In this thesis, the thermomechanical approach with internal variables has been thoroughly analyzed. This approach is based on the combination of thermodynamic principles and continuum mechanics. Therefore it reflects the physical essence of constitutive behavior of materials. Based on this approach, a one-dimensional constitutive model for the two-way shape memory effect and a one-dimensional constitutive model for piezoceramics have been developed, respectively. In modeling the two-way shape memory effect, a residual stress σ_re is introduced as a controlling parameter for the two-way shape memory effect. A further refinement of the transformation kinetics expression for two-way shape memory is derived. It is demonstrated that the material parameters required by this model can be calculated or measured using a standard materials testing apparatus. A numerical study is conducted and the effectiveness of this model is verified. In the constitutive modeling of piezoceramics, a new internal state variable is introduced to relate the macroscopic behavior of a piezoceramic with its micro-properties. A phenomenological formulation of polarization reversal is proposed, and then a fully-coupled thermo-electro-mechanical model is developed. It is shown that the theory developed can describe the electromechanical behavior of piezoceramics well. / Master of Science

Made available in DSpace on 2016-06-02T20:16:54Z (GMT). No. of bitstreams: 1 6611.pdf: 4783832 bytes, checksum: 1dc280ff47cc4df343ea92399b40fdd5 (MD5) Previous issue date: 2015-03-09 / Financiadora de Estudos e Projetos / The search for new lead-free piezoelectric materials has been a major goal of many scientists in recent years. The main cause is the replacement of widely used lead zirconate titanate (PZT) based ceramics due to the highly toxic characteristics of the lead element. Potassium sodium niobate based ceramics have shown high piezoelectric coefficients and a morphotropic phase boundary close to the composition (K0.5Na0.5)NbO3 (KNN), similar to that found in lead zirconate titanate. However, the preparation of highly dense KNN based ceramics is extremely difficult. In this work, the structural, mechanical and electrical properties of lead free ferroelectric ceramics with compositions Li0,03(K0,5Na0,5)0,97Nb0,8Ta0,2O3 + xwt% CuO (x = 0; 2 and 3.5) were studied. All the compositions, sintered at 1050ºC for 2 hours had high density, approximately 95% of the theoretical value. Rietveld refinement of the X ray diffraction patterns showed a mixture of both orthorhombic Bmm2 and tetragonal P4mm phases, for all compositions. Nevertheless, compositions with high CuO contents have mainly the tetragonal phase. Dielectric and dynamic mechanical analysis (DMA) measurements showed two polymorphic phase transitions with increasing temperature. Both phase transitions have diffuse character and they can be related with the transformation of the orthorhombic phase fraction in the tetragonal one, and with the transformation of the tetragonal ferroelectric phase to a cubic paraelectric one. The origin of the difference observed between the temperatures where both techniques, dielectric and mechanical, see the diffuse phase transition is discussed. The ceramic with 2wt% of CuO is electrically softer than the other compositions and it has the highest value of the piezoelectric coefficient d31. Also, in this work we studied the possibility of using high contents of CuO to promote the formation of liquid phase for obtaining and extracting single crystal seeds, which can be used for the texture of KNN-based ceramics. The ceramic Li0,03(Na0,5K0,5)0,97Ta0,2Nb0,8O3 + x wt% CuO with x=16, sintered at 1090ºC for 2 hours, is a perfect candidate for extracting grains which may be used as seeds. Furthermore, ceramics with x=13, sintered at 1110ºC for 2 hours, showed a partial melting of the material, which caused the growth of highly oriented grains. This material can be practically considered as a single crystal and, with a proper cut procedure, the desired single crystal seeds can be obtained. This method to obtain single crystal seeds, as proposed in this work, is very simple and novelty. / Nos últimos anos, o foco principal de muitos cientistas tem sido a procura de novos materiais piezoelétricos livres de chumbo. A causa principal é a substituição dos materiais baseados em titanato zirconato de chumbo (PZT), os quais são amplamente utilizados em aplicações piezoelétricas, devido à alta toxicidade do elemento chumbo. Cerâmicas baseadas em niobato de sódio e potássio têm mostrado altos coeficientes piezoelétricos e um contorno de fases morfotrópico próximo da composição (K0.5Na0.5)NbO3 (KNN), similar ao encontrado no titanato zirconato de chumbo. Porém, a preparação de cerâmicas baseadas em KNN com alta densidade é extremamente dificultosa. Neste trabalho foram estudadas as propriedades estruturais, mecânicas e elétricas de cerâmicas ferroelétricas livres de chumbo com composições Li0,03(K0,5Na0,5)0,97Nb0,8Ta0,2O3 + x %P CuO (x = 0; 2 e 3,5). Todas as cerâmicas sinterizadas a 1050ºC durante 2 horas apresentaram altas densidades, sendo aproximadamente 95% da densidade teórica. O refinamento pelo método de Rietveld dos perfis de difração de raios X mostrou que todas as composições apresentam uma mistura de ambas as fases, ortorrômbica Bmm2 e tetragonal P4mm. Porém, composições com altos teores de CuO apresentam a fase tetragonal como sendo majoritária. As medidas dielétricas e as de análise mecânico dinâmico (DMA) mostraram duas transições de fase polimórficas com o aumento da temperatura. Ambas transições de fase têm caráter difuso e estão relacionadas com a transformação da fração de fase ortorrômbica em tetragonal e com a transformação da fase tetragonal ferroelétrica para cúbica paraelétrica. Foi discutida a origem da diferença observada, nas temperaturas em que ambas as técnicas, dielétrica e mecânica, enxergam a transição de fase difusa. A cerâmica com 2%P de CuO mostrou-se mais mole eletricamente e apresentou um valor maior de coeficiente piezoelétrico d31 do que as outras composições estudadas. Também, neste trabalho foi estudada a possibilidade de usar altos teores de CuO para promover a formação de fase líquida e conseguir a formação e extração de sementes monocristalinas que possam ser utilizadas na textura de cerâmicas baseadas em KNN. A cerâmica de Li0,03(Na0,5K0,5)0,97Ta0,2Nb0,8O3 + x % P CuO com x=16, sinterizada a 1090ºC durante 2 horas, mostrou-se a candidata perfeita para a extração de grãos que possam ser utilizados como sementes. Por outro lado, a cerâmica com x=13, sinterizada a 1110ºC durante 2 horas, apresentou fusão parcial de material, o que promoveu o crescimento dos grãos altamente orientados de forma que esse material já pode ser considerado como sendo praticamente um monocristal e com um procedimento de corte adequado, podem ser obtidas as sementes monocristalinas desejadas. Esse procedimento de obtenção de sementes monocristalinas, proposto neste trabalho, é totalmente simples e inovador.

