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The Milazzo peninsula, North-Eastern Sicily, Italy, is the implantation site of potentially polluting anthropogenic activities. Among them, a refinery and a thermoelectric plant. An epidemiological study has shown a decrease of human health quality in the area, but there was no further research as to the reasons of this observation. The aim of this work is to better understand how the Milazzo peninsula's anthropogenic emissions impact the local human health and ecosystems. The Life Cycle Assessment calculating approach was chosen in order to study the consequences of the emissions resulting from the following local anthropogenic activities: the thermoelectric plant, the refinery, the road traffic, the illegal combustion of domestic waste. The Impact 2002+ and the ReCiPe 2008 global-scale models were chosen, as well as a site-specific approach. In order to conduct this site-specific calculation, Milazzo soils and seawater samples were gathered and the specific local parameters were deduced from their analyses. The global-scale results pointed out the waste combustion emissions and the thermoelectric plant as the main causes of the human health quality decrease, while the thermoelectric plant was pointed out as the anthropogenic activity causing the most environmental damages. The site-specific study applied to the soil and seawater ecotoxicity confirmed the important role of the thermoelectric plant's emissions in the damages upon the environment, especially the seawater. Moreover, the site-specific study also corrected the soil ecotoxic impact scores, showing the importance of both thermoelectric plant and illegal waste combustion contributions to the damaging of the environment. As a conclusion, LCA study as a whole enlightens and explains the previous observations of human health and ecosystem damages in the site of study while the site-specific study proved relevant in the peculiar area of Milazzo.

Les oxydes doubles lamellaires de cobalt et les oxydes de vanadium ont récemment suscité un vifintérêt suite à la découverte de leurs propriétés thermoélectriques prometteuses. Nos efforts visentà synthétiser de nouveaux composés dérivés de ces systèmes en utilisant la synthèse à l'étatsolide, l'échange d'ions et/ou les techniques hydrothermales. Afin de moduler et d'optimiser leurscaractéristiques thermoélectriques, nous avons ajusté la composition des oxydes de cobalt grâce àdes substitutions appropriées. Au sein du dioxyde de vanadium quasi-1D, nous avons considérétrois différentes structures polymorphes : M1, A et B. Nous avons exploré les différents systèmesen construisant l’ensemble des diagrammes de phases. Nous avons également étudié l'effet de lasubstitution du vanadium par le molybdène et le chrome sur la stabilité de ces structurespolymorphes et caractérisé leurs propriétés électroniques en relation avec les mécanismes detransition de phase. / Lamellar cobalt double oxides and vanadium oxides have recently attracted tremendous interestafter the discovery of their interesting thermoelectric properties. Our efforts aimed at synthesizingnovel related compounds using standard solid state, ion exchange and/or hydrothermaltechniques. In order to modulate and optimize their thermoelectric characteristics, we have tunedthe composition of cobalt double oxides by appropriate substitutions. In quasi 1D vanadiumoxides, the interplay between spin, charge and orbital degrees of freedom often leads toremarkable properties. Here we dealt with three different polymorphs of vanadium dioxide,namely M1, A and B. We explored the several novel systems by constructing systematic phasediagrams. We also studied the effect of Mo and Cr:V substitution on the stability of thesepolymorphs and characterized their electronic properties in relation with the structural phasetransition mechanisms. Finally, we explored their potentiality for thermoelectric applications.

