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Ceramic zinc stannate, Zn(_2)SnO(_4), was prepared from 1SnO(_2):2ZnO mixture using powders of the highest commercially available purity. The solid state reaction between the ZnO and the SnO(_2), thought to be an evaporation-recondensation mechanism, was found to start at ~ 900 ˚C (12 hours heating, rate 5 ˚C min(^-1)). However, the reaction did not go to completion in the timescale of the experiment unless the temperature was raised to~1300 C. In this case mono-phase, polycrystalline Zn(_2)SnO(_4) was produced, as confirmed by X-ray diffraction (XRD), scanning electron microscopy and energy dispersive X-ray analysis (EDAX). Further evidence for these reaction temperatures was obtained from thermal analysis experiments. As-sintered, Zn(_2)SnO(_4) was insulating (σ — 10(^19) Ω(^-1) cm(^-1)) although it could be made conductive, by a reduction heat-treatment. This entailed refiring the sintered pellets of Zn(_2)SnO(_4) in an atmosphere of mixture gas (25% H(_2) + 75% N(_2)) at ~ 450 ˚C for 14 hours (heating rate of 10 C min(^-1)). This reduced the conductivity to values of σ~1 x 10(^-2) Ω(^-1) cm(^-1) . XRD failed to reveal any changes in the phase of the material after the reduction treatment. Several dopants were investigated, the most successful of which was in, using a vapour phase method. Doping with In this way gave a significant change in the colour from white to dark grey together with a reduction in electrical resistivity, without recourse to further heating treatments. No change in the usual phase of the Zn(_2)SnO(_4) was detected. Doping with group V oxides, such as Nb(_2)O(_5), V(_2)O(_5) etc, produced changes in the colour from white to dark grey, but no reduction in the resistivity, unless further heating treatments were carried out in reducing ambients. When high concentrations of Nb were introduced an additional phase, possibly Nb(_2)Sn(_2)O(_7) was observed by XRD. Thin film Zn(_2)SnO(_4) was prepared by Electron Beam Evaporation using Zn2Sn04 sintered powder as the evaporant material. The thin films were deposited onto glass substrates, at a range of substrate temperatures between room temperature and 250 ˚C. XRD was used to confirm the formation of Zn(_2)SnO(_4), and provide estimates for the grain size, which varied from 20 to 25 nm. RHEED studies indicated that the grain size increased as the substrate temperature was increased. SEM revealed that the thin films were flat and uniform, with no cracks. The optical transmission of the thin films was about 88% for films deposited at 200 ˚C, but decreased significantly as the substrate temperature was decreased. The spectral dependence of complex refractive index (n&k) suggested that true thin film formation did not take place until the substrate temperature exceeded ~ 150 ˚C, and that the material was apparently a direct gap semiconductor with a band gap energy of ~1.95 eV. It was found that the main carrier transportation mechanism for doped, un- doped, and thin films of Zn(_2)SnO(_4) was variable range hopping, with a temperature dependence of the form exp(To/T)'^\ This result was consistent with Hall effect measurements, where high, temperature independent carrier concentrations of about 10(^17) cm(^-3) were obtained, along with low values of carrier mobility ( ~ 1 cm(^2) v(^-1) sec(^-1)) that obeyed the same temperature dependence as the conductivity, [exp(To/T)(^1/4)].

