally friendly waste-heat to useful energy converters based on organic polymers. The efficiency of heat to energy conversion by organic polymers tends to be higher than that for conventional semiconductors owing to the presence of narrow bands in organic polymer semiconductors.

An experimental investigation of the electronic transport properties of bismuth telluride nanocomposite materials is presented. The primary transport measurements are electrical conductivity, Seebeck coefficient and Hall effect. An experimental apparatus for measuring Hall effect and electrical conductivity was designed, constructed and tested. Seebeck coefficient measurements were performed on a commercial instrument. The Hall effect and Seebeck coefficient measurements are two of the most important tools for characterizing thermoelectric materials and are widely used in the semiconductor industry for determining carrier types, carrier concentration and mobility. Further, these transport parameters are used to determine the thermal to electrical conversion efficiency of a thermoelectric material. The Boltzmann transport equation was used to analyze the Seebeck coefficient, carrier mobility and electrical conductivity as a function of carrier concentration for eleven samples. The relationship between the electronic transport and material/composite composition is discussed.

O presente trabalho investiga o fenômeno termodifusivo em dispersões coloidais de nanopartículas magnéticas de óxidos de ferro em água (ferrofluidos), com a formação de dupla camada elétrica em torno das partículas. A estabilidade da partícula em solução é controlada pela concentração de íons. Ao estabelecer uma diferença de temperatura através da amostra líquida, ocorre o efeito de termodifusão (efeito Soret) das partículas e de íons em solução. Este efeito é o movimento das partículas para o lado frio ou quente do gradiente de temperatura. O acúmulo para um dos lados do gradiente de temperatura depende das características da solução. O efeito Soret de ferrofluidos em soluções ácidas e básicas é descrito a partir da determinação experimental das grandezas físicas envolvidas na difusão das partículas. O coeficiente Soret ST e o coeficiente de difusão são determinados em experimentos ópticos de lente de matéria, utilizando o aparato experimental de Varredura-Z, e de espalhamento Rayleigh forçado para termodifusão. Para investigar a resposta dos íons ao gradiente de temperatura, são realizadas medidas do potencial termoelétrico em uma célula termoelétrica, gerado a partir da difusão das cargas dispersas no líquido. O potencial superficial das partículas também é investigado experimentalmente, para descrever a interação das partículas com o campo termoelétrico. Os experimentos são realizados em função da temperatura da amostra e usados para descrever os resultados ST(T) das partículas, a partir de equações dos principais modelos teóricos. Os resultados mostram as diferenças e semelhanças do efeito Soret das nanopartículas em soluções ácidas e básicas, e que em ambos os casos a termodifusão de nanopartículas reflete o comportamento termodifusivo dos íons dispersos em solução. / This work investigates the thermal diffusion phenomena in colloidal dispersions of iron oxide magnetic nanoparticles dispersed in water (ferrofluid). The particles are stable in water due to electrical double layer around the particles, controlled by the ionic concentration. A temperature gradient throughout the ferrofluid sample causes the thermodiffusion (Soret effect) of dispersed particles and ions. This effect is the movement of particles to the cold or hot side of the temperature gradient. The particles migration for a given side depends on the characteristics of the sample. The Soret effect of ferrofluids in acidic and basic solutions is described by the experimental measurements of the physical parameters associated to particles diffusion. The Soret coefficient ST and the mass diffusion coefficient are measured in the matter lens experiment in the Z-scan experimental setup, and by the use of Thermal Diffusion Forced Rayleigh Scattering experiments. Concerning the ionic response to the temperature gradient the thermoelectric field generated by charges diffusion is measured in a thermoelectric cell. The surface potential of the particles is also measured to describe its interactions with the thermoelectric field. These experiments are made as function of the temperature of the sample and the results are applied to describe the ST(T) of particles by the use of equations from the main theoretical models. The results show differences and resemblances of the Soret effect in acidic and basic nanoparticles solutions. In both kind of solutions the thermodiffusion of nanoparticles is mainly ruled by the thermodiffusion of ions dispersed in solution.