[pt] Nesta tese foram estudados três sistemas nanoscópicos compostos de pontos quânticos (PQs). No primeiro deles foi analisada a denominada nuvem Kondo, ou a extensão da blindagem que os spins da banda de condução fazem do spin de uma impureza magnética embebida em uma matriz metálica e representada, no nosso caso, por um PQ. As propriedades da nuvem Kondo foram obtidas através da manifestação da ressonância Kondo na densidade de estados local nos sítios da matriz metálica e também através das correlações de spin entre o spin do elétron no PQ e os spins da banda de condução. Foi possível encontrar uma concordância entre as extensões da nuvem Kondo obtidas com ambos métodos. O segundo sistema estudado consiste em uma estrutura de três PQs alinhados e com o PQ central acoplado a dois contatos metálicos. Foi analisada a operação deste sistema como uma porta lógica quântica cujo funcionamento depende do estado de carga do PQ central. Foi feito um estudo dependente do tempo das propriedades do sistema e, em particular, da correlação dos spins dos PQs laterais. Mostramos que o efeito Kondo, refletido na condutância do sistema, pode ser uma ferramenta fundamental para conhecer o estado da porta quântica. Os primeiros dois sistemas foram tratados usando o método dos Bósons Escravos na aproximação de campo médio. Finalmente, foi estudado o transporte termoelétrico em um sistema de dois PQs quando um deles está acoplado a contatos metálicos unidimensionais. O sistema foi analisado no regime de resposta linear e não linear a um potencial externo no regime de bloqueio de Coulomb. Mostramos que a presença de ressonâncias Fano e de uma singularidade de Van-Hove na densidade de estados dos contatos unidimensionais perto do nível de Fermi são ingredientes fundamentais para o aumento da eficiência termoelétrica do dispositivo. O problema de muitos corpos foi resolvido na aproximação de Hubbard III que permite um estudo correto das propriedades de transporte deste sistema para T maior que TK, onde TK é a temperatura Kondo. / [en] In this thesis, were studied three nanoscopic quantum dot (QD) systems. First, the so-called Kondo cloud was analyzed, the extension of the conduction band spin screening of a magnetic impurity embedded in a metallic matrix and represented, in our case, by a QD. The Kondo cloud properties were obtained studying the way in which the local density of states of the metallic matrix sites reflects the Kondo resonance and also through the spin-spin correlations between the QD and the conduction band spins. It was possible to find a good agreement between the Kondo cloud extensions obtained using both methods. The second system consists of three aligned QDs with the central QD connected to two metallic leads. The operation of this system as a quantum gate was studied, which depends on the central QD charge. A time dependent study of the system properties and, in particular, of the lateral QDs spin correlation was developed. We showed that the Kondo effect, reflected in the conductance, could be a fundamental tool to measure the information contained in the quantum gate state. The first two systems were treated using the Slave Bosons Mean Field Approximation method. Finally, we studied the thermoelectric transport of a two QD system when one of them is connected to two onedimensional leads. The system was analyzed in the linear and nonlinear response to an external applied potential, always in the Coulomb blockade regime. It was found that the presence of Fano resonances and a Van-Hove singularity in the one-dimensional lead density of states near the Fermi level are fundamental ingredients to enhance thermoelectric efficiency. The many-body problem was treated in the Hubbard III approximation, which is a correct approach to study the transport properties for T greater than TK, where TK is the Kondo temperature.

La péninsule de Milazzo, au Nord-Est de la Sicile, en Italie, est le site d'implantation d'activités anthropiques potentiellement polluantes. Parmi elles, une raffinerie et une centrale thermoélectrique. Une étude épidémiologique a montré une diminution de la qualité de la santé humaine dans la zone, mais aucune recherche n'a approfondi les raisons de cette observation. Le but de ce travail est de mieux comprendre comment les émissions des activités anthropiques de la péninsule de Milazzo impactent la santé humaine à l'échelle locale ainsi que les écosystèmes. L'approche par l'Analyse du Cycle de Vie a été choisie afin d'étudier les conséquences des émissions provenant des activités anthropiques suivantes: la centrale thermoélectrique, la raffinerie, la circulation automobile, la combustion sauvage de déchets domestiques. Les modèles à l'échelle globale Impact2002+ et ReCiPe2008 furent choisis, ainsi qu'une approche site-spécifique. Afin de réaliser ces calculs à l'échelle site-spécifique, des échantillons de sols et d'eau marine provenant de Milazzo ont été rassemblés et les paramètres locaux spécifiques ont été déduits de leurs analyses. Les résultats à l'échelle globale on montré que la combustion des déchets ménagers et que la centrale thermoélectrique sont les activités anthropiques causant le plus de dommages environnementaux. L'étude site-spécifique appliquée à l'écotoxicité