Gotowa bibliografia na temat „Piezoelectric polycrystalline ceramics”

Sonar transducer performance is greatly impacted by the microstructural alignment of the ceramics from which they are fabricated. Textured ceramics are a desirable material source for these parts because their deliberately aligned microstructures allow for tailored anisotropic properties that rival those of single crystal ceramics, but they also maintain the mechanical robustness and bulk manufacturability of polycrystalline ceramics. Current methods for manufacturing textured ceramics, e.g., tape casting, severely limit design freedom and require excess material waste, and so the advantage of texturing has not been fully realized. This study is focused on the enhancement of direct ink writing of textured ceramics. Direct ink writing is an additive manufacturing (AM) technique that enhances design freedom on a macro and micro scale and reduces waste by producing near-net shape textured ceramics. However, shear stresses during the AM process affect the microstructural alignment of the ceramic in an extremely complex manner that is difficult to control directly. This study first validates a novel alignment metric, derived from a computational fluid dynamics model that simulates the printing process, against real-world data. Then, an optimization algorithm is used to maximize alignment with respect to the nozzle geometry.

High electric fields were delivered to specimens during imaging in the transmission electron microscopy (TEM) chamber to reveal details of electric field-induced phenomena in ferroelectric oxides. These include the polarization switching in nanometer-sized ferroelectric domains and the grain boundary cavitation in a commercial lead zirconate titanate (PZT) polycrystalline ceramic, the domain wall fracture in a Pb(Mg1/3Nb2/3)O3–PbTiO3 single crystal, and the transformation of incommensurate modulations in Pb0.99Nb0.02[(Zr1−xSnx)1−yTiy]0.98O3 (PZST100x/100y/2) polycrystalline ceramics. In the PZT ceramic, a cavitation process was uncovered for the electric field-induced intergranular fracture. In the ferroelectric single crystal, a preexisting crack was observed to deflect and to follow a 90° domain wall, indicating the presence of severe incompatible piezoelectric strains at thedomain wall. In the antiferroelectric PZST ceramics, the electric field-induced antiferroelectric-to-ferroelectric phase transformation was accompanied with the disappearance of incommensurate modulations.

Piezoelectric ceramics is a functional material that can convert mechanical energy into electrical energy and vice versa. It can find wide applications ranging from our daily life to high-end techniques and dominates a billion-dollar market. For half a century, the working horse of the field has been the polycrystalline PbZr1−xTixO3 (PZT), which is now globally resisted for containing the toxic element lead. In 2009, our group discovered a non-Pb piezoelectric material, (BaCa)(ZrTi)O3 ceramics (BZT-BCT), which exhibits an ultrahigh piezoelectric coefficient d33 of 560–620 pC/N. This result brought extensive interest in the research field and important consequences for the piezoelectric industry that has relied on PZT. In the present paper, we review the recent progress, both experimental and theoretical, in the BZT-BCT ceramics.

The complex, non-linear, irreversible, hysteretic behaviour of polycrystalline ferroelectric materials is the result of domain wall motion and correlates with the phase composition of the ceramic. This paper reports on our investigation of the ferroelectric polarization of PZT ceramics in dependence of temperature in the range between -175 and 150°C. We compare five commercial piezoelectric materials used in actuator applications. The obtained data, derived correlations, and material functions are very helpful for understanding the material properties in practical applications and give input values for temperature depended numerical hysteretic models [1].

Crystallographically engineered Relaxor-PT single crystals, specifically PMN-PT (Generation I) and PIN-PMN-PT/PMN-PZT (Generation II), offer much higher piezoelectric and electromechanical coupling coefficients (d33>1,500 pC/N, k33>0.9), when compared to polycrystalline PZT-5H ceramics (d33>600 pC/N, k33>0.75). Recently Ceracomp Co., Ltd. (www.ceracomp.com) has developed the solid-state single crystal growth (SSCG) technique and successfully fabricated Gen III PMN-PZT single crystals modified with acceptors or donors. The piezoelectric constants (d33) of (001) Gen III PMN-PZT single crystals were measured to be higher than 4,000 pC/N and thus about two times higher than those of PMN-PT/PZN-PT (Gen I) and PIN-PMN-PT/PMN-PZT (Gen II) single crystals. The Gen III PMN-PZT single crystals have been firstly applied to single crystal-epoxy composites, ultrasonic transducers, piezoelectric sensors, and piezoelectric actuators. In this paper we introduce the development of Gen III PMN-PZT single crystals, piezoelectric composites and multilayer single crystal actuators.