Made available in DSpace on 2016-06-02T20:19:24Z (GMT). No. of bitstreams: 1 6248.pdf: 27691207 bytes, checksum: cc929611cc4e506743fb3b9ce1730858 (MD5) Previous issue date: 2014-08-07 / Universidade Federal de Sao Carlos / Motivated by the great growth presented in the last decade in research on lead-free piezoelectric ceramics and the fact that some ceramic systems, as those based on bismuth, have been identified as promising candidates to substitute the lead zirconate titanate (PZT) in their present technological applications, was proposed as the objective of this work, study the effect of adding 𝐵𝑎𝑇 𝑖𝑂3 (BT) on the structural, electrical and anelastic properties exhibit by the system (1−𝑥)𝐵𝑖0.5𝑁𝑎0.5𝑇𝑖𝑂3−𝑥𝐵𝑎𝑇 𝑖𝑂3 (BNT-BT). The structural characterization was performed by the techniques of X-ray diffraction (XRD) and Raman spectroscopy. The morphological and compositional aspects (qualitative), in the calcined powders, and the sintered samples were studied by scanning electron microscopy (SEM). The ferroelectric and dielectric character of the compositions were obtained through characterization of ferroelectric hysteresis exhibit and using the technique of electrical impedance spectroscopy, respectively. Phase transitions and the possible mechanisms of anelastic relaxation were studied by the technique of mechanical spectroscopy. Samples were obtained by the method of solid state reaction, where it was possible to obtain compositions with 0.00 ≤ 𝑥 ≤ 0.08 with relative density greater than 95% and without the presence of spurious or secondary phases. On profiles of X-ray diffraction for the different studied sintered compositions was applied the method of Rietvelt refinement which allow the determination and confirmation of the crystal structures in the samples under study, and the presence of a morphotropic phase boundary (MPB) for the BNT-BT. The XRD results were corroborated by the results of Raman spectroscopy. The ferroelectric nature of the different compositions of BNT-BT system studied was confirmed. Electrical phase transitions (F-Af and Af-P) and structural transitions (R-T and T-C) exhibited by the BNT-BT were characterized by mechanical spectroscopy (using a dynamical mechanical analyzer (DMA)), and by electrical impedance spectroscopy, employing the results in complementing the electrical and structural phase diagram of this system. In addition to the phase transitions obtained, the technique of mechanical spectroscopy for compositions between 0.00 ≤ 𝑥 ≤ 0.03, allowed the observation of a complex process of anelastic relaxation that was associated with interactions and mobility of different defects present, which possibly contribute significantly to an increase of conductivity in these materials, which had not been previously reported in the literature. / Motivados pelo grande crescimento apresentado na última década nas pesquisas em cerâmicas piezoelétricas livres de chumbo e o fato de alguns sistemas cerâmicos, como os baseados em bismuto, já terem sido identificados como promissores candidatos à substituição do titanato zirconato de chumbo (PZT) em suas atuais aplicações tecnológicas, foi proposto como objetivo deste trabalho, estudar a influência da adição de 𝐵𝑎𝑇 𝑖𝑂3 (BT) sobre as propriedades estruturais, elétricas e anelásticas exibidas pelo sistema (1 − 𝑥)𝐵𝑖0,5𝑁𝑎0,5𝑇𝑖𝑂3 − 𝑥𝐵𝑎𝑇 𝑖𝑂3 (BNT-BT). A caracterização estrutural foi realizada por meio das técnicas de difração de raios-X (DRX) e espectroscopia Raman. Os aspectos morfológico e composicional (qualitativo), tanto dos pós calcinados, quanto das amostras sinterizadas foram estudados mediante microscopia eletrônica de varredura (MEV). O caráter ferroelétrico e dielétrico das composições estudadas foram obtidos por meio da caracterização da histerese ferroelétrica exibida e da técnica de espectroscopia de impedância elétrica, respectivamente. As transições de fase e os possíveis mecanismos de relaxação anelástica foram estudados utilizando a técnica de espectroscopia mecânica. As amostras foram obtidas pelo método de reação de estado sólido, onde foi possível obter composições com 0, 00 ≤ 𝑥 ≤ 0, 08 com densidades relativas maiores que 95% e sem a presença de fases espúrias ou secundárias. Aos perfis de difração de raios-X para as diferentes composições sinterizadas estudadas foi aplicado o método de refinamento Rietvelt que permitiu a determinação e confirmação das estruturas cristalinas nas amostras em estudo, além da presença de contorno de fase morfotrópico (CFM) para o BNT-BT. Os resultados de DRX foram corroborados por meio dos resultados de espectroscopia Raman. O carácter ferroelétrico das diferentes composições do sistema BNT-BT estudadas foi confirmado. Tanto as transições de fase elétricas, ferroelétricaantiferroelétrica (F-Af) e antiferroelétrica-paraelétrica (Af-P), quanto as transições estruturais, romboédrica-tetragonal (R-T) e tetragonal-cubica (T-C), exibidas pelo BNT-BT foram caracterizadas por espectroscopia mecânica (por meio de um analisador dinâmico mecânico(DMA)) e por espectroscopia de impedância elétrica, empregando-se os resultados obtidos na complementação do diagrama de fase elétrico e estrutural deste sistema. Além das transições de fase obtidas, a técnica de espectroscopia mecânica, para composições entre 0, 00 ≤ 𝑥 ≤ 0, 03, propiciou a observação de um processo de relaxação anelástica complexo que foi associado a interações e mobilidade de diferentes defeitos presentes, que possivelmente contribuem significativamente para um aumento de condutividade nestes materiais, que não haviam sido reportado anteriormente na literatura.