du sol et de l'eau de mer a confirmé l'importance du rôle des émissions de la centrale thermoélectrique dans les dommages sur l'environnement, en particulier sur l'eau de mer. De plus, l'étude site-spécifique a permis de corriger les scores d'impact du sol, montrant l'importance à la fois de la centrale thermoélectrique et de la combustion sauvage de déchets ménagers dans les dommages sur l'environnement. En conclusion, l'étude ACV a globalement montré et expliqué les observations précédentes concernant les dommages à la santé humaine et à l'environnement sur le site d'étude alors que l'étude site-spécifique s'est montrée pertinente pour la zone particulière de Milazzo. / The Milazzo peninsula, North-Eastern Sicily, Italy, is the implantation site of potentially polluting anthropogenic activities. Among them, a refinery and a thermoelectric plant. An epidemiological study has shown a decrease of human health quality in the area, but there was no further research as to the reasons of this observation. The aim of this work is to better understand how the Milazzo peninsula's anthropogenic emissions impact the local human health and ecosystems. The Life Cycle Assessment calculating approach was chosen in order to study the consequences of the emissions resulting from the following local anthropogenic activities: the thermoelectric plant, the refinery, the road traffic, the illegal combustion of domestic waste. The Impact 2002+ and the ReCiPe 2008 global-scale models were chosen, as well as a site-specific approach. In order to conduct this site-specific calculation, Milazzo soils and seawater samples were gathered and the specific local parameters were deduced from their analyses. The global-scale results pointed out the waste combustion emissions and the thermoelectric plant as the main causes of the human health quality decrease, while the thermoelectric plant was pointed out as the anthropogenic activity causing the most environmental damages. The site-specific study applied to the soil and seawater ecotoxicity confirmed the important role of the thermoelectric plant's emissions in the damages upon the environment, especially the seawater. Moreover, the site-specific study also corrected the soil ecotoxic impact scores, showing the importance of both thermoelectric plant and illegal waste combustion contributions to the damaging of the environment. As a conclusion, LCA study as a whole enlightens and explains the previous observations of human health and ecosystem damages in the site of study while the site-specific study proved relevant in the peculiar area of Milazzo.

O composto SbxCoSb3-x foi produzido em altas pressões e altas temperaturas em uma reação de auto-inserção a partir da escuterudita binária CoSb3. A reação de auto-inserção é caracterizada pelo colapso de átomos de Sb para o sítio 2a, no interior das cavidades formadas pelos átomos de Co e Sb na estrutura da escuterudita. A reação inversa, de desinserção de Sb, ocorre quando o composto SbxCoSb3-x é aquecido à pressão ambiente. O acompanhamento desta reação de desinserção por meio de medidas de calorimetria exploratória diferencial (DSC), difração de raios X (DRX) e de resistividade elétrica constitui o objetivo principal deste trabalho. A amostra de CoSb3 foi sintetizada conforme rota proposta pela literatura. A síntese foi confirmada por meio de DRX, e não foi observada a presença de fases contaminantes. Amostras cilíndricas da fase SbxCoSb3-x foram obtidas submetendo CoSb3 a pressões de 7,7 GPa e temperaturas de até 550ºC, com o auxílio de prensas hidráulicas e câmaras toroidais disponíveis no Laboratório de Altas Pressões e Materiais Avançados LAPMA no Instituto de Física da Universidade Federal do Rio Grande do Sul IF/UFRGS. A presença da fase SbxCoSb3-x foi comprovada por meio de análises de DRX. Para determinação da resistividade elétrica de amostras ricas de fase SbxCoSb3-x foi desenvolvido um sistema DC, aplicável a amostras cilíndricas de pequeno volume tal como as obtidas em altas pressões e altas temperaturas. A aferição do sistema foi feita através de medidas de resistividade elétrica de materiais de referência (NIST-SRM 1461 e NIST-SRM 8426). As medidas de DSC revelaram a presença de dois eventos térmicos. Um pico endotérmico foi observado em 118ºC e não está associado a alterações estruturais e nem a variações significativas na resistividade elétrica. O evento exotérmico, que inicia em 180ºC, constitui a assinatura da desinserção dos átomos de Sb do interior da escuterudita, como verificado por análises de DRX e medidas elétricas. Após aquecimento até 350ºC, a amostra rica na fase SbxCoSb3-x retorna à fase estável, CoSb3. A reação de desinserção obedece a uma cinética de primeira ordem, cuja entalpia de transição é de aproximadamente 50 J /g e uma energia de ativação de 83 kJ/mol. A resistividade elétrica à temperatura ambiente de amostras ricas em SbxCoSb3-x é cerca de dez vezes inferior à do CoSb3. Este resultado, aliado possivelmente a uma baixa condutividade térmica, sugere que a fase de auto-inserção SbxCoSb3-x pode constituir um material termoelétrico de alto desempenho. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-06-03T19:52:12Z No. of bitstreams: 1 Dissertacao Fernanda Miotto.pdf: 1202367 bytes, checksum: b66708b3e1d417eab6ba5104702a3458 (MD5) / Made available in DSpace on 2014-06-03T19:52:12Z (GMT). No. of bitstreams: 1 Dissertacao Fernanda Miotto.pdf: 1202367 bytes, checksum: b66708b3e1d417eab6ba5104702a3458 (MD5) / The compound SbxCoSb3-x was produced at high pressures and high temperatures in a self-insertion reaction from the binary skutterudite CoSb3. The self-insertion reaction is characterized by the collapse of Sb atoms to the 2a site, into the cage formed by the Co and Sb atoms in the skutterudite structure. The opposite reaction, i.e., Sb desinsertion, occurs when the SbxCoSb3-x compound is heated at room pressure. This desinsertion reaction was followed by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD) and electrical resistivity measurements, and its study constitutes the main objective of this work. The CoSb3 sample was synthesized as described in the literature. The synthesis was confirmed by XRD, and the presence of contaminant phases was not observed. Cylindrical samples of the SbxCoSb3-x phase were obtained by submitting CoSb3 at pressures of 7.7 GPa and temperatures up to 550ºC, with the aid of a toroidal high pressure cell available at the Laboratório de Altas Pressões e Materiais Avançados - LAPMA in the Instituto de Física of the Universidade Federal do Rio Grande do Sul - IF/UFRGS. The presence of the SbxCoSb3-x phase was confirmed by XRD analysis. In order to determine the electrical resistivity of samples rich in SbxCoSb3-x phase, a DC system was developed which is applicable to small volume cylindrical samples such as those obtained at high pressures and high temperatures. The calibration of the DC system was made by measurements of the electrical resistivity of reference materials (NIST-SRM 1461 and NIST-SRM 8426). The DSC measurements revealed the presence of two thermal events. An endothermic peak was observed at 118ºC which is not associated to structural changes neither significant variation in the electrical resistivity. The exothermic event that starts at 180ºC is the signature of the desinsertion of Sb atoms from the skutterudite cage, as verified by XRD analysis and electrical measurements. After heating to 350°C, the sample rich in the SbxCoSb3-x phase converts back to the stable phase, CoSb3. The desinsertion reaction follows a first-order kinetics, with a transition enthalpy of approximately 50 J/g and an activation energy of 83 kJ/mol. The electrical resistivity at room temperature of samples rich in SbxCoSb3-x is about ten times smaller than that of CoSb3. This result, along with a possible low thermal conductivity, suggests that SbxCoSb3-x may constitute a high performance thermoelectric material.

Due to the aggressive downscaling of the CMOS technology, power and current densities are increasing inside the chip. The limiting current conduction capacity(106 Acm−2)and thermal conductivity(201Wm−1K−1 for Al and 400 Wm−1K−1 for Cu) of the existing interconnects materials has given rise to different electro-thermal issues such a shot-spot formation, electromigration, etc. Exploration of new materials with high thermal conductivity and current conduction has thus attracted much attention for future integrated circuit technology. Among all the elemental materials, carbon nanomaterials (graphene and carbon nanotube) possess exceptionally high thermal (600-7000 Wm−1K−1) and current( ~108 -109 Acm−2)conduction properties at room temperature, which makes them potential candidate for interconnect materials. At the same time development of efficient energy harvesting techniques are also becoming important for future wireless autonomous devices. The excess heat generated at the hot-spot location could be used to drive an electronic circuit through a suitable thermoelectric generator. As the See beck coefficient of graphene is reported to be the highest among all elementary semiconductors, exploration of thermoelectric properties of graphene is very important. This thesis investigates the electrothermal and thermoelectric properties of metallic single walled carbon nanotube (SWCNT) and single layer graphene (SLG) for their possible applications in thermal management in next generation integrated circuits. A closed form analytical solution of Joule-heating equation in metallic SWCNTs is thus proposed by considering a temperature dependent lattice thermal conductivity (κ) on the basis of three-phonon Umklapp, mass-difference and boundary scattering phenomena. The solution of which gives the temperature profile over the SWCNT length and hence the location of hot-spot(created due to the self-heating inside the chip) can be predicted. This self-heating phenomenon is further extended to estimate the electromigration performance and mean-time-to-failure of metallic SWCNTs. It is shown that metallic SWCNTs are less prone to electromigration. To analyze the electro-thermal effects in a suspended SLG, a physics-based flexural phonon dominated thermal conductivity model is developed, which shows that κ follows a T1.5 and T−2 law at lower(<300 K) and higher temperature respectively in the absence of isotopes(C13 atoms). However in the presence of isotopic impurity, the behavior of κ sharply deviates from T−2 at higher temperatures. The proposed model