(K0.48Na0.52)NbO3-0.03Bi0.5Na0.5ZrO3 (KNNS-0.03BNZ) ceramics were prepared doped with 3 mol% Bi0.5Na0.5ZrO3 (BNZ), and the effect of sintering temperature on dielectric and piezoelectric properties of KNNS-0.03BNZ was also investigated. KNNS-0.03BNZ ceramics at all sintering temperatures exhibit a single perovskite structure, and the change of sintering temperature has no significant effect on the phase composition of KNNS 0.03BNZ ceramics. The Raman shifts of the ν1 and ν5 vibration modes have irregular changes in all sintering temperature ranges, indicating that there are polycrystalline phases coexisting in this region. With the change of sintering temperature, Tc slightly shifts to the high temperature direction, and TR-T slightly shifts to the high temperature direction, dielectric constant εr continuously increases, while dielectric loss tanδ firstly decreasing and then increasing. Thanks to the presence of a small amount of liquid phase in the ceramics sintered at 1160 ℃, piezoelectric coefficient d33 reaches 280 pC/N.

Mestrado em Engenharia de Materiais
This work is about lead-free ceramic materials intended for electromechanical applications and candidates to replace lead-based electroceramics. One of the most widely used piezoelectric ceramics is lead zirconate titanate (PZT). However, it contains more than 60% of lead and it is toxic for humans and environment. In 2003, a directive from European Union has prohibited the use of potentially hazardous elements as lead. Due to the lack of competitive materials for PZT replacement an exception was created until a competitive alternative be found. Potassium and sodium niobate due to its high Curie temperature and moderate piezoelectric properties is currently one of the most promising lead-free materials for PZT substitution. However, its effective industrial adoption requires, among others, optimization of its properties. In this context, in this work we initially studied the effect of dopants, texturing and sintering temperature of KNN ceramics. For this purpose KNN ceramics doped with i) 1.5 mol% CuO + 2.0 mol% Li2O, ii) 1.5 mol% CuO + 4.0 mol% Li2O and iii) 1.5 mol% CuO + 0.5 mol% MnO using different sintering temperatures (1050, 1065 and 1080 °C) were prepared. In addition in order to maximize the preferential crystallographic orientation of the ceramic KNN (texturing), in this case in the direction (h00), KNN single crystals were produced. These crystals were used as seeds in the texturing process KNN ceramics. It was found that the composition doped with copper and manganese was the only single phase one of the studied compositions. Dense (> 95%) ceramics, textured and non-textured, and with a high Lotgering factor among the studied compositions (≈ 20%) were prepared. The dependence of the dielectric properties of the Lotgering factor was demonstrated. In the attempt to optimize the Lotgering factor to top up the piezoelectric properties, the effect of the quantity of added crystals, heating and cooling rate and duration of sintering cycle were studied for the composition doped with copper and manganese. To this end, KNN textured ceramics and doped with 1.5 mol% of CuO and 0.5 mol% MnO, using 2.5, 5.0 and 10.0 wt% of single crystals were processed. For the same composition the heating rate of 2 °C/min and 20 °C/min and sintering level between 4 and 24 h was varied. Dense single phase KNN ceramics with an increase in the Lotgering factor from ≈20% to ≈38% for KNN ceramics doped with 1.5 mol% of copper and 0.5 mol% of manganese, textured with 5 wt% crystals and sintered at 1065 °C for 24 h with a heating rate/cooling of 10 °C/min have been achieved. These ceramics exhibit a relative permittivity at room temperature ≈ 300 for a Curie temperature value which remained high (TC ≈ 400 °C). The piezoelectric coefficient increased (d33 = 65 pC/N) with increased texturing. Despite the value of the piezoelectric coefficient achieved is still modest, the obtained piezoelectric voltage constant revealed values (g33 = 23.9 * 10-3 Vm/N) comparable to the values reported for certain compositions of commercial PZT, showing clearly competitive opportunities in applications (such as piezoelectric sensors) for KNN ceramics. The results of this study definitely contribute to the knowledge in the field of lead-free piezoelectric materials.