The study of ferroelectric LiNbO<SUB>3</SUB> and LiTaO<SUB>3</SUB> doped with transition metals involves the characterisation of LiNbO<SUB>3</SUB>/LiTaO<SUB>3</SUB> solid solutions in the systems Li<SUB>2</SUB>O-Nb<SUB>2</SUB>O<SUB>5</SUB>-M<SUB>x</SUB>O<SUB>y</SUB> and Li<SUB>2</SUB>O-Ta<SUB>2</SUB>O<SUB>5</SUB>-M<SUB>x</SUB>O<SUB>y</SUB> (M = Cr, Mn, Fe, Co, Ni, Cu). Compounds were made by solid state reaction at temperatures between 1000 and 1500°C, depending on the system studied. The emphasis of this work is on the characterisation of the defect structure of LiNbO<SUB>3</SUB>/LiTaO<SUB>3</SUB> solid solutions using phase diagram determination, X-ray and neutron powder diffraction, EXAFS, ESR and optical spectroscopy. The valence of the incorporated cations was studied by magnetic measurements. The electrical properties of these materials have been investigated using AC impedance spectroscopy. It can be shown that the physical properties of LiNbO<SUB>3</SUB> and LiTaO<SUB>3</SUB> depend strongly on the defects in the structure which can be controlled by purposeful doping with other cations. Structural refinements of the X-ray and neutron powder diffraction data have shown that the defects arising from nonstoichiometry are accommodated by vacancies created on the Li site. This affects the structure when doped with third cations, giving rise to complex substitution mechanisms Spectroscopic studies have shown that the dopants (Cr<SUP>3+</SUP>, Mn<SUP>2+</SUP>/Mn<SUP>3+</SUP>, Co<SUP>2+</SUP>, Ni<SUP>2+</SUP>, Cu<SUP>+</SUP>, Cu<SUP>2+</SUP>) are shifted from the central octahedral position towards the adjacent empty octahedron. The electrical properties of LiNbO<SUB>3</SUB> and LiTaO<SUB>3</SUB>, measured by AC impedance spectroscopy, depend strongly on the dopant content: the conductivity generally rises, whereas the activation energy for the electrical conductivity drops with increasing dopant concentration. The microstructure of electroceramics can also be probed by AC impedance spectroscopy and it was shown that the texture of all samples was bad due to poor sintering of the pellets. Longer sintering times did not improve the quality of the ceramics which exhibit a large pore size distribution. An important aspect for future work would be the quality improvement of LiNbO<SUB>3</SUB>/LiTaO<SUB>3</SUB> based ceramics.

NKN doped samples, (100-x)NKN-xSBN (0 ≤ x ≤ 10) were produced using the conventional mixed oxide route with 0.45 wt% Fe2O3 sintering aid (xSBNF). After 20-24 hours mixing, samples were calcined at 850°C and sintered at 1100–1140°C (± 180°C/hour) for 4 hours. By XRD 4 mol% SBN was found to be the solubility limit for single phase structure. By SEM, second phases were visible when 2 ≤ x ≤ 4; their structure was subsequently shown to be tungsten bronze type (TBT). 2-4 SBNF samples were high density, over 96% theoretical. For x = 0, TC = 457°C, TO-T = 234°C, Pr = 22 μC/cm2 and EC = 16.5 kV/cm. TC was found to decrease by 14.7°C and TO-T by 9.0°C per 1 mol% addition SBN. 2SBNF was the optimal formulation in terms of microstructure and electrical properties, with average grain size 3 μm, Pr = 25 μC/cm2 and EC = 8.8 kV/cm, ρ = 4.7 kΩm and Q = 1.16 eV. This material comprised approximately 90% orthorhombic and 10% tetragonal phases coexisting. Pseudo-cubic lattice parameters are a’ = c’ = 3.947180 Å, and b’ = 3.999996 Å for orthorhombic phase; the tetragonal has a’ = c’ = 3.989798 Å, and b’ = 3.975777 Å.Synchrotron XRD studies were undertaken as a function of temperature on 99.5NKN-0.5CuO + 0.6 wt% Nb2O5 solid and powder samples. The data were Rietveld refined. The solid sample underwent two polymorphic phase transitions at 300°C and 515°C; the latter was between two tetragonal phases: lattice parameters for the tetragonal phase (300-520°C) were a’ = c’ = 4.99557 Å, and b’ = 4.0363 Å; high temperature tetragonal (>500°C) exhibited a’ = c’ = 4.9519 Å, and b’ = 4.4941 Å. The powder sample of the same formulation exhibited more, smaller transformations. It was only orthorhombic at temperatures <140°C with a’ = c’ = 4.10680 Å, and b’ = 4.02620 Å. Above 140°C both orthorhombic and tetragonal phases were present. Another significant transformation occurred at 360°C where the structural unit cell parameters changed significantly. Parameter lengths are provided. P-E data was characterised by Pr = 19.9 μC/cm2 and EC = 13.5 kV/cm. Synchrotron X-ray diffraction analysis of 94 NKN-6LiTaO3 showed that tetragonal phase was present at 20-390°C, although an orthorhombic phase was identified at 20-200°C and again at 340-390°C just before the cubic transition temperature at 390°C. This is a new observation for NKN. A new and simple method for tape casting was developed to reduce powder wastage, enabling thick films of 50 μm to be cast. The reactive templated grain growth (RTGG) method was employed to orient 95NKN-5LiNbO3 and 94NKN-6LiNbO3 samples; CuO was utilised as a sintering aid. Pre-cursor BNN and NN template particles were produced using the molten salt synthesis (MSS) method, using a salt to oxide ratio of 1:1. Resulting NN particles were 15 μm wide and 0.5 μm thick. Eight layered 6LN + 0.4 wt% tapes produced using 10 wt% template particles resulted in 210 μm thick tapes with 67% orientation when sintered at 1150°C. Resulting properties include TC = 440ºC and TO-T = 70ºC, 25 kΩ resistance and capacitance 21.6 pF.

Compósitos cerâmicos planares de titanato zirconato de bário, BaTi1-xZrxO3, foram produzidos e os efeitos da quantidade de Zr4+ em suas propriedades funcionais foram estudados. As amostras foram fabricadas pelo método convencional de processamento cerâmico e pela técnica de deposição de fitas cerâmicas a partir de BaTi1-xZrxO3 com x=0, 0,05, 0,1, 0,15 e 0,2 sintetizados pelo método hidrotermal e pelo método dos precursores poliméricos. Foram realizadas caracterizações estrutural (difração de Raios X pelo método do pó e espectroscopia Raman), composicional (espectroscopia por dispersão de energia), microestrutural (microscopia eletrônica de varredura, ensaios de dilatometria) e funcional (permissividade elétrica, coeficiente piezoelétrico d33, coeficiente piroelétrico e histerese ferroelétrica). Além disso, a regra da mistura de fase foi utilizada para prever a permissividade elétrica dos compósitos e as tensões mecânicas internas e seus efeitos na permissividade elétrica e na temperatura de Curie de policristais de BaTiO3 foram simulados. As análises dos dados e as discussões foram realizadas considerando o modelo fenomenológico de Devonshire, a modificação de Forsbergh deste modelo para incluir efeitos de tensões mecânicas bidimensionais e o modelo de policristal tetragonal de BaTiO3 sugerido por Buessem. Os resultados mostram a existência de tensões residuais bidimensionais que surgem após o resfriamento dos compósitos devido às diferenças nos coeficientes de expansão térmica das fases constituintes. Os métodos de obtenção das amostras afetaram o tamanho final dos grãos e as espessuras das interfaces dos compósitos, sendo que, em geral, eles são menores e mais finos nas fitas cerâmicas homogêneas do que nas correspondentes cerâmicas homogêneas. Os compósitos apresentaram deslocamento da Tc para maiores temperaturas e aumento do grau de difusividade da transição. A presença das tensões mecânicas residuais e as características microestruturais, juntamente com os modelos utilizados, explicam qualitativamente a permissividade elétrica obtida. Concluí-se que a quantidade de Zr4+ modifica o comportamento das camadas durante a sinterização e altera o coeficiente de dilatação. Estas mudanças geram tensões mecânicas residuais que afetam a microestrutura e as propriedades funcionais dos compósitos. Portanto, a produção de compósitos cerâmicos ferroelétricos deve considerar a correlação existente entre microestrutura e tensões residuais para que suas propriedades sejam otimizadas. / Planar BaTi1-xZrxO3 ceramic composites had their functional properties investigated. These composites were obtained by the conventional ceramic processing technique and by tape casting technique. Furthermore, BaTi1-xZrxO3 