L’effet magnétoélectrique (ME) se traduit par la possibilité d’induire une magnétisation à l’aide d’un champ électrique (effet direct) ou celle d’induire une polarisation électrique à l’aide d’un champ magnétique (effet inverse). Les composites laminés qui possèdent de grands coefficients ME ont généré beaucoup d’intérêt dans le domaine des capteurs, des modulateurs, des interrupteurs et des inverseurs de phase. Dans cette thèse, nous présentons les performances de composites dits laminés à deux ou trois couches. Il a été montré que l’on pouvait obtenir des performances en conversion magnéto-électrique directe en associant des phases magnétostrictives et piézoélectriques. Une modélisation de leur comportement basée sur un oscillateur mécanique a été proposée. Elle a été en particulier utilisée pour simuler le couplage mécanique entre deux couches. Une autre approche pour développer des dispositifs originaux a consisté à utiliser un champ magnétique alternatif pour induire des courants de Foucault dans des électrodes métalliques et une Force de Lorentz en présence d’un deuxième champ magnétique continu. Si ces électrodes recouvrent un matériau piézoélectrique, la force de Lorentz sera alors convertie en signal électrique suivant l’effet direct. Cette approche permet donc de développer des dispositifs de conversion électromagnétique sans phase magnétique. Différents prototypes utilisant un bimorphe piézoélectrique, un film de PVDF et une céramique piézoélectrique ont été réalisés et caractérisés. Un signal électrique proportionnel à la composante continue du champ magnétique a été mis en évidence, ce qui ouvre des applications pour la détection magnétique. Cette thèse s’est également intéressée à l’augmentation du coefficient d’électrostriction par injection de charges électriques en utilisant la technique de décharge Corona. Cette étude a été réalisée sur du polypropylène, connu pour sa capacité à stocker des charges électriques. Le mécanisme de stockage de charge et l’effet sur l’électrostriction ont été étudiées par la mesure du potentiel de surface, la mesure des courants thermo-stimulés, la calorimétrie différentielle et l’interférométrie Laser. L’injection de charges a contribué à une augmentation de la permittivité et par la même à celle du coefficient d’électrostriction, en accord avec un modèle simple de distribution de charges dans l’échantillon. / Magnetoelectric (ME) interactions in matter correspond to the appearance of magnetization by means of an electric field (direct effect) or the appearance of electric polarization by means of a magnetic field (converse effect). The composite laminates which possess large ME coefficient, have attracted much attention in the field of sensors, modulators, switches and phase inverters. In this thesis, we report on the ME performances of the bi- and tri- layered composites. It is shown that their ME couplings can be achieved by combining magnetostrictive and piezoelectric layers. A model based on a driven damped oscillation is established for the piezoelectric/magnetostrictive laminated composite. It is used to simulate the mechanical coupling between the two layers. In addition, we report that the ME coupling can be achieved without magnetic phase but only with eddy current induced Lorentz forces in the metal electrodes of a piezoelectric material induced by ac magnetic field. The models based on the Lorentz effect inducing ME coupling in PZT unimorph bender, polyvinylidene fluoride (PVDF) film and PZT ceramic disc are thus established. The results show the good sensitivity and linear ME response versus dc magnetic field change. Thus, the room temperature magnetic field detection is achievable using the product property between magnetic forces and piezoelectricity. Besides, we report on the electrostrictive performance of cellular polypropylene electret after high-voltage corona poling. We use the Surface Potential test, Thermal Stimulated Depolarization Current experiment and Differential Scanning Calorimetry experiment to analyse its charge storage mechanism. The result show that the electrostrictive coefficient and relative permittivity of the charged samples increase. Last but not least, in order to explain this phenomenon, a mathematic model based on the charged sample has been established.