Este trabalho é acerca de materiais cerâmicos isentos de chumbo destinados a aplicações electromecânicas e candidatos à substituição de electrocerâmicos à base de chumbo. O titanato zirconato de chumbo (PZT) é o cerâmico piezoeléctrico mais utilizado em todo o mundo. No entanto, contém mais de 60 wt% de chumbo que é um elemento tóxico para os seres humanos e para o ambiente. Em 2003, a União Europeia aprovou uma directiva proibindo e restringindo o uso de elementos potencialmente perigosos como o chumbo. Devido à inexistência de materiais aptos para a substituição do PZT, foi feita uma exceção até ser encontrado um material alternativo competitivo. O niobato de potássio e sódio (K0.5Na0.5NbO3, KNN), devido à sua elevada temperatura Curie e propriedades piezoeléctricas moderadas, é um dos materiais isentos de chumbo mais promissores para substituição do PZT. No entanto, a sua efetiva adopção industrial requer, entre outros aspectos, a optimização das suas propriedades. Neste contexto, estudou-se neste trabalho o efeito de dopantes, da temperatura de sinterização e da texturização em cerâmicos de KNN. Foram fabricados cerâmicos de KNN dopados com i) 1,5 mol% CuO + 2,0 mol% Li2O, ii) 1,5 mol%CuO + 4,0 mol% Li2O e iii) 1,5 mol% CuO + 0,5 mol% MnO e sinterizados a diferentes temperaturas (1050, 1065 e 1080 ºC). Complementarmente com o objectivo de maximizar a orientação cristalográfica preferencial dos cerâmicos de KNN (texturização), neste caso segundo a direcção (h00), foram produzidos monocristais de KNN. Estes cristais foram usados como sementes no processo de texturização de cerâmicos de KNN. Verificou-se que a composição dopada com cobre e manganês foi a única das composições estudadas que se apresentou monofásica. Foram conseguidos cerâmicos, texturizados e não texturizados, densos (> 95 %) e com factor de Lotgering mais elevado dentre as composições estudadas (≈ 20 %). Foi possível demonstrar a dependência das propriedades dieléctricas do factor de Lotgering. Na tentativa de optimizar o factor de Lotgering para majorar as propriedades piezoeléctricas, foi estudado, para a composição dopada com cobre e manganês, o efeito da quantidade de monocristais adicionada, da taxa de aquecimento e arrefecimento e da duração do patamar de sinterização. Para tal, foram processados cerâmicos de KNN texturizados e dopados com 1,5 mol% de CuO e 0,5 mol% MnO, usando 2,5 wt%, 5,0 wt% e 10,0 wt% de monocristais. Para a mesma composição foi variada a taxa de aquecimento entre 2 ºC/min e 20 ºC/min e o patamar de sinterização entre 4 e 24 h. Foram conseguidos cerâmicos densos e monofásicos e um incremento no factor de Lotgering de ≈20 % para ≈38 %, para cerâmicos de KNN dopados com 1.5 mol % de cobre e 0.5 mol % de manganês, texturizados com 5 wt% de monocristais e sinterizados a 1065 ºC por 24 h com uma taxa de aquecimento / arrefecimento de 10 ºC/min. Estes cerâmicos exibem uma permitividade relativa de ≈ 300 à temperatura ambiente, para um valor da temperatura de Curie que se manteve elevado (TC ≈ 400 ºC). O coeficiente piezoeléctrico aumentou (d33 = 65 pC/N) com o aumento de texturização. Apesar do valor do coeficiente piezoelétrico conseguido ser ainda modesto, a constante de voltagem piezoeléctrica destes cerâmicos revelou valores (g33 = 23.9*10-3 Vm/N) comparáveis com os valores apresentados por certas composições de PZT comercial, mostrando claramente oportunidades competitivas em aplicações (nomeadamente como sensores piezoeléctricos) de cerâmicos de KNN. Os resultados obtidos neste trabalho contribuem para o conhecimento na área dos materiais piezoeléctricos isentos de chumbo.