x=0, 0.05, 0.1, 0.15 and 0.2 were synthesized by the polymeric precursors method and by the hydrothermal synthesis to study the synthesis influences and to study the effect of Zr4+ on the functional properties of the composites. Structural characterization (X-Ray powder diffraction and Raman spectroscopy), compositional analysis (energy dispersive X-Ray spectroscopy), microestrutural evaluation (scanning electron microscopy, dilatometry measurements) and functional properties characterization (electrical permittivity, piezoelectric coefficient d33, pyroelectric coefficient and ferroelectric hysteresis) were performed. Furthermore, the composites electrical permittivity was predicted by the simple mixture and the internal mechanical stress distribution and it´s effects on both, electrical permittivity and Curie´s temperature (Tc) of BaTiO3 polycrystals, were simulated. The analyses and discussions were supported by 1- Devonshire´s phenomenological theory, 2- Forsbergh´s modification to Devonshire´s theory to include the two-dimensional stress effects on Tc and 3- Buessem´s BaTiO3 tetragonal polycrystal model. The results show that the sintered composites present two-dimensional residual stresses after cooling due to the constrained sintering of the layers and their thermal expansion coefficient mismatch. The methods of sample preparation led to differences in grain size and interface thickness, with the homogeneous ceramic tapes presenting smaller grain sizes and thinner thickness than the conventional homogeneous ceramics. On the other hand, the composites showed a Tc shift to higher temperatures, a more diffuse phase transition and residual mechanical stresses. Concluding, the Zr4+ substitution of Ti4+ modifies the layer´s sintering behavior and their thermal expansion coefficient. These changes lead to microstructure modifications that affect the functional properties of planar BaTi1-xZrxO3 composites. Thus, the design of ferroelectric composites should take into consideration the correlations between microstructure and residual stresses in order to optimize their functional properties.

abstract: Because of their favorable ionic and/or electronic conductivity, non-stoichiometric oxides are utilized for energy storage, energy conversion, sensing, catalysis, gas separation, and information technologies, both potential and commercialized. Charge transport in these materials is influenced strongly by grain boundaries, which exhibit fluctuations in composition, chemistry and atomic structure within Ångstroms or nanometers. Here, studies are presented that elucidate the interplay between macroscopic electrical conductivity, microscopic character, and local composition and electronic structure of grain boundaries in polycrystalline ceria-based (CeO2) solid solutions. AC impedance spectroscopy is employed to measure macroscopic electrical conductivity of grain boundaries, and electron energy-loss spectroscopy (EELS) in the aberration-correction scanning transmission electron microscope (AC-STEM) is used to quantify local composition and electronic structure. Electron diffraction orientation imaging microscopy is employed to assess microscopic grain boundary character, and links these macro- and nanoscopic techniques across length scales. A model system, CaxCe1-xO2-x-δ, is used to systematically investigate relationships between nominal Ca2+ concentration, grain boundary ionic conductivity, microscale character, and local solute concentration. Grain boundary conductivity varied by several orders of magnitude over the composition range, and assessment of grain boundary character highlighted the critical influence of local composition on conductivity. Ceria containing Gd3+ and Pr3+/4+ was also investigated following previous theoretical work predicting superior ionic conductivity relative to state-of-the-art GdxCe1-xO2-x/2-δ. The grain boundary conductivity was nearly 100 times greater than expected and a factor four enrichment of Pr concentration was observed at the grain boundary, which suggested