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Phase switching behaviour in lead-free Na0.5Bi0.5TiO3-based ceramicsWang, Ge January 2017 (has links)
This PhD project is focused on three lead-free ferroelectric solid solutions, which are specifically Na0.5Bi0.5TiO3-KNbO3(NBT-KN), Na0.5Bi0.5TiO3-NaNbO3(NBT-NN) and Na0.5Bi0.5TiO3-BaTiO3(NBT-BT), to evaluate the effects of composition, electric field and temperature on structural and electrical properties. Novel observations of both reversible and irreversible electric field-induced phase switching were made in both NBT-KN and NBT-NN ceramics. The NBT-KN solid solution is the primary focus of this thesis. All compositions were observed to be cubic in the as-sintered, unpoled state. However, a well-defined ferroelectric hysteresis P-E loop was obtained for compositions with low KN contents, indicating that an irreversible phase transition from a weak-polar relaxor ferroelectric (RF) to a long-range ordered metastable ferroelectric (FE) state had occurred during the measurement procedure. Both the unpoled and poled ceramic powders were examined using high resolution synchrotron XRD. For the poled state, a rhombohedral R3c structure was identified for compositions with low KN content, confirming the occurrence of the irreversible electric field-induced structural transformation from cubic to rhombohedral. In contrast, a cubic structure was retained for high KN contents, giving rise to reversible phase switching evidenced by constricted P-E hysteresis loops. Similar behaviour was observed for NBT-NN system. An 'in-situ' electric field poling experiment was conducted using high energy synchrotron XRD. In certain NBT-KN compositions the structural transformation, from cubic to mixed phase cubic+rhombohedral and finally single phase rhombohedral, occurred progressively with increasing cycles of a bipolar electric field. Similar behaviour was observed for NBT-NN compositions having low NN contents. Furthermore, the distributions of domain orientation and lattice strain over a range of orientations relative to the poling direction were determined for NBT-KN, NBT-NN and NBT-BT ceramics exhibiting the rhombohedral phase. By combining the structural information with the results of dielectric and ferroelectric measurements, a phase diagram was constructed to illustrate the influence of temperature and composition on the stability of the metastable ferroelectric and relaxor ferroelectric states for the NBT-KN system. Furthermore, the phase transition temperatures obtained from dielectric measurements were correlated with the ferroelectric and thermal depolarisation characteristics for each of the NBT-KN, NBT-NN and NBT-BT systems.
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Influência da adição de BaTiO3 nas propriedades estruturais, elétricas e anelásticas de cerâmicas piezoelétricas de Bi0,5Na0,5TiO3-BaTiO3Diaz, Julio Cesar Camilo Albornoz 07 August 2014 (has links)
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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.
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Structural, Ferroelectric, Piezoelectric and Phase Transition Studies of Lead Free (Na0.5Bi0.5)TiO3 Based CeramicsGarg, Rohini January 2013 (has links) (PDF)
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.
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Optimalizace mikrostruktury pokročilých keramických materiálů využitím konvenčních a nekonvenčních slinovacích metod / Tailoring of microstructure of advanced ceramic materials by conventional and non-conventional sintering approachesPrajzler, Vladimír January 2021 (has links)
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.
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