The thermoelectric properties of bismuth telluride based thermoelectric (TE) materials are well-characterized, but comparatively little has been published on the thermomechanical properties. In this paper, dynamic mechanical analysis (DMA) and differential scanning calorimetry data for bismuth telluride based TE materials is presented. The TE materials' tan delta values, indicative of viscoelastic energy dissipation modes, approached that of glassy or crystalline polymers, were greater than ten times the tan delta of structural metals, and reflected the anisotropic nature of TE materials. DMA thermal scans showed changes in mechanical properties versus temperature with clear hysteresis effects. These results showed that the application of DMA techniques are useful for evaluation of thermophysical and thermomechanical properties of these TE materials.

No description available.

The combustion of ultra-lean fuel to air mixtures provides an efficient way to convert the chemical energy of hydrocarbons into useful power. Conventional burning techniques of a mixture have defined flammability limits beyond which a flame cannot self-propagate due to heat losses. Matrix stabilized porous medium combustion is an advanced technique in which a solid porous matrix within the combustion chamber accumulates heat from the hot gaseous products and preheats incoming reactants. This heat recirculation extends the standard flammability limits and allows the burning of ultra-lean fuel mixtures, conserving energy resources, or the burning of gases of low calorific value, utilizing otherwise wasted resources. The heat generated by the porous burner can be harvested with thermoelectric devices for a reliable method of generating electricity for portable electronic devices by the burning of otherwise noncombustible mixtures. The design of the porous media burner, its assembly and testing are presented. Highly porous (~80% porosity) alumina foam was used as the central media and alumina honeycomb structure was used as an inlet for fuel and an outlet for products of the methane-air combustion. The upstream and downstream honeycomb structures were designed with pore sizes smaller than the flame quenching distance, preventing the flame from propagating outside of the central section. Experimental results include measurements from thermocouples distributed throughout the burner and on each side of the thermoelectric module along with associated current, voltage and power outputs. Measurements of the burner with catalytic coating were obtained for stoichiometric and lean mixtures and compared to the results obtained from the catalytically inert matrix, showing the effect on overall efficiency for the combustion of fuel-lean mixtures