electronic conduction that was cited as the origin of the enhanced conductivity. This finding inspired the development of two EELS-based experimental approaches to elucidate the effect of Pr enrichment on grain boundary conductivity. One employed ultra-high energy resolution (~10 meV) monochromated EELS to characterize Pr inter-bandgap electronic states. Alternatively, STEM nanodiffraction orientation imaging coupled with AC-STEM EELS was employed to estimate the composition of the entire grain boundary population in a polycrystalline material. These compositional data were the input to a thermodynamic model used to predict electrical properties of the grain boundary population. These results suggest improved DC ionic conduction and enhanced electronic conduction under AC conditions. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016

Compósitos cerâmicos planares de titanato zirconato de bário, BaTi1-xZrxO3, foram produzidos e os efeitos da quantidade de Zr4+ em suas propriedades funcionais foram estudados. As amostras foram fabricadas pelo método convencional de processamento cerâmico e pela técnica de deposição de fitas cerâmicas a partir de BaTi1-xZrxO3 com x=0, 0,05, 0,1, 0,15 e 0,2 sintetizados pelo método hidrotermal e pelo método dos precursores poliméricos. Foram realizadas caracterizações estrutural (difração de Raios X pelo método do pó e espectroscopia Raman), composicional (espectroscopia por dispersão de energia), microestrutural (microscopia eletrônica de varredura, ensaios de dilatometria) e funcional (permissividade elétrica, coeficiente piezoelétrico d33, coeficiente piroelétrico e histerese ferroelétrica). Além disso, a regra da mistura de fase foi utilizada para prever a permissividade elétrica dos compósitos e as tensões mecânicas internas e seus efeitos na permissividade elétrica e na temperatura de Curie de policristais de BaTiO3 foram simulados. As análises dos dados e as discussões foram realizadas considerando o modelo fenomenológico de Devonshire, a modificação de Forsbergh deste modelo para incluir efeitos de tensões mecânicas bidimensionais e o modelo de policristal tetragonal de BaTiO3 sugerido por Buessem. Os resultados mostram a existência de tensões residuais bidimensionais que surgem após o resfriamento dos compósitos devido às diferenças nos coeficientes de expansão térmica das fases constituintes. Os métodos de obtenção das amostras afetaram o tamanho final dos grãos e as espessuras das interfaces dos compósitos, sendo que, em geral, eles são menores e mais finos nas fitas cerâmicas homogêneas do que nas correspondentes cerâmicas homogêneas. Os compósitos apresentaram deslocamento da Tc para maiores temperaturas e aumento do grau de difusividade da transição. A presença das tensões mecânicas residuais e as características microestruturais, juntamente com os modelos utilizados, explicam qualitativamente a permissividade elétrica obtida. Concluí-se que a quantidade de Zr4+ modifica o comportamento das camadas durante a sinterização e altera o coeficiente de dilatação. Estas mudanças geram tensões mecânicas residuais que afetam a microestrutura e as propriedades funcionais dos compósitos. Portanto, a produção de compósitos cerâmicos ferroelétricos deve considerar a correlação existente entre microestrutura e tensões residuais para que suas propriedades sejam otimizadas. / Planar BaTi1-xZrxO3 ceramic composites had their functional properties investigated. These composites were obtained by the conventional ceramic processing technique and by tape casting technique. Furthermore, BaTi1-xZrxO3 x=0, 0.05, 0.1, 0.15 and 0.2 were synthesized by the polymeric precursors method and by the hydrothermal synthesis to study the synthesis influences and to study the effect of Zr4+ on the functional properties of the composites. Structural characterization (X-Ray powder diffraction and Raman spectroscopy), compositional analysis (energy dispersive X-Ray spectroscopy), microestrutural evaluation (scanning electron microscopy, dilatometry measurements) and functional properties