Dans cette thèse nous proposons de développer un système d’imagerie ultrasonore innovante de micro- défauts basé sur l’utilisation conjointe de techniques d’acoustique non linéaire et du concept de "transducteur à cavité chaotique". Ce transducteur correspond à la combinaison d’une céramique piézoélectrique collée sur une cavité de forme chaotique et du principe de retournement temporel. La faisabilité et les performances de ce nouveau système sont explorées par des simulations numériques. Des paramètres optimaux d’utilisation pour une implémentation expérimentale sont proposés. Une grande partie des travaux menés dans le cadre de cette thèse se concentre sur le développement d’outils numériques permettant l’amélioration de telles techniques d’imagerie. Un schéma d’éléments finis de type Galerkin Discontinu (GD) est étendu à l’élastodynamique non linéaire. Un type de zone absorbante parfaitement adaptée, appelée "Nearly Perfectly Matched Layer" (NPML) a aussi été développé. Dans le cas de matériaux orthotropes, comme des problèmes de stabilité apparaissent, un mélange de NPML et de zone atténuante, dont on contrôle la proportion respective, est introduit afin de stabiliser les NPML. Une validation expérimentale du concept de "transducteur à cavité chaotique" pour la focalisation dans un milieu solide, réverbérant ou non, en utilisant une seule source est réalisée. Les méthodes de retournement temporel et de filtre inverse sont présentées et comparées. La démonstration expérimentale qu’un "transducteur à cavité chaotique" peut être utilisé conjointement avec les méthodes d’inversion d’impulsion afin de réaliser une image de non linéarités localisées est présentée / In this thesis we propose the development of an innovative micro-damage imaging system based on a combination of Nonlinear Elastic Wave Spectroscopy techniques and “chaotic cavity transducer” concept. It consists of a combination of a PZT ceramic glued to a cavity of chaotic shape with the time reversal principle. The feasibility and capabilities of these new ideas is explored by numerical simulations, and optimal operational parameters for experimental implementation are suggested based on the modelling support. A large part of the research work conducted in this thesis is concentrated on the development of numerical simulation tools to help the improvement of such nonlinear imaging methods. A nodal Discontinuous Galerkin Finite Element Method (DG-FEM) scheme is extended to nonlinear elasto-dynamic including source terms. A Perfectly Matched Layer absorbing boundary condition well adapted to the DG-FEM scheme, called Nearly Perfectly Matched Layer (NPML), is also developed. In the case of orthotropic material as stability problems appear, a mixture of NPML and sponge layer, with a controllable ratio of these two kinds of absorbing layers, is introduced. The experimental validation of “chaotic cavity transducer” to focalize in reverberant and non-reverberant solid media with only one source is made. Classical time reversal, inverse filter and 1 Bit time reversal process are discussed and compared. The experimental demonstration of the use of a “chaotic cavity transducer”, in combination with the pulse inversion and 1-bit methods, to obtain an image of localized nonlinearity is made. This opens the possibility for high resolution imaging of nonlinear defects

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / As cerâmicas piesoelétricas estudadas neste trabalho (Pb1,03Zr0,53Ti0,47O3, Pb1,03Zr0,525Nb0,05Ti0,465Fe0,005O3, Pb1,03Zr0,515Nb0,015Ti0,465Fe0,005O3, Pb1,03Zr0,525Nb0,005Ti0,455Fe0,015O3 e Pb1,03Zr0,515Nb0,015Ti0,455Fe0,015O3) foram sinterizadas a 1200oC e 1250oC por 3,5 h a fim de que suas propriedades piesoelétricas fossem investigadas. Nas composições dos PZT obtidas, a matriz e os dopantes empregaram óxidos como matérias primas. As misturas dos óxidos precursores foram calcinadas a 850oC por 3,5 h para obtenção da fase PZT. Os precursores, os pós e os corpos de prova de PZT foram caracterizados quanto às microestruturas, densidades e propriedades físicas. Após a conformação dos pós e a sinterização, os materiais cerâmicos foram polarizados para caracterização de suas propriedades piesoelétricas através de um impedancímetro na faixa de freqüência de 100 KHz a 200 KHz. Os resultados de dispersão de laser dos precursores revelaram aglomeração do óxido de chumbo e óxido de zircônio. As composições calcinadas apresentaram tamanho de partícula na faixa de 0,44 μm a 0,63 μm. As análises de densidade por método de Arquimedes indicaram uma boa densificação dos corpos de prova sinterizados e pouca influência da temperatura de sinterização com uma escala de valores de 95,73 a 97,65% da densidade teórica. As análises de microscopia eletrônica de varredura revelaram que os sinterizados contendo concentrações diferentes de dopantes exibem uma correlação do tipo e teor de dopante com a natureza da fratura, sendo transgranular, quando dopante ferro for predominante e intergranular, quando o dopante Nb for predominante. Também, o aumento da temperatura de sinterização resultou em fratura transgranular independente do tipo e da concentração de dopante, exceto para baixo teor de dopante da composição equimolar, cujos resultados não foram consistentes com a literatura sobre o material. No que diz respeito às propriedades piesoelétricas, revelou-se que a combinação da variação da composição com a temperatura foi favorável para o aumento dos valores da constante dielétrica da formulação equimolar com maior percentual de dopantes. Já o efeito da temperatura com a composição surtiu um efeito muito negativo para os valores de fator de qualidade mecânica da formulação dopada com mais ferro. Para os valores de constante de freqüência da formulação com maior percentagem de nióbio, o efeito da temperatura com a composição gerou um efeito positivo. / The piezoelectric ceramics studied in this work, Pb1.03Zr0.53Ti0.47O3, Pb1.03Zr0.525Nb0.05Ti0.465Fe0.005O3, Pb1.03Zr0.515Nb0.015Ti0.465Fe0.005O3, Pb1.03Zr0.525Nb0.005Ti0.455Fe0.015O3 and Pb1.03Zr0.515Nb0.015Ti0.455Fe0.015O3, were all of them sintered between 1200oC and 1250oC for 3.5h. After