Climate change is a subject of deep distress in today’s world. Over dependence on hydrocarbon has resulted in serious environmental problems. Rising sea level, global warming and ozone layer depletion are the mainstream of any discuss world over. The collective goal of cutting carbon emission by the year 2020has prompted the search for clean, alternative energy sources. This effort are already yielding good reward as other forms of energy such as solar, wind, nuclear and hydro have received huge investment and renew interest over the past decade. Thermoelectric materials over the past decades have been tipped to replace conventional means of power generations as these materials have the ability to convert heat to electrical energy and vice versa. They are simple, have no moving parts and use no greenhouse gases. But the major drawback of these materials is their low conversion efficiency. Hence there is a need to enhance the efficiency of thermoelectric material to fulfill their undeniable potentials. A parameter called the thermoelectric figure of merit, ZT defines the efficiency of a thermoelectric material. ZT relates three non-mutually exclusive transport properties namely Seebeck coefficient, electrical conductivity and thermal conductivity. Efficient thermoelectric material should possess high Seebeck coefficient, high electrical conductivity and low thermal conductivity. Hence, one of the interesting ideas in the area of thermoelectric research is the concept of designing a bulk material with high density of phonon scattering centers so has to reduce the lattice contribution to thermal conductivity but at the same time have minimum impact oncharge carriers. This is usually achieved by utilizing interphase and grain boundaries which are localized defects to scatter phonons. The volume fraction of the grain/interphase boundaries can be control through phase modification and microstructure design. This thesis is centered on Bi-Sb-Te systems which are the present room temperature state of the earth thermoelectric material. The investigation revolves around developing a new kind of microstructure in the well-studied Bi-Sb-Te system that shows tremendous potential as a means to reduce lattice contribution to thermal conductivity. The idea of having both p and n-type thermoelectric material preferably from the same material was also a motivation in our investigation. The thesis isdivided into six chapters. The first chapter introduces the concept of thermoelectricity i.e. the direct conversion of thermal energy into electricity. The physics involved and contribution of individual to the science of thermoelectricity were enumerated. Efficiency, optimization and material selection for better thermoelectric performance were briefly enumerated. Prospective materials that are currently been investigated for better thermoelectric properties were also mentioned. The structure of the Bi-Sb-Te system which is the focus of this thesis is present in this chapter including doping effect on the thermoelectric performance of the system as well as the various methods present been employed to improve the thermoelectric properties of the system. Finally the chapter enumerates the scope and object of the present thesis. The different experimental procedures adopted in the present thesis arediscussed in chapter 2. The details of different processing routes followed to synthesize flame-melted ingots, flame-melted + low temperature milled (cryo milling) + spark plasma sintering (SPS) alloy and flame-melted + melt spinning + spark plasma sintering (SPS) alloy, are discussed followed by the various structural and functional characterization techniques. The unique advantage of the spark plasma sintering techniques over the conventional sintering method was talked out in detail. The structural characterizations performed on the synthesized alloys include XRD, SEM and whilethe functional characterizations comprised of Hall measurement, Seebeck coefficient, electrical resistivity and thermal conductivity measurements. Thermoelectric properties of selected composition of Bi-Sb-Te synthesized via flame-melting are presented in chapter 3.Detail study of four analyzed compositions namelyBi24Sb20Te56, Bi20Sb12Te69, Bi16Sb5Te79 and Bi29Sb11Te60resulted in four unique microstructure and different volume fraction of primary and secondary phases. The resultant morphologies of the microstructure were observed to have influence the thermoelectric behavior corresponding to each composition. The sole influence of anti-structural defects on the conductivity type and the role of microstructure morphologies and length scale were understood in this chapter. Samples with segregated Te and a solid solution BiSbTe3(eutectic morphology) form an n-type thermoelectric material while samples with only solid solution BiSbTe3 forms a p-type thermoelectric material. Pair of n-type and p-type material was obtained without the introduction of external dopant.The pair shows good compatibility factorsuitable for thermoelectric device. In chapter 4, the thermoelectric properties of four selected composition of Bi-Sb-Te synthesized via low temperature milling plus spark plasma sintering is addressed. The analyzed compositions are as follows Bi24Sb20Te56, Bi18Sb11Te71, Bi17Sb6Te77, and Bi28Sb15Te57 respectively. The effect of low temperature milling combine with the prospect of minimum grain growth of spark plasma sintering on the thermoelectric properties of the selected compositions were determined. Samples with eutectic morphology which would otherwise scatter charge carriers were observed to have the highest carrier mobility as a result of high volume fraction of Te phase which serves as a donor injecting excess electrons into the system. The impact of small grain size was observed on the transport properties of the sample Bi28Sb15Te57 with the highest electrical resistivity, the best Seebeck coefficient and the lowest thermal conductivity. Pair of n-type and p-type material was obtained without the introduction of external doping elements. The pairshows good compatibility factor suitable for segmented thermoelectric device. Chapter 5 narrates the thermoelectric properties of four compositions namely Bi30Sb13Te58, Bi23Sb13Te65, Bi18Sb5Te77 and Bi23Sb20Te58subjected to melt spinning plus spark plasma sintering.High cooling rate obtained during melt spinning process was observed in this chapter to cause a shift of composition which resulted in a microstructure morphology with eutectic colonies that is predominantly Te rich. These Te rich colonies in the sample Bi30Sb13Te58 was observed to change the conductivity type of the sample from an otherwise p-type to n-type while also aiding bipolar conduction which was detrimental to the overall thermoelectric performance of the alloy. Segregated Te in the form of eutectic morphology helps to inject excess electron into the bulk of the sample Bi23Sb13Te65 and Bi18Sb5Te77hereby increases the observed electrical conductivity which by virtue of the microstructure morphology is expected to be low. As a result of the processing routes, all four compositions in this chapter shown-type conductivity. Chapter 6 presents the summary of the important conclusions drawn from this work.