Doutoramento em Ciência e Engenharia de Materiais
K0.5Na0.5NbO3 (KNN), is the most promising lead free material for substituting lead zirconate titanate (PZT) which is still the market leader used for sensors and actuators. To make KNN a real competitor, it is necessary to understand and to improve its properties. This goal is pursued in the present work via different approaches aiming to study KNN intrinsic properties and then to identify appropriate strategies like doping and texturing for designing better KNN materials for an intended application. Hence, polycrystalline KNN ceramics (undoped, non-stoichiometric; NST and doped), high-quality KNN single crystals and textured KNN based ceramics were successfully synthesized and characterized in this work. Polycrystalline undoped, non-stoichiometric (NST) and Mn doped KNN ceramics were prepared by conventional ceramic processing. Structure, microstructure and electrical properties were measured. It was observed that the window for mono-phasic compositions was very narrow for both NST ceramics and Mn doped ceramics. For NST ceramics the variation of A/B ratio influenced the polarization (P-E) hysteresis loop and better piezoelectric and dielectric responses could be found for small stoichiometry deviations (A/B = 0.97). Regarding Mn doping, as compared to undoped KNN which showed leaky polarization (P-E) hysteresis loops, B-site Mn doped ceramics showed a well saturated, less-leaky hysteresis loop and a significant properties improvement. Impedance spectroscopy was used to assess the role of Mn and a relation between charge transport – defects and ferroelectric response in K0.5Na0.5NbO3 (KNN) and Mn doped KNN ceramics could be established. At room temperature the conduction in KNN which is associated with holes transport is suppressed by Mn doping. Hence Mn addition increases the resistivity of the ceramic, which proved to be very helpful for improving the saturation of the P-E loop. At high temperatures the conduction is dominated by the motion of ionized oxygen vacancies whose concentration increases with Mn doping. Single crystals of potassium sodium niobate (KNN) were grown by a modified high temperature flux method. A boron-modified flux was used to obtain the crystals at a relatively low temperature. XRD, EDS and ICP analysis proved the chemical and crystallographic quality of the crystals. The grown KNN crystals exhibit higher dielectric permittivity (29,100) at the tetragonal-to-cubic phase transition temperature, higher remnant polarization (19.4 μC/cm2) and piezoelectric coefficient (160 pC/N) when compared with the standard KNN ceramics. KNN single crystals domain structure was characterized for the first time by piezoforce response microscopy. It could be observed that <001> - oriented potassium sodium niobate (KNN) single crystals reveal a long range ordered domain pattern of parallel 180° domains with zig-zag 90° domains. From the comparison of KNN Single crystals to ceramics, It is argued that the presence in KNN single crystal (and absence in KNN ceramics) of such a long range order specific domain pattern that is its fingerprint accounts for the improved properties of single crystals. These results have broad implications for the expanded use of KNN materials, by establishing a relation between the domain patterns and the dielectric and ferroelectric response of single crystals and ceramics and by indicating ways of achieving maximised properties in KNN materials. Polarized Raman analysis of ferroelectric potassium sodium niobate (K0.5Na0.5)NbO3 (KNN) single crystals was performed. For the first time, an evidence is provided that supports the assignment of KNN single crystals structure to the monoclinic symmetry at room temperature. Intensities of A′, A″ and mixed A′+A″ phonons have been theoretically calculated and compared with the experimental data in dependence of crystal rotation, which allowed the precise determination of the Raman tensor coefficients for (non-leaking) modes in monoclinic KNN. In relation to the previous literature, this study clarifies that assigning monoclinic phase is more suitable than the orthorhombic one. In addition, this study is the basis for non-destructive assessments of domain distribution by Raman spectroscopy in KNN-based lead-free ferroelectrics with complex structures. Searching a deeper understanding of the electrical behaviour of both KNN single crystal and polycrystalline materials for the sake of designing optimized KNN materials, a comparative study at the level of charge transport and point defects was carried out by impedance spectroscopy. KNN single crystals showed lower conductivity than polycrystals from room temperature up to 200 ºC, but above this