that, their piezoelectric properties were investigated. In the present work, oxides were used as raw material in both, matrices and dopants. The mixture of the precursor oxides were calcinaned at 850oC during 3.5h for obtaining the PZT phase. The precursor oxides, the powders and the PZT samples went through characterization tests in order to have their microstructures, densities and physical properties correctly determined. After the powders had been conformed and performed the sinterization process, the PZT ceramics were polarized and their piezoelectric properties determined by using an impedancemeter working in the frequency from 100 KHz to 200 KHz. The obtained results from laser dispersion had revealed agglomeration of lead and zirconium oxide. The calcined samples presented particle sizes from 0.44 μm to 0.63 μm. The density analyses using the Archimedes method indicated a good densification of the sintered samples and a weak influence of the sintering temperature on the obtained density values, whose values ranged from 95.73 to 97.65 % of the theoretical density value. Analysis performed using the scanning electron microscopy technique (MEV) revealed that the sintered samples had showed a correlation between the type and concentration of the dopant with their fracture mode, which were transgranular when Fe prevails over the Nb as dopant, and intergranular, when is the Nb that prevails over the Fe as dopant. By the other side, from increasing the sintering temperature resulted transgranular fractures, independently of which type and content of dopant had been used, except for the equimolar case with relatively low content of dopant, whose results were not consistent with the literature related to this material. About the piezoelectric properties, the results had showed that the combination of the dopant composition with the sintering temperature had brought better values of dielectric constant for the equimolar formulation with more content of dopant. Relating to the mechanical quality factor, from the combination of the dopant composition with the sintering temperature had decreased the factor when Fe prevails over Nb and increased the frequency factor when is the Nb that prevails over the Fe.

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / As cerâmicas piesoelétricas estudadas neste trabalho (Pb1,03Zr0,53Ti0,47O3, Pb1,03Zr0,525Nb0,05Ti0,465Fe0,005O3, Pb1,03Zr0,515Nb0,015Ti0,465Fe0,005O3, Pb1,03Zr0,525Nb0,005Ti0,455Fe0,015O3 e Pb1,03Zr0,515Nb0,015Ti0,455Fe0,015O3) foram sinterizadas a 1200oC e 1250oC por 3,5 h a fim de que suas propriedades piesoelétricas fossem investigadas. Nas composições dos PZT obtidas, a matriz e os dopantes empregaram óxidos como matérias primas. As misturas dos óxidos precursores foram calcinadas a 850oC por 3,5 h para obtenção da fase PZT. Os precursores, os pós e os corpos de prova de PZT foram caracterizados quanto às microestruturas, densidades e propriedades físicas. Após a conformação dos pós e a sinterização, os materiais cerâmicos foram polarizados para caracterização de suas propriedades piesoelétricas através de um impedancímetro na faixa de freqüência de 100 KHz a 200 KHz. Os resultados de dispersão de laser dos precursores revelaram aglomeração do óxido de chumbo e óxido de zircônio. As composições calcinadas apresentaram tamanho de partícula na faixa de 0,44 μm a 0,63 μm. As análises de densidade por método de Arquimedes indicaram uma boa densificação dos corpos de prova sinterizados e pouca influência da temperatura de sinterização com uma escala de valores de 95,73 a 97,65% da densidade teórica. As análises de microscopia eletrônica de varredura revelaram que os sinterizados contendo concentrações diferentes de dopantes exibem uma correlação do tipo e teor de dopante com a natureza da fratura, sendo transgranular, quando dopante ferro for predominante e intergranular, quando o dopante Nb for predominante. Também, o aumento da temperatura de sinterização resultou em fratura transgranular independente do tipo e da concentração de dopante, exceto para baixo teor de dopante da composição equimolar, cujos resultados não foram consistentes com a literatura sobre o material. No que diz respeito às propriedades piesoelétricas, revelou-se que a combinação da variação da composição com a temperatura foi favorável para o aumento dos valores da constante dielétrica da formulação equimolar com maior percentual de dopantes. Já o efeito da temperatura com a composição surtiu um efeito muito negativo para os valores de fator de qualidade mecânica da formulação dopada com mais ferro. Para os valores de constante de freqüência da formulação com maior percentagem de nióbio, o efeito da temperatura com a composição gerou um efeito positivo. / The piezoelectric ceramics studied in this work, Pb1.03Zr0.53Ti0.47O3, Pb1.03Zr0.525Nb0.05Ti0.465Fe0.005O3, Pb1.03Zr0.515Nb0.015Ti0.465Fe0.005O3, Pb1.03Zr0.525Nb0.005Ti0.455Fe0.015O3 and Pb1.03Zr0.515Nb0.015Ti0.455Fe0.015O3, were all of them sintered between 1200oC and 1250oC for 3.5h. After that, their piezoelectric properties were investigated. In the present work, oxides were used as raw material in both, matrices and dopants. The mixture of the precursor oxides were calcinaned at 850oC during 3.5h for obtaining the PZT phase. The precursor oxides, the powders and the PZT samples went through characterization tests in order to have their microstructures, densities and physical properties correctly determined. After the powders had been conformed and performed the sinterization process, the PZT ceramics were polarized and their piezoelectric properties determined by using an impedancemeter working in the frequency from 100 KHz to 200 KHz. The obtained results from laser dispersion had revealed agglomeration of lead and zirconium oxide. The calcined samples presented particle sizes from 0.44 μm to 0.63 μm. The density analyses using the Archimedes method indicated a good densification of the sintered samples and a weak influence of the sintering temperature on the obtained density values, whose values ranged from 95.73 to 97.65 % of the theoretical density value. Analysis performed using the scanning