characterization (electrical permittivity, piezoelectric coefficient d33, pyroelectric coefficient and ferroelectric hysteresis) were performed. Furthermore, the composites electrical permittivity was predicted by the simple mixture and the internal mechanical stress distribution and it´s effects on both, electrical permittivity and Curie´s temperature (Tc) of BaTiO3 polycrystals, were simulated. The analyses and discussions were supported by 1- Devonshire´s phenomenological theory, 2- Forsbergh´s modification to Devonshire´s theory to include the two-dimensional stress effects on Tc and 3- Buessem´s BaTiO3 tetragonal polycrystal model. The results show that the sintered composites present two-dimensional residual stresses after cooling due to the constrained sintering of the layers and their thermal expansion coefficient mismatch. The methods of sample preparation led to differences in grain size and interface thickness, with the homogeneous ceramic tapes presenting smaller grain sizes and thinner thickness than the conventional homogeneous ceramics. On the other hand, the composites showed a Tc shift to higher temperatures, a more diffuse phase transition and residual mechanical stresses. Concluding, the Zr4+ substitution of Ti4+ modifies the layer´s sintering behavior and their thermal expansion coefficient. These changes lead to microstructure modifications that affect the functional properties of planar BaTi1-xZrxO3 composites. Thus, the design of ferroelectric composites should take into consideration the correlations between microstructure and residual stresses in order to optimize their functional properties.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Neste trabalho, foram investigadas as propriedades estruturais e dielÃtricas da fase monoclÃnica da cerÃmica ferroelÃtrica Na2Nb4O11 com adiÃÃo de diÃxido de titÃnio (TiO2) e PentÃxido de vanÃdio (V2O5) nas proporÃÃes de 2, 5 e 10% em massa. Os pÃs Na2Nb4O11 foram produzidos pelo mÃtodo convencional de reaÃÃo em estado sÃlido. ApÃs a calcinaÃÃo, as amostras foram prensadas na forma de pastilhas cilÃndricas e, em seguida, sinterizadas. O estudo da estrutura e da composiÃÃo das amostras foi feito atravÃs de difraÃÃo de raios-X e Refinamento Rieteveld e um estudo da morfologia foi realizado atravÃs de Microscopia EletrÃnica de Varredura. As medidas de densidade foram obtidas atravÃs da picnometria. A caracterizaÃÃo dielÃtrica foi realizada na faixa de radiofrequÃncias e de micro-ondas. Em ambos os casos, foram realizados um estudo das propriedades em relaÃÃo à variaÃÃo da temperatura para possÃvel aplicaÃÃo em dispositivos que atuam em RadiofrequÃncia e Microondas. O objetivo principal desse trabalho foi obter ressoadores dielÃtricos cerÃmicos com permissividade dielÃtrica alta, baixas perdas dielÃtricas e estabilidade tÃrmica, pois essas propriedades sÃo necessÃrias para as aplicaÃÃes em filtros e antenas dielÃtricas. Nas medidas realizadas em temperatura ambiente de 25ÂC obtivemos um alto valor da permissividade dielÃtrica (&#949;âr = 129.29 ) com o NN2V ( 2% de V2O5) e um valor da tangente de perda, relativamente baixo ( tan&#948; = 3.25x10-2 ) em 1 MHz. Na temperatura de 400ÂC e numa frequÃncia fixa de 1 MHz, foi obtido um alto valor da permissividade dielÃtrica com &#949;âr= 358.23 e um valor de perda dielÃtrica em torno de 3,49 x10-1 para amostra NN2Ti. A medida do coeficiente de temperatura da frequÃncia de ressonÃncia (&#964;f) mostrou a possibilidade de atingir a estabilidade tÃrmica (&#964;f = 0) com o aumento do nÃvel de adiÃÃo de V2O5. Para a amostra NN00, obtivemos um &#964;f= -3378,42 ppm/ÂC. Com a adiÃÃo do V2O5, este valor vai se aproximando do zero e atinge &#964;f = -1348,618ppm/ÂC para o NN10V. As medidas na faixa de micro-ondas foram obtidas utilizando-se o mÃtodo Hakki-Coleman. Uma simulaÃÃo numÃrica foi realizada com cada amostra, verificando-se a reciprocidade com os dados experimentais. Neste estudo obtivemos uma cerÃmica NN10V, Ãtil para a aplicaÃÃo em dispositivos de antenas omnidirecionais de baixo ganho.