Thermoelectric materials are playing an increasingly significant role in the global effort to develop sustainable energy technologies. Consequently, the demand for materials with greater thermoelectric efficiency has stimulated the development of state-of-the-art interstitially doped skutterudite-based materials. However, since intermetallics are often embrittled by interstitial substitution, optimal skutterudite-based device design, manufacture, and operation require thorough assessment of the fracture toughness of interstitially doped skutterudites. This research determines whether the fracture toughness of skutterudites is sacrificed upon interstitial doping. Both pure and interstitially doped cobalt antimonide skutterudites were synthesized via a solid-state technique in a reducing atmosphere with antimony vapor. Their crystal structures were analyzed by X-ray diffraction, and then sintered by hot uniaxial pressing into dense pellets. The electronic properties of the sintered samples were characterized. Fracture toughness of the pure Co₄Sb₁₂ and interstitially doped In₀.₁Co₄Sb₁₂ samples was evaluated by the Vicker's indentation technique and by loading beam-shaped singe-edge vee-notched bend specimens (SEVNB) in 4-point flexure. The intrinsic crack-tip toughness of both materials was determined by measuring the crack-tip opening displacements (COD's) of radial cracks introduced from Vicker's indentations. The intrinsic crack-tip toughness of both pure Co₄Sb₁₂ and interstitially doped In₀.₁Co₄Sb₁₂ were found to be similar, 0.523 and 0.494 MPa√m, respectively. The fracture toughness of both pure and interstitially doped skutterudites, derived from SEVNB specimens in 4-point flexure were also found to be statistically identical, 0.509 and 0.574 MPa√m , respectively, and are in agreement with the intrinsic crack-tip toughness values. However, the magnitude of the toughness was found to be much lower than previously reported. Moreover, fracture toughness values derived from Vickers's indentations were found to be misleading when compared to the results obtained from fracture toughness tests carried out on the micronotched (SEVNB) specimens loaded in 4-point flexure. / Graduation date: 2012

Thermoelectric materials are playing a larger role in the global effort to develop diverse, efficient, and sustainable energy technologies: primarily through power-generating thermoelectric modules. The principal components of thermoelectric modules are solid-state thermoelectric materials – typically heavily doped semiconductors – that convert heat directly into electricity. However, this conversion efficiency is too low to supplant traditional energy technologies – severely limiting the distribution of clean and sustainable thermoelectric energy technologies. Efforts to enhance thermoelectric efficiency, which have been underway for decades, have been slow to realize appreciable gains in thermoelectric efficiency. However, a key advance in improving efficiency – the New Paradigm in thermoelectric material research – has been the development of thermoelectric nanocomposites. Thermoelectric nanocomposites show improved efficiency; however, they are often synthesized from highly toxic elements via energetically intense and costly synthesis procedures. Therefore, this research focuses on the discovery and development of a novel procedure for synthesizing thermoelectric nanocomposites – attrition enhanced nanocomposite synthesis – from open cage-like skutterudite-based materials. With further optimization, high-performance power-generating thermoelectric materials can be produced via this technique. Therefore, attrition-enhanced nanocomposite synthesis may play a small, though instrumental, role in achieving sustainable electrical power. / Graduation date: 2012 / Access restricted to the OSU Community at author's request from Jan. 6, 2012 - Jan. 6, 2013

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

Cette thèse présente une étude de l'élaboration et des propriétés structurales, ainsi que des propriétés électriques, des couches minces de matériaux thermoélectriques de type Mg2Si-Mg2Sn. Les couches minces polycristallines du composé Mg2Sn et des solutions solides Mg2Si1-xSnx ont été réalisées sur plusieurs types de substrat, à température ambiante, par la technique de dépôt par co-pulvérisation assistée par plasma micro-onde multi-dipolaire. L'influence des paramètres de dépôt sur les propriétés structurales et électriques des couches élaborées a été étudiée. Ainsi, la composition chimique des couches a été parfaitement contrôlée par le biais de la polarisation indépendante des cibles des éléments constituants. La composition de phase, ainsi que la microstructure des couches, ont été trouvées dépendant de la pression de dépôt, de la distance entre des cibles et le substrat, de la puissance micro-onde et de la configuration du réacteur de dépôt. Ces propriétés structurales, à leur tour, ont un fort impact sur les propriétés électriques des couches déposées. Les couches minces Mg2Sn dopé en Ag, déposées avec la condition de dépôt optimale, ont présenté un facteur de puissance à température ambiante comparable à celui des matériaux actuellement utilisés. Les couches minces des solutions solides Mg2Si1-xSnx présentent, pourtant, des facteurs de puissance encore modestes résultant notamment des faibles conductivités électriques. / This thesis presents a study of the deposition and structural as well as electrical properties of thin films of thermoelectric materials Mg2Sn-Mg2Si. Polycrystalline thin films of the Mg2Sn compound and solid solutions Mg2Si1-xSnx were deposited on several types of substrate at room temperature, by co-sputtering assisted by microwave plasma. The influence of deposition parameters on structural and electrical properties of deposited films was studied. Thus, the chemical composition of layers was fully controlled by the means of the independent polarization of target of constituent elements. Phase composition and microstructure of deposited films were found depending on the deposition pressure, on the distance between targets and the substrate, on the microwave power, as well as on the configuration of the deposition reactor. These structural properties, in turn, have a strong impact on the electrical properties of the deposited films. Mg2Sn thin films doped with Ag, deposited under optimal condition, presented a power factor at room temperature comparable to conventional thermoelectric materials. Thin films of solid solutions Mg2Si1-xSnx present, however, power factors still modest due in particular to low electrical conductivities.