electron microscopy technique (MEV) revealed that the sintered samples had showed a correlation between the type and concentration of the dopant with their fracture mode, which were transgranular when Fe prevails over the Nb as dopant, and intergranular, when is the Nb that prevails over the Fe as dopant. By the other side, from increasing the sintering temperature resulted transgranular fractures, independently of which type and content of dopant had been used, except for the equimolar case with relatively low content of dopant, whose results were not consistent with the literature related to this material. About the piezoelectric properties, the results had showed that the combination of the dopant composition with the sintering temperature had brought better values of dielectric constant for the equimolar formulation with more content of dopant. Relating to the mechanical quality factor, from the combination of the dopant composition with the sintering temperature had decreased the factor when Fe prevails over Nb and increased the frequency factor when is the Nb that prevails over the Fe.

Ferroelectric materials, especially the polycrystalline ceramics, are very promising material for a variety of applications such as high permittivity dielectrics, ferroelectric memories, piezoelectric sensors, piezoelectric/electrostrictive transducers, electrooptic devices and PTC thermistors. Among the ferroelectric based piezoelectric ceramics the lead–zirconate-titanate Pb(Zr1-xTix)O3 (PZT) have dominated transducer and actuator market due to its excellent piezoelectric and dielectric properties, high electromechanical coupling, large piezoelectric anisotropy, ease of processing and low cost. However, the toxicity of lead based compounds has raised serious environmental concerns and therefore has compelled the researchers to look for new lead free alternatives with good piezoelectric and ferroelectric properties. (Na0.5Bi0.5)TiO3 (NBT) and its solid solution is one of the leading lead free piezoceramic ceramics due to their interesting ferroelectric, piezoelectric, electromechanical and dielectric property. The parent compound NBT is a ferroelectric with a moderately high Curie temperature (~250 oC), large ferroelectric polarization (~40µC/cm2) polarization, promising piezoelectric properties with 0.08% strain and longitudinal piezoelectric coefficient (d33) ~ 80 pC/N. X-ray and neutron diffraction studies in the past have shown that NBT exhibits rhombohedral (R3c) at room temperature. Neutron diffraction studies have suggested that NBT undergo a gradual rhombohedral to tetragonal (P4bm) transformation in a temperature region 200-320 ºC. Though the structure and phase transition behavior of NBT has been extensively investigated for over six decades now, this subject has again become debatable in recent few years, with some group reporting formation of orthorhombic phase above room temperature and another group suggesting monoclinic distortion at room temperature using high resolution x-ray diffraction technique. Interestingly the intermediate orthorhombic instability, reported by electron diffraction studies, has never been captured by neutron diffraction method though neutron diffraction is an equally powerful tool for studying (oxygen) octahedral tilts in perovskites. Needless to mention, the understanding of the subtle structural distortions have great significance with regard to the determination of the structure-piezoelectric property correlations in NBT based piezoceramics. The present thesis deals with such subtle structural issues in great detail. The systems investigated in the thesis are Ca and Ba modified NBT. While the Ca modified system was chosen to understand the subtle orthorhombic instability that has been reported above room temperature (only) by detailed electron diffraction work, Ba-modified NBT is the most investigated among the NBT-derived piezoelectric material systems and this thesis attempts to address some of the very complex nature of the structure-piezoelectric property correlation of this system. The first chapter of the thesis provides a brief introduction to the field of ferroelectrics, perovskite structure and their phase transition. A brief exposure to the conventional lead based relaxor ferroelectric and piezoelectric material is provided. A detailed overview of the existing knowledge related to room temperature structure of NBT and its phase transition studies with temperature has been discussed in the later part of this chapter. The second chapter includes various the experimental techniques that have been employed to synthesis and characterize the specimens under investigation. The third chapter deals with the phase transition behaviour of Ca modified NBT as a function of composition and temperature in the dilute concentration region. This work was carried out with the view to obtain a better understanding and compliment the intrinsic high temperature orthorhombic instability in NBT reported by electron diffraction technique. Interestingly, inspite of the fact that neutron diffraction method is a very sensitive tool for investigating subtle change in the nature of octahedral tilt in oxide perovskites, the intermediate orthorhombic distortion proposed by the electron diffraction studies has so far never been captured in any of the neutron diffraction studies. In this work we have verified the genuineness of the intrinsic instability with regard to the non-polar orthorhombic structure using neutron powder diffraction by adopting a special strategy which helped in capturing the characteristic signatures (the superlattice reflections) of the orthorhombic phase in the neutron powder diffraction patterns. It was found that small fraction of Ca-substitution (8-10 mol %) was good enough to amplify the magnitude of the orthorhombic (Pbnm) distortion, without altering the sequence of the structural evolution with temperature of the parent compound (NBT) itself, and stabilizing it at the global length scale at lower temperatures than pure NBT. This chapter presents the innovative approach that was used to extract reliable information about the very complex