of κ is found to be in excellent match with the available experimental data over a wide range of temperatures and can be utilized for an efficient electro-thermal analysis of encased/supported graphene. By considering the interaction of electron with in-plane and flexural phonons in a doped SLG sheet, a physics-based electrical conductance(σ) model of SLG under self-heating effect is also discussed that particularly exhibits the variation of electrical resistance with temperature at different current levels and matches well with the available experimental data. To investigate the thermoelectric performance of a SLG sheet, analytical models for See beck effect coefficient (SB) and specific heat (Cph) are developed, which are found to be in good agreement with the experimental data. Using those analytical models, it is predicted that one can achieve a thermoelectric figure of merit(ZT) of ~ 0.62 at room temperature by adding isotopic impurities(C13 atoms) in a degenerate SLG. Such prediction shows the immense potential of graphene in waste-heat recovery applications. Those models for σ, κ, SB and Cph are further used to determine the time evolution of temperature distribution along suspended SLG sheet through a transient analysis of Joule-heating equation under the Thomson effect. The proposed methodology can be extended to analyze the graphene heat-spreader theory and interconnects and graphene based thermoelectrics.

nÃo hà / O uso racional de recursos à pauta recorrente nas discussÃes acerca do desenvolvimento sustentÃvel e tem estimulado o projeto de equipamentos mais eficientes quanto ao consumo de energia elÃtrica. Agentes regulamentadores e certificadores estabelecem regras para o funcionamento e para a classificaÃÃo de eletrodomÃsticos quanto ao consumo de energia elÃtrica a fim de formalizar a relaÃÃo entre o desempenho dos mesmos e a manutenÃÃo indefinida dos recursos. Nesse contexto, lanÃa-se mÃo do projeto de um controlador preditivo baseado em modelo aplicado à regulaÃÃo da temperatura do reservatÃrio de Ãgua gelada de um refrigerador termoelÃtrico obedecendo as especificaÃÃes da norma internacional ANSI18 que determina condiÃÃes funcionais para bebedouros com refrigeraÃÃo mecÃnica incorporada, concomitantemente buscando atender aos requisitos para a certificaÃÃo ENERGY STAR quanto ao critÃrio de eficiÃncia energÃtica. Para tanto foram realizadas as etapas de i) Modelagem e IdentificaÃÃo do Processo: foi desenvolvido um modelo em termos de funÃÃo de transferÃncia do sistema de refrigeraÃÃo termoelÃtrico de fluidos atravÃs de modelagem fenomenolÃgica; foram realizados experimentos para a identificaÃÃo de parÃmetros de modelos discretos pelo mÃtodo caixa branca; foi desenvolvido critÃrio de seleÃÃo de modelo baseado na capacidade de simulaÃÃo e caracterÃsticas do resÃduo de simulaÃÃo; ii) Estudo do Controlador Preditivo Baseado em Modelo: foi projetado e implementado na planta um controlador preditivo baseado em um dos modelos parametrizados para regulaÃÃo da temperatura do reservatÃrio interno; foi analisado o desempenho do controlador segundo a norma regulamentadora; iii) Estudo da EficiÃncia do Controlador: foi analisado o desempenho do controlador quanto a capacidade do protÃtipo em atender aos requisitos que o qualificam à obtenÃÃo de certificado segundo critÃrio de eficiÃncia energÃtica para regulaÃÃo da temperatura interna do reservatÃrio e, por fim, realizado um estudo comparativo entre a estratÃgia de controle biestÃvel aplicada atualmente ao processo e a estratÃgia proposta. / The rational use of resources is a recurring theme in sustainable development discussions and has stimulated the development of more efficient electrical power consumption appliances. Regulators and Certifiers agencies set standards for the functionality requirements and for the electric power consumption classification of devices in order to formalize the relationship between performance and maintenance of these resources indefinitely. Thus a model based predictive controller was applied to a thermoelectric cooler to attain the international standard ANSI18 specifications for water cooler dispensers and to meet ENERGY STAR$ iny^{ extregistered}$ energy efficiency requirements. A phenomenological linear model was obtained and the respective parameters were identified by using least squares algorithm; experiments were performed to identify the parameters of the discrete transfer functions; a model criterion selection based on simulation capabilities and residue characteristics was developed; a model based predictive controller was designed and applied using one of the models identified; the controller performance was analyzed attending to the ANSI18 standard and according to energy performance certificates; a comparative study between the bistable control and the proposed strategy was made for performance analysis. Simulation and experimental tests have shown compromise between the simulation capability and residue characteristic criterion. The closed loop system behavior allowed energy saving in standby temperature regulating compared to thermostat control mode. The new control strategy achieved ENERGY STAR energy-efficiency criteria certification requirements infeasible for traditional regulation.