temperature polycrystalline KNN displays lower conductivity. The low temperature (T < 200 ºC) behaviour reflects the different processing conditions of both ceramics and single crystals, which account for less defects prone to charge transport in the case of single crystals. As temperature increases (T > 200 ºC) single crystals become more conductive than polycrystalline samples, in which grain boundaries act as barriers to charge transport. For even higher temperatures the conductivity difference between both is increased due to the contribution of ionic conduction in single crystals. Indeed the values of activation energy calculated to the high temperature range (T > 300 ºC) were 1.60 and 0.97 eV, confirming the charge transport due to ionic conduction and ionized oxygen vacancies in single crystals and polycrystalline KNN, respectively. It is suggested that single crystals with low defects content and improved electromechanical properties could be a better choice for room temperature applications, though at high temperatures less conductive ceramics may be the choice, depending on the targeted use. Aiming at engineering the properties of KNN polycrystals towards the performance of single crystals, the preparation and properties study of (001) – oriented (K0.5Na0.5)0.98Li0.02NbO3 (KNNL) ceramics obtained by templated grain growth (TGG) using KNN single crystals as templates was undertaken. The choice of KNN single crystals templates is related with their better properties and to their unique domain structure which were envisaged as a tool for templating better properties in KNN ceramics too. X-ray diffraction analysis revealed for the templated ceramics a monoclinic structure at room temperature and a Lotgering factor (f) of 40% which confirmed texture development. These textured ceramics exhibit a long range ordered domain pattern consisting of 90º and 180º domains, similar to the one observed in the single crystals. Enhanced dielectric (13017 at TC), ferroelectric (2Pr = 42.8 μC/cm2) and piezoelectric (d33 = 280 pC/N) properties are observed for textured KNNL ceramics as compared to the randomly oriented ones. This behaviour is suggested to be due to the long range ordered domain patterns observed in the textured ceramics. The obtained results as compared with the data previously reported on texture KNN based ceramics confirm that superior properties were found due to ordered repeated domain pattern. This study provides an useful approach towards properties improvement of KNN-based piezoelectric ceramics. Overall, the present results bring a significant contribution to the pool of knowledge on the properties of sodium potassium niobate materials: a relation between the domain patterns and di-, ferro-, and piezo-electric response of single crystals and ceramics was demonstrated and ways of engineering maximised properties in KNN materials, for example by texturing were established. This contribution is envisaged to have broad implications for the expanded use of KNN over the alternative lead-based materials.
O niobato de sódio e de potássio, K0.5Na0.5NbO3 (KNN), é o material isento de chumbo mais promissor para substituir o titanato zirconato de chumbo (PZT), que ainda é o líder de mercado utilizado para sensores e actuadores. Para tornar o KNN verdadeiramente competitivo, é necessário compreender e melhorar as suas propriedades. Esse objectivo é perseguido no presente trabalho através de diferentes abordagens, visando o estudo das propriedades intrínsecas do KNN e a subsequente identificação de estratégias apropriadas, como por exemplo a dopagem e a texturização, para desenhar melhores materiais à base de KNN para as aplicações pretendidas. Assim, no presente trabalho, fabricaram-se e caracterizaram-se cerâmicos de KNN dopado e não dopado, de KNN não estequiométrico e de KNN texturizado. Adicionalmente cresceram-se e caracterizaram-se cristais simples de KNN de elevada qualidade. Os cerâmicos de KNN (não dopado, dopado com Mn e não-estequiométrico (NST)) foram preparados pelo método convencional de mistura de óxidos, tendo-se subsequentemente medido as suas propriedades eléctricas e analisadas as respectivas estruturas e microestruturas. No caso dos cerâmicos dopados com Mn bem como no dos cerâmicos NST verificou-se existir uma estreita janela de composição monofásica associada à dopagem e não estequiometria na posição-A. Nos cerâmicos NST a variação da razão (A/B) influencia o ciclo de histerese da polarização ferroeléctrica (P-E), verificandose a obtenção de respostas dieléctricas e piezoeléctricas melhoradas para pequenos desvios da estequiometria (A/B = 0.97). No que se refere ao KNN dopado com Mn, quando comparado com o KNN não dopado cujos ciclos de histerese são