phase transition behaviour, involving coexistence of the various similar looking but crystallographically different phases in different temperature regimes by Rietveld analysis of temperature dependent neutron powder diffraction pattern in conjunction with temperature dependent dielectric and ferroelectric characterization of the specimens. The detailed study revealed the following sequence of structural evolution with temperature: Cc+Pbnm →Pbnm + P4/mbm → P4/mbm →Pm3 m. The fourth chapter gives a detail account of the structure-property correlations and the phase transition behaviour of (1-x)(Na0.5Bi0.5)TiO3 – (x)BaTiO3 (0≤x≤0.10), the most important solid solution series with NBT as reported in the literature. The phase transformation behaviour of this system has been investigated as a function of composition (0<x≤0.10), temperature, electric field and mechanical-impact by Raman scattering, ferroelectric, piezoelectric measurements, x-ray and neutron powder diffraction methods. The structure of the morphotropic phase boundary (MPB) compositions of this system, which is interesting from the piezoelectric property point of view, has been under controversy for long. While some groups report the structure to be pseudocubic, other groups suggest it to be combination of rhombohedral and tetragonal. A perusal of the literature suggests that the reported nature and composition range of MPB is dependent on the method of synthesis and characterization technique used. In the present study, crystal structure of the NBT-BT solid solution has been investigated at the close interval near the MPB (0.05≤x≤0.10). Though x-ray diffraction study revealed three distinct composition ranges characterizing different structural features in the equilibrium state at room temperature: (i) monoclinic (Cc) + rhombohedral (R3c) for 0≤x≤0.05, (ii) “cubic-like” for 0.06≤x≤0.0675 and (iii) MPB like for 0.07≤x<0.10, Raman and neutron powder diffraction studies revealed identical symmetry for the cubic like and the MPB compositions. Both the cubic like compositions and the MPB compositions exhibit comparatively large d33. In the later part of this chapter this apparent contradiction is resolved by the fact that the cubic like structure transforms irreversibly to MPB after electric poling, a procedure which involves applying high dc electric field (well above the coercive field) to the pellet before carrying out the piezoelectric measurements. The effect of electrical field and mechanical impact has been studied for all the three different composition range, and it was found that electric field and mechanical impact both led to irreversible phase transformation in the same direction, though the transformation with mechanical impact remains incomplete in comparison to electric field. The most pronounced effect was observed for the cubic like compositions 0.06≤x≤0.0675 – they undergo phase separation to rhombohedral and tetragonal phases by electrical and mechanical perturbations. In the non-perturbed state the cubic-like critical compositions mimics features of relaxor ferroelectrics and extremely short coherence length (~ 40-50 Å) of the out-of-phase octahedral tilts. In the poled state this coherence length grows considerably and the system behaves like a normal ferroelectric. This confirmed a strong coupling between the lattice, octahedral tilts and polarization degrees of freedom. Neutron diffraction study of compositions exhibiting cubic-like and the MPB like revealed that the traditional P4bm tetragonal structure model fails to account for the intensity of the superlattice reflections. Thus the tetragonal structure stabilized above room temperature in pure NBT is different from the tetragonal phase observed at room temperature in the NBT-BT system. The results of the effect of mechanical impact and electric field has also been reported in this chapter for the critical composition exhibiting MPB (x=0.07). A detailed structural analysis of the precritical compositions, x≤0.05, revealed coexistence of ferroelectric phases (Cc+R3c) in equilibrium state (annealed specimens). This transforms to single phase (R3c) state after poling. Thus though the precritical (x≤0.05) and critical compositions (0.06≤x<0.10) of NBT-BT exhibits coexistence of ferroelectric phases in the equilibrium state, the fact that the electric poling makes the specimen single phase, R3c, after poling for the precritical compositions and retains the two phase nature of the critical compositions makes the critical compositions exhibit considerably higher piezoelectric response than the precritical compositions. Chapter five is dedicated to phase transition behaviour of the post critical compositions of (1-x)(Na0.5Bi0.5)TiO3–(x)BaTiO3 (0.16≤x≤1) using temperature dependent XRD, dielectric and ferroelectric studies. Though structurally the entire composition range is tetragonal, several notable features were revealed during detailed examination of the structural and dielectric behaviour. This study is also important from the view point that pure BT is a major component of multilayer ceramic capacitors and that an increase in the Curie point would be a welcome step for better temperature stability of the device. NBT does this. The transition temperature increases from 120 ºC for pure BT to 275 ºC for x=0.30 along with simultaneous increase in c/a ratio from 1.009 (pure BT) to 1.02 (x=0.30). Detailed analysis of temperature and frequency dependent dielectric data revealed deviation from Curie-Weiss and suggests a gradual transformation to relaxor-ferroelectric state as the NBT concentration increases in BT. The measure of frequency dispersion ‘γ’ parameter was determined from modified Curie-Weiss law for various compositions in the system. The ferroelectric and piezoelectric properties have also been investigated in detail for this composition range and an attempt has been made to correlate the composition variation of these properties with their structural parameters. This chapter shows a systematic correlation between all physical quantities such as Curie point, piezoelectric coefficient, polarization and tetragonality as a function of composition.