O composto SbxCoSb3-x foi produzido em altas pressões e altas temperaturas em uma reação de auto-inserção a partir da escuterudita binária CoSb3. A reação de auto-inserção é caracterizada pelo colapso de átomos de Sb para o sítio 2a, no interior das cavidades formadas pelos átomos de Co e Sb na estrutura da escuterudita. A reação inversa, de desinserção de Sb, ocorre quando o composto SbxCoSb3-x é aquecido à pressão ambiente. O acompanhamento desta reação de desinserção por meio de medidas de calorimetria exploratória diferencial (DSC), difração de raios X (DRX) e de resistividade elétrica constitui o objetivo principal deste trabalho. A amostra de CoSb3 foi sintetizada conforme rota proposta pela literatura. A síntese foi confirmada por meio de DRX, e não foi observada a presença de fases contaminantes. Amostras cilíndricas da fase SbxCoSb3-x foram obtidas submetendo CoSb3 a pressões de 7,7 GPa e temperaturas de até 550ºC, com o auxílio de prensas hidráulicas e câmaras toroidais disponíveis no Laboratório de Altas Pressões e Materiais Avançados LAPMA no Instituto de Física da Universidade Federal do Rio Grande do Sul IF/UFRGS. A presença da fase SbxCoSb3-x foi comprovada por meio de análises de DRX. Para determinação da resistividade elétrica de amostras ricas de fase SbxCoSb3-x foi desenvolvido um sistema DC, aplicável a amostras cilíndricas de pequeno volume tal como as obtidas em altas pressões e altas temperaturas. A aferição do sistema foi feita através de medidas de resistividade elétrica de materiais de referência (NIST-SRM 1461 e NIST-SRM 8426). As medidas de DSC revelaram a presença de dois eventos térmicos. Um pico endotérmico foi observado em 118ºC e não está associado a alterações estruturais e nem a variações significativas na resistividade elétrica. O evento exotérmico, que inicia em 180ºC, constitui a assinatura da desinserção dos átomos de Sb do interior da escuterudita, como verificado por análises de DRX e medidas elétricas. Após aquecimento até 350ºC, a amostra rica na fase SbxCoSb3-x retorna à fase estável, CoSb3. A reação de desinserção obedece a uma cinética de primeira ordem, cuja entalpia de transição é de aproximadamente 50 J /g e uma energia de ativação de 83 kJ/mol. A resistividade elétrica à temperatura ambiente de amostras ricas em SbxCoSb3-x é cerca de dez vezes inferior à do CoSb3. Este resultado, aliado possivelmente a uma baixa condutividade térmica, sugere que a fase de auto-inserção SbxCoSb3-x pode constituir um material termoelétrico de alto desempenho. / The compound SbxCoSb3-x was produced at high pressures and high temperatures in a self-insertion reaction from the binary skutterudite CoSb3. The self-insertion reaction is characterized by the collapse of Sb atoms to the 2a site, into the cage formed by the Co and Sb atoms in the skutterudite structure. The opposite reaction, i.e., Sb desinsertion, occurs when the SbxCoSb3-x compound is heated at room pressure. This desinsertion reaction was followed by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD) and electrical resistivity measurements, and its study constitutes the main objective of this work. The CoSb3 sample was synthesized as described in the literature. The synthesis was confirmed by XRD, and the presence of contaminant phases was not observed. Cylindrical samples of the SbxCoSb3-x phase were obtained by submitting CoSb3 at pressures of 7.7 GPa and temperatures up to 550ºC, with the aid of a toroidal high pressure cell available at the Laboratório de Altas Pressões e Materiais Avançados - LAPMA in the Instituto de Física of the Universidade Federal do Rio Grande do Sul - IF/UFRGS. The presence of the SbxCoSb3-x phase was confirmed by XRD analysis. In order to determine the electrical resistivity of samples rich in SbxCoSb3-x phase, a DC system was developed which is applicable to small volume cylindrical samples such as those obtained at high pressures and high temperatures. The calibration of the DC system was made by measurements of the electrical resistivity of reference materials (NIST-SRM 1461 and NIST-SRM 8426). The DSC measurements revealed the presence of two thermal events. An