The rapid increase in thermoelectric (TE) materials R&D is a consequence of the growing need to increase energy efficiency and independence through waste heat recovery. TE materials enable the direct solid-state conversion of heat into electricity, with little maintenance, noise, or cost. In addition, these compact devices can be incorporated into existing technologies to increase the overall operating efficiency. High efficiency TE materials would enable the practical solid-state conversion of thermal to electrical energy. Optimizing the interdependent physical parameters to achieve acceptable efficiencies requires materials exhibiting a unique combination of properties. This research reports two methods of thermoelectric enhancement: lattice strain effects in silicon-germanium alloy type I clathrates and the nanostructured enhancement of lead chalcogenides. The synthesis and chemical, structural, and transport properties characterization of Ba8Ga16SixGe30-x type I clathrates with similar Ga-to-group IV element ratios but with increasing Si substitution (4 < x < 14) is reported. Substitution of Si within the Ga-Ge lattice framework of the type I clathrate Ba8Ga16Ge30 results in thermoelectric performance enhancement. The unique dependences of carrier concentration, electrical resistivity, Seebeck coefficient, and carrier effective mass on Si substitution level, may imply a modified band structure with Si substitution. These materials were then further optimized by adjusting the Ga-to-group IV element ratios. Recent progress in a number of higher efficiency TE materials can be attributed to nanoscale enhancement. Many of these materials demonstrate increased Seebeck coefficient and decreased thermal conductivity due to the phenomenological properties of nanometer length scales. To satisfy the demands of bulk industrial applications requires additional synthesis techniques to incorporate nanostructure directly within a bulk matrix. This research investigates, for the first time, dense dimensional nanocomposites prepared by densifying nanocrystals synthesized employing a solution-phase reaction. Furthermore, the carrier concentration of the PbTe nanocomposites can be adjusted by directly doping the nanocrystals, necessary for power factor optimization. These materials were fully characterized using a low temperature TE transport measurement system, and exhibit enhanced power factors when compared to bulk polycrystalline PbTe with similar carrier concentrations.

Thermoelectric phenomena couple thermal and electric currents, allowing for solid-state conversion of heat into electricity. For decades Radioisotope Thermoelectric Generators have supplied power to NASA satellites and deep space probes. A more accessible application to consumers is the automotive industry's aspiration to incorporate thermoelectrics into active waste heat recovery systems. Higher power demands require these new thermoelectric devices to operate at higher temperatures and higher efficiencies, justifying new materials research. Recently, clathrates have gained interest for thermoelectric applications due to the unique properties they possess.These properties are directly related to their crystal structure. Therefore, clathrates are not only of interest from the standpoint of potential thermoelectric applications but are also of scientific interest as they presents an opportunity to investigate fundamental properties of group-IV elements in novel crystal structures. Clathrates are a class of novel open-structured materials in which molecules or atoms of one species are completely enclosed within a framework comprised of another species. This work presents a systematic investigation of the electrical properties of type I clathrate alloys, specifically Si-Ge alloys, for the first time. A series of Ba8Ga16-ySixGe30-x+y clathrates with varying Si content were synthesized and their structural and transport properties were studied. Two additional series of type I clathrates were also synthesized and characterized and their properties compared to those of the Si-Ge alloys in order to develop an understanding of their structure-property relationships. The increasing Si content correlates to a dramatic increase in Seebeck coefficient even as the resistivity decreases, suggesting the complex interaction between the Ba and the Si substitution within the Ga16Ge30 framework significantly modifies the band structure.

<p>The demand for more accurate measurements is increasing in today’s industry. One reason for this is to optimize production and thus maximize profits. Another reason is that in some cases government regulations dictate that supervision of certain parameters must be followed. At Preemraff Lysekil there are basically four reasons for measuring skin temperatures inside fired process heaters, namely; because of government regulations, in order to estimate the load of the fired process heater, to estimate the lifetime of the tubes inside the fired process heater and finally, to determine the need of decoking. However, only the first three of these reasons are applied to H2301/2/3. The current skin thermocouple design has been in use for many years and now the question of how well it measures surface temperature has risen. Furthermore a new weld-free design is under consideration to replace the old skin thermocouple design. Another question is therefore how well the new design can measure the surface temperature under the same operating conditions as the old one. In order to evaluate this, three–dimensional computer simulations were made of the different designs. As this thesis will show, the differences in calculated skin thermocouple temperature and calculated surface temperature is about the same for the two designs. However, the current design will show a lower temperature than the surface temperature, while the new design will show a higher temperature. Regarding the core of the skin thermocouple designs, namely the thermocouple, no hard conclusions can be drawn, although the industry appears to favor type ’N’ over type ’K’.</p>