Avec la demande sans cesse renouvelée de matériaux éco-compatibles pour l’électronique de demain, les polymères conducteurs se sont imposés comme une alternative intéressante aux matériaux déjà existants. Ils doivent leur popularité principalement à leurs propriétés électriques, optoélectroniques, thermo-chromiques, luminescentes et mécaniques, couplées à leur bonne processabilité et leur faible impact environnemental. Parmi eux, le poly(3,4-ethylenedioxythiophene) (PEDOT) est certainement le plus connu est le plus utilisé. De nombreuses études se sont focalisées sur l’optimisation de sa conductivité électrique et des progrès remarquables ont été réalisés. Cependant, la compréhension fine de la relation structure/propriétés de ce matériau reste à élucider. C’est ainsi que dans le cadre de cette thèse nous avons décidé de plusieurs objectifs qui sont (1) la synthèse de PEDOT hautement conducteurs à structure contrôlée et optimisée, (2) l’étude des propriétés électriques, structurales et de transport électroniques dans ces PEDOT, (3) l’étude de leurs propriétés thermoélectriques et (4) l’étude de leur stabilité sous différentes conditions afin de valider leurs potentielles applications. Ainsi, après une revue de la littérature sur le PEDOT, nous étudions l’amélioration de la conductivité électrique du PEDOT:OTf et du PEDOT:Sulf, qui atteint dorénavant des valeurs à hauteur de 5400 S cm-1. Différentes techniques de caractérisation nous ont permis de mener une étude exhaustive de leurs propriétés électriques et structurales ainsi que des mécanismes de transport électronique qui en découlent. Nous nous sommes ensuite intéressés à deux de leurs propriétés thermoélectriques, l’effet Joule et l’effet Seebeck, le premier pour des applications en chauffage et le deuxième pour la récupération d’énergie. L’utilisation pour la première fois du PEDOT comme film chauffant flexible transparent est d’ailleurs présentée. On démontre par exemple que PEDOT:Sulf présente une résistance carrée de 57 Ω sq-1 pour 87.8 % de transparence et qu’une température de 138 °C peut être atteinte lorsqu’on applique 12 V. Cette thèse se conclut sur l’étude de la stabilité de nos matériaux de PEDOT sous différentes atmosphères ainsi que l’étude des mécanismes de dégradation. / With the rising demand of flexible, low cost and environmentally friendly materials for future technologies, organic materials are becoming an interesting alternative to already existing inorganic ones. Organic photovoltaics, organic light emitting diodes, organic field effect transistors, organic thermoelectricity, organic transparent electrodes are all evidences of how organic materials are sought for tomorrow. Materials which can fulfill the requirements specifications of future technologies are conducting polymers, which owe their popularity to their outstanding electrical, optoelectronic, thermochromic, lighting and mechanical properties. Moreover, they exhibit good processability even on flexible substrates and low environmental impact. Poly(3,4-ethylenedioxythiophene) (PEDOT) is certainly the most known and most used conducting polymer because it is commercially available and shows great potential for organic electronics. Studies dedicated to PEDOT films have led to high conductivity enhancements. However, an exhaustive understanding of the mechanisms governing such enhancement is still lacking, hindered by the semi-crystalline nature of the material itself. In such a context, this thesis has four objectives which are (1) the synthesis of PEDOT materials with an optimized and controlled structure to enhance the electrical properties, (2) the thorough characterization of the as-synthesized PEDOT in order to understand the charge transport mechanisms, (3) the study of their thermoelectric properties and (4) the study of their stability under different environments and stresses. Thus, after a literature review on PEDOT materials, we present the enhancement of the electrical conductivity of PEDOT:OTf and PEDOT:Sulf up to 5400 S cm-1 via a structure and dopant engineering, and then thoroughly study their electrical and electronic transport properties. Subsequently, two thermoelectric properties of PEDOT are investigated, namely its resistive Joule heating ability and its Seebeck effect, for both heating and energy harvesting applications. A novel application of PEDOT as flexible transparent heater is demonstrated in the first case. PEDOT:Sulf for example exhibited a sheet resistance of 57 Ω sq-1 at 87.8 % transmittance and reached a steady state temperature of 138 °C under 12 V bias. Finally, this thesis is concluded with the ageing and stability of our PEDOT based materials under different environmental stresses. While PEDOT is stable under mild conditions, heavy degradations can occur under harsh conditions. The degradation mechanisms are then investigated in this last part.