endothermic peak was observed at 118ºC which is not associated to structural changes neither significant variation in the electrical resistivity. The exothermic event that starts at 180ºC is the signature of the desinsertion of Sb atoms from the skutterudite cage, as verified by XRD analysis and electrical measurements. After heating to 350°C, the sample rich in the SbxCoSb3-x phase converts back to the stable phase, CoSb3. The desinsertion reaction follows a first-order kinetics, with a transition enthalpy of approximately 50 J/g and an activation energy of 83 kJ/mol. The electrical resistivity at room temperature of samples rich in SbxCoSb3-x is about ten times smaller than that of CoSb3. This result, along with a possible low thermal conductivity, suggests that SbxCoSb3-x may constitute a high performance thermoelectric material.

Dans une première partie, une nouvelle méthodologie, précise et hautement sensible de caractérisation des paramètres thermiques de liquides par radiométrie photothermique est ici présentée. Deux configurations expérimentales sont proposées. Elles ont été testées et validées avec des matériaux liquides usuels aux paramètres thermiques connus. Par la suite, cette démarche a été utilisée pour l'étude de polymères dispersés dans des cristaux liquides. Les propriétés thermiques dynamiques de chaque échantillon ont été mesurées en fonction de l'amplitude du champ électrique appliqué à une fréquence donnée aussi bien qu'en fonction de la fréquence du champ électrique à une amplitude fixe. Cette étude a montré que les propriétés thermiques étaient sujettes aux effets du champ de dépolarisation aux basses fréquences. La seconde partie de ce manuscrit décrit la nouvelle technique photothermique basée sur l'effet thermoélectrique. Cette technique est utile pour caractériser thermiquement les matériaux thermoélectriques sans avoir à recourir à un capteur extérieur pour mesurer le changement de température. Une étude théorique et expérimentale est présentée. Ces expériences ont été réalisées avec des composites polyaniline/nanotubes de carbone par mesure de la tension générée par l'échantillon thermoélectrique chauffé par un faisceau laser. Des mesures additionnelles à l'aide de la radiométrie infrarouge sur ces mêmes échantillons ont été entreprises et les résultats sont en bon accord avec ceux précédemment trouvés. Enfin, la possibilité d'utiliser les matériaux thermoélectriques comme capteur photothermique au travers d'une cavité résonnante à ondes thermiques est évoquée. / Primarily, newly developed, high sensitive and accurate methods for thermal characterization of liquids using photothermal radiometry are presented. Two experimental configurations are suggested, tested and validated with usual liquid materials. These methods are used to study polymer dispersed liquid crystal samples. Dynamic thermal properties of samples are analysed verses amplitude varying applied electric field with constant frequency as well as versus frequency varying electric field with constant amplitude. Our results clearly show the thermal properties of the samples are prone to depolarizing field effects at the lower frequencies of the applied electric field. The experimental results are modeled against existing theories to predict electric properties of the sample composites. Second part of the manuscript describes the development of a novel photothermal technique based on thermoelectric effect. This technique is particularly useful for thermally characterizing thermoelectric materials without using a separate sensor for measuring induced temperature changes. A theoretical and experimental study is presented. The experiments are done on polyaniline - carbon nanotube composite pellets by measuring Seebeck voltage generated by the samples upon heating by a modulated laser beam. Additional infrared radiometry experiments are done on the same samples and the results are in good agreement with those previously found. Later on, the possibility of photothermoelectric materials to be used as sensors for finding thermal transport properties of materials with a thermal wave resonant cavity is suggested.