The thermoelectric properties and microstructure of two families of misfit type layered structure cobaltites were investigated for thermoelectric applications. Firstly, Bismuth strontium cobaltite ceramics with the formulations Bi2+xSr2Co2Oy (x=0, 0.1 and 0.2), Bi1.74Sr2Co1.8Oy and Bi2Sr2Co1.8Oy were produced using solid-state reaction (MO) method. The same powders were also used to produce ceramics by Spark Plasma Sintering (SPS) fabrication technique. SEM, high resolution XRD and HRTEM techniques has been employed to characterise the microstructure and crystal structures of the ceramics. Figure of merit (ZT) was also determined from measurement of electrical resistivity, Seebeck coefficient and thermal conductivity. Together with the above, calcium cobaltite of formulation Ca3-xBixCo3O9 (x=0 and 0.3) was also produced via MO and SPS routes. The same characterisation techniques were used for characterisation of calcium cobaltite. For Bi2+xSr2Co2Oy ceramics, it was found that SPS fabrication is essential to obtain high density samples. Excess bismuth has a major role in the adjustment of the microstructure and thermoelectric properties. The room temperature microstructure contains two minor phases with compositions of CoO and Bi0.75Sr0.25O1.26. The crystal structure of the main phase was successfully indexed and refined as misfit type structure having monoclinic symmetry with I2/a space group. A high ZT of 0.12 was achieved in both x=0.1 and 0.2 MO samples. For Bi2Sr2Co1.8Oy ceramics, the microstructure contains only one minor phase, Bi0.75Sr0.25O1.26. A high ZT of 0.16 was obtained at 900 K for this composition. For Bi1.74Sr2Co1.8Oy, it was not possible to obtain high density ceramics by MO route and SPS fabrication was necessary. However, SPS sample showed a low ZT of 0.04 at 900 K.For ceramics of formulation Ca3-xBixCo3O9 (x=0 and 0.3), it was difficult to obtain high density calcium cobaltite ceramics by MO route and SPS fabrication was found to be essential. In addition to improved density, SPS produced textured microstructure. Similar to bismuth strontium cobaltite, excess bismuth played a major role in microstructure development and thermoelectric properties. Single phase and high density Ca3Co4O9 ceramics were obtained by SPS. A minor phase of Bi2Ca2Co2Oy was found in the microstructure of Ca3-xBixCo3O4 (x=0.3) samples. A high ZT of 0.25 was obtained for Ca3Co4O9 SPS samples at 900 K through improvement of power factor. In-situ synchrotron XRD in the temperature range of 300-1223 K was performed on both Bi2Sr2Co2Oy and Ca3Co4O9 to obtain their high temperature structural characteristics. The crystal structure of both compounds remains unchanged till 1223 K. For, Bi2Sr2Co2Oy the CoO and Bi0.75Sr0.25O1.26 minor phases disappear above 1073 K and a new minor phase containing (Bi-Sr-O) or (Bi-Co-O) starts forming. On heating, the lattice volume and coefficient of thermal expansion change linearly for both compounds. Thermal expansion coefficient was found to be 0.0000353-0.0000343 and 0.0000296-0.0000288 K-1 over the temperature range of 300-1223 K for Bi2Sr2Co2Oy and Ca3Co4O9 respectively.