Submitted by Kamila Costa (kamilavasconceloscosta@gmail.com) on 2015-08-06T14:48:56Z No. of bitstreams: 1 Dissertação - Zeane V Borges.pdf: 2189307 bytes, checksum: 3fce099edb43ceed11ff4ab744e1f3f5 (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-08-07T14:07:07Z (GMT) No. of bitstreams: 1 Dissertação - Zeane V Borges.pdf: 2189307 bytes, checksum: 3fce099edb43ceed11ff4ab744e1f3f5 (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-08-07T14:08:30Z (GMT) No. of bitstreams: 1 Dissertação - Zeane V Borges.pdf: 2189307 bytes, checksum: 3fce099edb43ceed11ff4ab744e1f3f5 (MD5) / Made available in DSpace on 2015-08-07T14:08:30Z (GMT). No. of bitstreams: 1 Dissertação - Zeane V Borges.pdf: 2189307 bytes, checksum: 3fce099edb43ceed11ff4ab744e1f3f5 (MD5) Previous issue date: 2015-06-08 / FAPEAM - Fundação de Amparo à Pesquisa do Estado do Amazonas / The nanostructured SnSe2 alloy was produced by Mechanical Alloying technique and their structural, thermal and optical properties were investigated by x-ray diffraction (XRD) combined with Rietveld Method (RM), differential scanning calorimetry (DSC), absorbance measurements and photoacoustic absorption spectroscopy (PAS). After characterized in the as milled conditions, the sample was annealed at 450˚C in order to evaluate the influence of the interfacial component in their physical properties. The XRD measurements allowed structurally characterize the samples, as well quantify the volume fractions occupied by crystalline and interfacial components. The DSC measurements showed that the melting process of SnSe2 phase, occurs in two-step for both samples. The UV–Vis absorption spectrum showed direct allowed transitions for milled and annealed samples, with band gap of 1.02 eV and 1.48 eV, respectively. Moreover, electronic transition of type direct forbidden was found in the sample annealed with optical band gap of 0.94 eV. PAS measurements provided the thermal diffusivity (𝛼𝑠) for both samples. A reduction of 45% in the thermal diffusivity value of milled sample was observed, when compared with the annealed sample. / A liga nanoestruturada SnSe2 foi produzida pela técnica Mechanical Alloying e suas propriedades estruturais, térmicas e ópticas foram investigadas por difração de Raios X (DRX) combinado com o Método de Rietveld (MR), calorimetria diferencial de varredura (DSC), medidas de absorbância óptica e espectroscopia de absorção fotoacústica (PAS). Após caracterizada nas condições como moída, a amostra foi tratada termicamente na temperatura de 450˚C a fim de avaliar, a influência da componente interfacial nas suas propriedades físicas. As medidas de DRX permitiram caracterizar estruturalmente as amostras, bem como quantificar as frações volumétricas ocupadas pelas componentes cristalina e interfacial. Medidas de DSC mostraram que o processo de fusão da fase SnSe2, ocorre em duas etapas para ambas as amostras. Os espectros de absorção UV-Vis mostraram transições diretas permitidas para as amostras moída e tratada termicamente, com energias de band gap de 1.02 eV e 1.48 eV, respectivamente. Além disso, transição eletrônica do tipo proibida direta foi encontrada na amostra tratada com energia de band gap de 0.94 eV. Medidas de PAS forneceram o valor da difusividade térmica (𝛼) para ambas as amostras. Uma redução de aproximadamente 45% no valor da difusividade térmica da amostra moída, quando comparada com a amostra tratada termicamente, foi observada.