The demand for more accurate measurements is increasing in today’s industry. One reason for this is to optimize production and thus maximize profits. Another reason is that in some cases government regulations dictate that supervision of certain parameters must be followed. At Preemraff Lysekil there are basically four reasons for measuring skin temperatures inside fired process heaters, namely; because of government regulations, in order to estimate the load of the fired process heater, to estimate the lifetime of the tubes inside the fired process heater and finally, to determine the need of decoking. However, only the first three of these reasons are applied to H2301/2/3. The current skin thermocouple design has been in use for many years and now the question of how well it measures surface temperature has risen. Furthermore a new weld-free design is under consideration to replace the old skin thermocouple design. Another question is therefore how well the new design can measure the surface temperature under the same operating conditions as the old one. In order to evaluate this, three–dimensional computer simulations were made of the different designs. As this thesis will show, the differences in calculated skin thermocouple temperature and calculated surface temperature is about the same for the two designs. However, the current design will show a lower temperature than the surface temperature, while the new design will show a higher temperature. Regarding the core of the skin thermocouple designs, namely the thermocouple, no hard conclusions can be drawn, although the industry appears to favor type ’N’ over type ’K’.

In this work, patterns in the behavior of different classes and types of thermoelectric materials are observed, and an alchemy that could help engineer a highly efficient thermoelectric is proposed. A method based on cross-correlation of Seebeck waveforms is also presented in order to capture physics of magnetic transition. The method is used to compute Curie temperature of LaCoO3 with an accuracy of 10K. In total, over 26 systems are analyzed, and 19 presented: Chalcogenides (PbSe, PbTe, Sb2Te3, Ag2Se), Skutterudites and Clathrates (CoSb3, SrFe4Sb12, Cd (CN)2, CdC, Ba8Ga16Si30*), Perovskites (SrTiO3, BaTiO3, LaCoO3, CaSiO3, Ce3InN*, YCoO3*), Half-Heuslers (ZrNiSn, NbFeSb, LiAlSi, CoSbTi, ScPtSb*, CaMgSi*), and an assorted class of thermoelectric materials (FeSi, FeSi2, ZnO, Ag QDSL*). Relaxation time is estimated from experimental conductance curve fits. A maximum upper bound of zT is evaluated for systems that have no experimental backing. In general, thermoelectric parameters (power factor, Seebeck coefficient and zT) are estimated for the aforementioned crystal structures. Strongly correlated systems are treated using LDAU and GGAU approximations. LDA/GGA/L(S)DA+U/GGA+U approach specific errors have also been highlighted. Densities of experimental results are estimated.

abstract: This study analyzes the thermoelectric phenomena of nanoparticle suspensions, which are composed of liquid and solid nanoparticles that show a relatively stable Seebeck coefficient as bulk solids near room temperature. The approach is to explore the thermoelectric character of the nanoparticle suspensions, predict the outcome of the experiment and compare the experimental data with anticipated results. In the experiment, the nanoparticle suspension is contained in a 15cm*2.5cm*2.5cm glass container, the temperature gradient ranges from 20 °C to 60 °C, and room temperature fluctuates from 20 °C to 23°C. The measured nanoparticles include multiwall carbon nanotubes, aluminum dioxide and bismuth telluride. A temperature gradient from 20 °C to 60 °C is imposed along the length of the container, and the resulting voltage (if any) is measured. Both heating and cooling processes are measured. With three different nanoparticle suspensions (carbon nano tubes, Al2O3 nanoparticles and Bi2Te3 nanoparticles), the correlation between temperature gradient and voltage is correspondingly 8%, 38% and 96%. A comparison of results calculated from the bulk Seebeck coefficients with our measured results indicate that the Seebeck coefficient measured for each suspension is much more than anticipated, which indicates that the thermophoresis effect could have enhanced the voltage. Further research with a closed-loop system might be able to affirm the results of this study. / Dissertation/Thesis / M.S. Mechanical Engineering 2010