Neste trabalho, cerâmicas de BaTiO3 foram preparadas pelo método de Pechini com o propósito de estudar as suas propriedades dielétricas, incluindo as anomalias dielétricas de origem interfacial nestes ferroelétricos. Após calcinação das soluções precursoras a 600 oC por 2h, os pós compactados foram sinterizados a várias temperaturas entre 1150 e 1450 oC. Subseqüentemente, foram realizadas caracterizações (micro)estruturais aplicando as técnicas de microscopia eletrônica de varredura e difração de raios X, além de estudos dielétricos utilizando a técnica de espectroscopia de impedância. Destas caracterizações, verificou-se a obtenção de materiais cerâmicos com tamanhos de grãos variando entre 0,8 e 37 micrometros ao aumentar a temperatura de sinterização. Os resultados de dinâmica térmica de densificação indicam a contribuição de dois mecanismos independentes: (i) sinterização com participação de fase líquida, induzindo altas densidades dos materiais a partir de ~1300 oC (perto do ponto eutético), e (ii) sinterização via reação de estado sólido, implicando alta sinterabilidade mesmo abaixo dos 1300 oC, em se tratando de pós nanométricos, ou seja, com alta densidade de defeitos e, portanto, processos de difusão iônica intensificados. Por outro lado, a resposta dielétrica dos grãos evidenciou o cumprimento da lei de Curie-Weiss, típica de ferroelétricos, enquanto um fenômeno de anomalia dielétrica (não cumprimento desta lei) foi observado para as respostas totais destes materiais em altas temperaturas e baixas freqüências. A análise dos resultados de espectroscopia de impedância via circuito equivalente, sendo considerado o modelo de camadas (grãos e contornos de grãos) em série, revelou a predominância das propriedades dielétricas das interfaces intergranulares como a causa desta anomalia. Considerando a relação entre propriedades macroscópicas e microscópicas no modelo, a variação da intensidade da anomalia é discutida em função do tamanho dos grãos, sendo este parâmetro uma medida (função inversa) da densidade das interfaces intergranulares. Em geral, este trabalho revela uma excelente correlação entre microestruturas, circuito equivalente e propriedades dielétricas exibidas por estes materiais eletrocerâmicos. / BaTiO3 ceramics were prepared in this work, following the Pechinis method, with the purpose of studying their dielectric properties, including especially the occurrence and characteristics of dielectric anomalies associated to internal interfaces, as often found in ferroelectrics. After calcination of the precursor solutions at 600 oC for 2h, the synthesized green compacts were sintered at several temperatures from 1150 to 1450 oC. Subsequently, (micro)structural characterizations were carried out by applying scanning electron microscopy and X-ray diffraction techniques, followed by dielectric measurements using the impedance spectroscopy technique. From these characterizations, the production of ceramic bodies with average grain sizes varying from 0.8 to 37 micrometer was verified when increasing the sintering temperature. The results of thermal dynamics of densification indicate the contribution of two independent mechanisms, namely (i) liquid phase-assisted sintering, inducing high materials density from ~1300 oC (close to the eutectic point) above, and (ii) solid-state sintering, implying high sinterability even below 1300 oC, as dealing with nanoparticles-sized powders, meaning high density of surface defects and, thus, enhanced ionic diffusion processes. On the other hand, while the dielectric response of the grains satisfied the Curie-Weiss law, typical of ferroelectrics, a dielectric anomaly (departure from this law) phenomenon was observed for the total dielectric response of these materials towards higher temperatures and lower frequencies. The analysis of the results from impedance spectroscopy via equivalent circuit, involving consideration of the series layer (grains and grain boundaries) model, revealed that the predominance of the dielectric properties from the intergranular interfaces is responsible for occurrence of this anomaly. Considering the relation between macroscopic and microscopic properties holding in this model, the variation of the anomaly strength is here discussed in terms of the value of average grain size in these ceramics, a microstructural parameter that represents a measure (inverse function) of the density of the intergranular interfaces. In general, the present study reveals a really good correlation between microstructures, equivalent circuit and dielectric properties exhibited by these electroceramic materials.