não saturados, verificou-se que a dopagem no lugar B conduz a uma curva (P-E) mais saturada e a uma melhoria significativa de propriedades. Usou-se a espectroscopia de impedância para esclarecer o papel do Mn, tendo-se estabelecido uma correlação entre defeitos/transporte de carga e a resposta ferroeléctrica do K0.5Na0.5NbO3 (KNN) e do KNN dopado com Mn. À temperatura ambiente a condução eléctrica no KNN, associada ao transporte por buracos, é minimizada pela dopagem com Mn. A adição de Mn incrementa assim a resistividade do cerâmico, o que permite melhorar a saturação do ciclo (P-E). A temperaturas elevadas a condução passa a ser dominada pela movimento de lacunas de oxigénio ionizadas cuja concentração aumenta com a dopagem com Mn. Preparam-se também cristais simples de KNN recorrendo-se a um método de fluxo de alta temperatura. Usou-se um fluxo modificado com adição de B2O3 para crescer cristais a uma temperatura relativamente baixa. Caracterizou-se a qualidade química e cristalográfica dos cristais por análise de DRX, EDS e ICP. Os cristais obtidos exibiram propriedades com valores elevados, designadamente uma permitividade dieléctrica de 29,100 à temperatura de transição da fase tetragonal para fase cúbica, uma polarização remanescente 19,4 μC/cm2 e um coeficiente piezoeléctrico de 160 pC/N, valores estes superiores aos dos cerâmicos convencionais de KNN. Usou-se pela primeira vez a microscopia de força piezoeléctrica para caracterizar a estrutura de domínios dos monocristais de KNN. Foi possível observar que os cristais simples de KNN orientados segundo <001>, evidenciaram um padrão de estrutura de domínios, com domínios de 180º dispostos paralelamente e domínios de 90º dispostos em zig-zag. Com base na comparação entre cristais e cerâmicos de KNN é possível sustentar-se que a presença nos cristais simples de um tal padrão de domínios ordenados com longo alcance, ausente nos cerâmicos, é responsável pelas propriedades melhoradas dos cristais simples de KNN. Espera-se que os presentes resultados, ao estabelecerem uma relação entre o padrão de estrutura de domínios, uma espécie de impressão digital, e a resposta dielétrica e ferroelétrica dos cristais simples e ao indicarem vias para se atingirem propriedades maximizadas em materiais de KNN, venham a ter fortes implicações na expansão do uso dos materiais de KNN. Caracterizaram-se também os monocristais ferroeléctricos de KNN por espectroscopia de Raman, obtendo-se pela primeira vez evidências que permitem a atribuir a estrutura cristalina de simetria monoclínica ao KNN. As intensidades dos fonões A′ , A" e A' + A" foram calculadas teoricamente e comparadas com os dados experimentais em função da rotação de cristal, o que permitiu a determinação precisa dos coeficientes do tensor Raman para modos (non-leaking) em KNN monoclínico. No contexto da literatura este estudo confirma que a atribuição da simetria monoclínica é mais adequada do que a ortorrômbica. Este estudo constitui ainda uma base para a avaliação não-destrutiva da distribuição de domínios por espectroscopia Raman em materiais ferroelétricos isentos de chumbo, à base de KNN e com estruturas complexas. Procurando aprofundar a compreensão do comportamento eléctrico dos cristais simples e dos cerâmicos de KNN, com o objectivo de desenhar materiais com propriedades optimizadas, realizou-se um estudo comparativo ao nível de defeitos e transporte de carga, usando-se para tal a espectroscopia de impedância. Os monocristais apresentam menor condutividade do que os materiais policristalinos homólogos para temperaturas até 200 ºC ao passo que, acima desta temperatura, são os materiais policristalinos quem apresenta menor condutividade. O comportamento de baixa temperatura (T < 200 ºC) reflecte as diferentes condições de processamento dos cerâmicos e dos cristais, que são responsáveis pelo menor teor de defeitos transportadores de carga no caso dos cristais simples. À medida que a temperatura aumenta, (T > 200 ºC) os monocristais tornam-se agora mais condutores do que as amostras policristalinas nas quais as fronteiras de grão actuam como barreiras ao transporte de carga eléctrica. Para temperaturas ainda mais elevadas a diferença de condutividade entre cristais e cerâmicos é incrementada devido à contribuição da condução iónica nos cristais. Efectivamente, para a gama de temperatura elevada (T > 300 ºC),calcularam-se valores da energia de activação de 1,60 e 0,97 eV que confirmam um transporte de carga associado a condução iónica e a lacunas de oxigénio ionizadas, em cristais simples e em cerâmicos, respectivamente. Sugere-se assim que, dependendo da aplicação em em vista, os cristais, com baixo teor de defeitos e propriedades electromecânicas melhoradas serão uma