Oxide ceramics have been increasingly researched for high temperature thermoelectric (TE) applications. SrTiO3 based materials are promising candidates due to its chemical and thermal stability. In this study, oxide ceramics of composition (1-x)SrTiO3-(x)La1/3NbO3 (0 smaller or equal to x smaller or equal to 0.3) were prepared by single-step solid state sintering in Ar/5%H2 at 1700 K. The density of all the samples prepared was above 90%. All the samples were predominantly single-phase compositions crystallised with a cubic structure in Pm ̅3m space group. The impact of oxygen deficiency, A-site vacancies and mixed oxidation states of Ti3+/Nb4+ on electrical and thermal transport properties was assessed. Optimum TE properties were obtained for x=0.2 (Sr0.8La0.067Ti0.8Nb0.2O(3-delta) = L2), which has 13.4% A-site vacancies. The ZT values improved from 0.2 to 0.27 at 1000 K, with an increase in sintering time from 8 hours to 48 hours, due to increased carrier concentration. Complex interplay of oxygen vacancies and excess donor substitution on A/B-sites of L2 (substituting 5-10% Sr/Ti with La/Nb) exhibited 35% improvement in ZT values, whilst maintaining the A-site vacancies and core-shell structures within grains, which reduced the thermal conductivity by ~50% compared to undoped SrTiO3 samples, due to strong phonon scattering. A facile method to incorporate metallic inclusions (2.5 wt% Fe/Cu) at grain boundaries in L2 ceramics is demonstrated. The modified compositions displayed a maximum ZT of ~0.37 at 1000 K for L2 samples containing metallic inclusions due to increased carrier concentration (5.5 x 10^21 carriers/cm^3) and carrier mobility (2.4 cm^2/(V.s).The addition of graphene/Graphene Oxide (GO) flakes in L2 ceramics has been investigated to improve the electrical conductivity of L2 composites without significantly increasing the thermal conductivity. Spark plasma sintering (SPS) of the composite powders at 1473 K and 50 MPa produced dense samples (>95% relative density) with a homogeneous dispersion of graphene/GO flakes, for loadings smaller or equal to 1.0 wt%. The effect of interaction and distribution of graphene/GO flakes within the ceramics on TE properties is investigated. The composite samples demonstrate anisotropic ZT values, with 20% improvement in the direction normal to the orientation of graphene flakes. A novel sintering method has been proposed which has strong industrial potential. The L2 based composites were sintered in Air at 1700 K (ramp rate: ±300 K/min), whilst samples were covered uniformly. Strong reducing conditions and evolution of secondary phases in the microstructure helped achieve, the very low electrical resistivity of ~3.0 x 10^(-6) ohm.m at room temperature. Secondary phases, sub-micron voids in the grains and A-site vacancies reduced the lattice thermal conductivity (~2.0 W/m.K), comparable to the lowest lattice thermal conductivity achievable (~1.5 W/m.K) at 1000 K and obtain a maximum ZT of 0.4 at 1000 K for L210G-Air/C composites.

[pt] Cerâmicas termomióticas vem despertando interesse devido a sua propriedade de apresentar, sob aquecimento, uma expansão térmica baixa, próxima a zero ou negativa. Essa propriedade é proveniente de uma vibração transversal do ânion, que resulta numa aproximação de átomos em determinadas direções. A família A2M3O12 (A = um cátion trivalente e M = Mo6 positivo ou W6 positivo) apresenta uma transição de fase de monoclínica para ortorrômbica, sendo somente a fase ortorrômbica que apresenta o comportamento termomiótico. Essa família, especificamente, vem sendo bastante pesquisada, pois possui a vantagem de permitir uma vasta flexibilidade química, sem mudar de estrutura cristalina e por consequência, permitir ajustes no coeficiente de expansão térmica de acordo com a aplicação a qual o material se destina. A expansão térmica próxima à zero pode levar a uma promissora alta resistência ao choque térmico. Esse trabalho teve como objetivo, estudar as propriedades térmicas e mecânicas do Al2W3O12 que possui baixa expansão térmica positiva com o objetivo de determinar sua resistência ao choque térmico pela figura de mérito de Hasselman. Para isso, todas as suas propriedades térmicas (expansão térmica e condutividade) e mecânicas (módulo de elasticidade e resistência mecânica) foram obtidas experimentalmente apresentando um valor promissor de 120K (comparável ao da safira) para resistência ao choque térmico pela figura de mérito de Hasselman sob condições severas de aquecimento. A partir desse resultado foi desenvolvido uma segunda pesquisa com o objetivo de refinar a microestrutura e aumentar a densidade relativa da cerâmica maciça do Al2W3O12 e assim incrementar suas propriedades mecânicas. Uma síntese por co-precipitação, seguida de uma prensagem isostática e uma sinterização desenvolvida em três etapas foram implementadas, obtendo-se um aumento de 91 porcento para 96 porcento na densidade relativa, com aumento de 19 porcento no módulo de elasticidade e de 35 porcento na dureza vickers se comparados aos resultados obtidos pela amostra sinterizada anteriormente pelo método convencional de sinterização em uma etapa. No terceiro estágio desta tese foi estudada a expansão térmica de uma novo material (In0,5(ZrMg)0,75Mo3O12) com promissora expansão térmica próxima a zero (10-7 K-1), a partir do cálculo da regra das misturas. O material foi sintetizado por evaportação total.e seu coeficiente de expansão térmica intrínseco determinado in situ por difração de Raios-X foi de 1,6x10-7 K-1 na faixa de temperatura de 100 a 500 graus Celsius, enquanto o coeficiente de expansão térmica maciço, medido por dilatometria, foi de 6,68 x 10-7 K-1, na faixa de temperatura de 100 a 800 graus Celsius. Esse material apresenta uma transição de fase de monoclínica para ortorrômbica na temperatura de 82 graus