Tato doktorská práce se zabývala mikrostrukturálním vývojem vybraných oxidových keramických materiálů během konvenčního slinování (CS), rychlého slinování (RRS), flash slinování (FS) a slinování pomocí plazmatu (SPS). S ohledem na keramiku pro strukturální aplikace byly pomocí RRS připraveny relativně velké (1 cm3), bez defektní a téměř hutné pelety oxidu hlinitého a yttriem stabilizovaného oxidu zirkoničitého (YSZ) s homogenní mikrostrukturou. RRS bylo také shledáno jako optimální metoda pro přípravu vysoce hutné bezolovnaté piezoelektrické keramiky s podobnými vlastnostmi, jako byly získány po časově a energeticky náročnějším CS. Metoda SPS dále zlepšila vlastnosti bezolovnaté piezoelektrické keramiky a produkovala plně hutné vzorky, což je dobrým předpokladem pro translucenci a z níž vyplývajícím optoelektrickým vlastnostem. Nejoptimálnějších výsledků – plné hustoty a vysokých piezoelektrických vlastností – bylo dosaženo kombinací SPS a RRS. Analýzy provedené v této studii také poukázaly na důležitost eliminace těkavých nečistot před rychlým ohřevem. Jinak totiž dochází k zachycení těchto látek ve slinuté keramice, což ve výsledku limituje její konečnou hustotu. Ukázalo se, že nízké konečné hustoty RRS YSZ jsou spojeny se zachycením zbytkového chloru pocházejícího ze syntézy prášku. Pokud byl zbytkový chlor odstraněn vysokoteplotním žíháním keramických kompaktů před zahájením RRS, byly touto metodou získány téměř plně hutné YZS vzorky. Negativní vliv zbytkového chloru na zhutnění byl viditelný také u flash slinovaných YSZ vzorků. Navíc FS YSZ často vede ke zrychlení růstu zrn v jádře vzorku, v důsledku vyšší teploty a elektrochemické redukce. Ve spektru procesních parametrů použitých v rámci této práce dokonce došlo k abnormálnímu růstu zrna (AGG). Silně bimodální distribuce velikosti zrn ukázaná v této práci nebyla dříve nalezena u flash slinutého YSZ. AGG byl vysvětlen dvěma přispívajícími faktory – relativně velkou velikostí vzorku, která vedla k lokalizaci elektrického proudu a vzniku horkých míst (z angl. hot-spots), a celkově akcelerovanou kinetikou růstu zrn v jádře vzorku způsobenou elektrochemickou redukcí.

The master’s thesis deals with the piezoelectric coefficients, the resonance frequency and especially the piezoelectric constants verification. With the assistance of several devices, for instance LCR-meter HIOKI 3532, impedance analyzer Agilent 4294A and LCR-meter Agilent E4980A, the resonance and the anti-resonance frequencies as well as impedance and capacitance of samples are measured. The paper opens with the theory of the piezoelectric phenomenon and the difference between direct and indirect piezoelectric phenomenon, it also describes the basic behaviour of a piezoelectric ceramic element during mechanical straining or applied voltage. Further, the paper concerns the description of various piezoelectric constants and their calculations. Subsequent part of the paper is devoted to the temperature dependence of the main piezoelectric parameters of PZT ceramics. The materials coefficients are delineated as a function of temperature of the piezoelectric charge coefficients dij, relative permittivity r, electromechanical coupling factor kij and frequency constants Ni. One of the chapters also determines the piezoelectric charge constant d33 of PZT ceramics by laser interferometer and compares it with the value measured by resonance methods. The surface displacement was measured by a single-beam interferometer Polytec OFV-5000. The results of measurements of piezoelectric charge coefficients d33 acquired by the first and the second method are identical. The last section of the paper is focused on different methods of experimental studies on the characteristics of heat transfer by diffusing heat through conduction between the silver-plated surface of cylinder made of PZT ceramics. The effect on the resonance and the anti-resonance frequencies is monitored. There after, the real heat, determined by thermo camera and the physical model of heat transfer created in program COMSOL Multiphysics, is analysed.