escolha indicada para aplicações a temperaturas próximas da temperatura ambiente ao passo que, para altas temperaturas, os cerâmicos, menos condutores, serão a opção mais indicada. Com o objectivo de desenhar as propriedades dos materiais policristalinos de KNN na mira de um desempenho semelhante ao dos cristais simples, prepararam-se e estudaram-se as propriedades de cerâmicos de (K0.5Na0.5)0.98Li0.02NbO3 (KNNL) com orientação (00l), usando cristais simples de KNN como partículas modelo para produzir cerâmicos texturizados por crescimento de grão modelado ( do inglês “template grain growth”). A escolha dos cristais simples como partículas modelo baseou-se no facto destas possuírem boas propriedades, aqui usadas como ferramenta indutora de melhores propriedades nos cerâmicos de KNN. A análise DRX revelou que os cerâmicos preparados com partículas modelo evidenciavam uma estrutura monoclínica à temperatura ambiente e um fator de Lotgering (f) de 40 %, o que confirma o desenvolvimento de textura cristalográfica. Estes cerâmicos texturizados apresentam um padrão de domínios ordenado com longo alcance que consiste em domínios de 90º e de 180º, semelhante ao observado nos cristais simples. Observaram-se valores elevados de constante dieléctrica (13017 na transição de fase C/T), de polarização ferroelétrica (2Pr = 42,8 μC/cm2) e de coeficiente piezoelétrico (d33 = 280 pC/N ) nos cerâmicos KNNL texturizados, quando comparados com os cerâmicos não orientados. Sugerese que esta resposta eléctrica se deve ao padrão de domínioordenados, observado nas amostras texturizadas. Os resultados obtidos, quando comparados com dados anteriormente reportados para cerâmicos de KNN texturizados confirmam a superioridade das propriedades obtidas, que se atribui à estrutura de domíneos observada. Este estudo fornece uma abordagem que pode ser de grande utilidade para a melhoria das propriedades dos cerâmicos piezoelétricos à base de KNN. Globalmente considerados, os presentes resultados configuram um importante contributo para o conjunto dos conhecimentos sobre as propriedades do niobato de sódio e de potássio: demonstrou-se que existe uma relação entre o padrão de estrutura de domínios e a resposta dieléctrica, ferroeléctrica e piezoeléctrica de cristais simples e de cerâmicos de KNN e apontou-se uma via para a melhoria das propriedades dos cerâmicos através da texturização. Prevê-se assim que este contributo tenha um impacto significativo na viabilização do uso generalizado do KNN em detrimento dos materiais à base de chumbo.

Ferroelectric and piezoelectric polycrystalline ceramics exhibiting large electromechanical response are sought after in electronic devices such as actuators, transducers in sonar, sensors, accelerators, aerospace, telecommunication, automotive industries, and ultrasonic motors. Ever since the discovery of large electromechanical performance at the morphotropic phase boundary (MPB) composition x=0.52 of Pb (ZrxTi1-x)O3 (PZT), a solid solution of lead zirconate and lead titanate, significant efforts and development has been made in understanding of various aspects contributing to these superlative properties. Morphotropic phase boundary (MPB) compositions separate ferroelectric phases with two different crystallographic symmetries (rhombohedral and tetragonal in PZT) and this inter-ferroelectric structural instability at MPB results in exceptional electromechanical response. This understanding of the significance of composition driven interphase instability led to exploration of new MPB based systems. Lead titanate (PbTiO3), an end member of PZT solid solution is a classical displacive ferroelectric which was discovered way back in 1950. PbTiO3 with tetragonal (P4mm) structure has one of the highest values of tetragonal distortion (c/a ≈ 1.063) among the ferroelectric perovskites and large spontaneous polarization (Ps). This encouraged research community to exploration of various ferroelectric, piezoelectric ceramic with solid solution of lead titanate. PbTiO3 based ferroelectric and piezoelectric ceramics like Pb (ZrxTi1-x) O3 (PZT), (1-x) PbTiO3-(x) BiScO3 (PT-BS), PMN-PT have since dominated the research field owing to their superior electromechanical properties. The focus of the thesis has been on PbTiO3 and its solid solution namely, Pb (ZrxTi1-x) O3 PZT, (1-x) PbTiO3-(x)Bi(Ni1/2Hf1/2)O3 PT-BNH, (1-x)PbTiO3-(x)Bi(Ni1/2Zr1/2)O3 PT-BNZ, (1-x) PbTiO3-(x)BiScO3 (PT-BS) PTBS, (1-x)Pb(Mg1/3Nb2/3)O3-(x)PbTiO3 PMN-PT. We have also fine-tuned various parameter to enhance the piezoelectric performance and demonstrate the energy harvesting application of these ferroelectric ceramic as a composite in flexible polymer matrix.

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