Celsius o que limita seu uso como material termomiótico em temperaturas abaixo de 100 graus Celsius. / [en] Thermomiotic ceramics have been arousing interest due to their property of presenting a low, near or zero thermal expansion under hearing. This property comes from a transverse vibration of the anion, which results in an approximation of atoms in certain crystallographic axes. The A2M3O12 family (A = a trivalent cation and M = Mo6 positive or W6 positive) presents a phase transition from monoclinic to orthorhombic, with only the orthorhombic phase exhibiting thermomiotic behavior. This family is widely researched since it has the advantage of allowing a wide chemical flexibility without changing the crystalline structure and consequently allowing adjustments in the coefficient of thermal expansion according to the application, which the material is intended. Thermal expansion close to zero can lead to a promising high thermal shock resistance. This work aimed to study the thermal and mechanical properties of Al2W3O12 that has low thermal expansion with the goal of determining its thermal shock resistance by the Hasselman figure of merit. For this, all its thermal properties (thermal expansion and conductivity) and mechanical (Young modulus and mechanical strength) were obtained experimentally and presented a promising value of 120K (comparable to sapphire) for thermal shock resistance by the figure of merit of Hasselman under severe heating. A second research was developed with the goal of refining the microstructure and increasing the relative density of the Al2W3O12 bulk ceramics and thus increasing its mechanical properties. A synthesis by co-precipitation, folled by an isostatic pressing and a three steps sintering were carried out, obtaining an increase of 91 percent to 96 percent in the relative density, with increase of 19 percent in modulus of elasticity and 35 percent in Vickers hardness when compared to conventional sintering. The thermal expansion of a new material (In0,5(ZrMg)0,75Mo3O12) with promising thermal expansion close to zero (10-7 K1), calculated by mixing rule was studied in the third chapter of this thesis. The material was synthesized by total evaporation. Its intrinsic thermal expansion coefficient was determined in situ by X-ray diffraction and presented a value of 1.6x10-7 K-1 in the temperature range of 100 to 500 Celsius degrees, while the coefficient of expansion of the bulk obtained by dilatometry, was 6.68 x 10-7 K-1, in the temperature range of 100 to 800 Celsius degrees. This material presents a phase transition from monoclinic to orthorhombic at 82 Celsius degrees, which limits its use as thermomiothic material at temperatures above 100 Celsius degrees.

Monitoring the working environment of laboratories and industries for pollutants is of primary concern to ensure the healthiness of working personnel. Semiconducting metal oxides (SMOs) are sensitive to the gas ambience and can be tuned for sensing purpose. As SMOs are not selective, an array of sensors with differential selectivity may resolve to great extent. The objective of the thesis is to understand the physicochemical properties and gas sensing characteristics of Cr1-xFexNbO4. Applying principal component analysis to the sensor response data either for selection of features or for differentiation of analysts is also of concern. Preparation of Cr1-xFexNbO4, phase characterization, lattice parameters estimation, morphological and micro chemical analysis (SEM & EDX), electrical characterization by direct current (DC & AC) in the temperature range of 423 K to 573 K, weighted magnetic moment of iron and chromium deduced from susceptibility measurements, spin nature of iron and surface compositions of different valences of chromium and iron deduced from X-ray photoelectron spectroscopy of are presented. The wide dynamic range hydrogen sensing characteristics of CrNbO4 bulk pellets at different temperatures along with the cross-sensitivity towards NH3, NOx(NO+NO2) and PG (petroleum gas) are investigated. The preparation of Cr1-xFexNbO4 thick and thin films by screen-printing and PLD are also presented. The thick films are tested at different temperatures towards hydrogen. The n-type or p-type nature of thick films towards hydrogen with varying iron concentration in Cr1-xFexNbO4 is reported. The thin films are characterized for phase formation, morphology by XRD, SEM and AFM. XPS performed surface characterization. Electrical resistance measurements at different temperatures and preliminary experiments on hydrogen sensing are presented. The probable hydrogen sensing mechanism of CrNbO4 was revealed by X-ray photoelectron spectroscopy. The experimentally observed reduction in metal ion oxidation states upon interacting with hydrogen is best illustrated by Kröger Vink notation. Principal component analysis was applied for three different types of studies: i) The fit parameters of the transient response of CrNbO4 thick films towards hydrogen are analyzed for finding out the better feature for calibration, ii) Different thick films of CrNbO4, Cr0.5Fe0.5NbO4 and FeNbO4 operated at various temperatures for testing H2 and VOCs are analyzed for redundancy in sensor behaviour and iii) Cr0.8Fe0.2NbO4 thick films are studied for sensing H2, NH3 and their mixtures and usefulness of PCA in resolving them in PC-space. In addition, H2 and VOCs are tested at different temperatures and redundancy in temperature is deduced to construct a sensor array with a minimum number of sensors. Finally, a sensor array consisting of Cr0.8Fe0.2NbO4 thick films, operating at different temperatures is built, and qualitative discrimination of analysts in PC-space is demonstrated. Finally, the major findings of the present investigations and suggestions for future aspects of experimentation are provided